WO2021039536A1 - Method for producing polymer compound, polymer compound, composition, electrochromic element, display device, and dimming device - Google Patents

Abstract

The present invention is a method for producing a polymer compound, the method including: coordinating a first organic ligand to a first metal ion to obtain a metal complex, wherein the first organic ligand has one coordinating group LIG¹ capable of coordinating to the first metal ion and a substituent A, and the first metal ion has a coordination number at least n times the number of coordination sites of LIG¹; performing a cross-coupling reaction of a ligand precursor with the metal complex to obtain a second organic ligand having LIG² and LIG¹ coordinated to the first metal ion, wherein the ligand precursor has a substituent B which can be involved in the cross-coupling reaction corresponding to the substituent A, and a coordinating group LIG² capable of coordinating to a second metal ion different from the first metal ion; and coordinating, to LIG², the second metal ion having a coordination number of at least m times the number of coordination sites of LIG² and differing from the first metal ion, to obtain a polymer compound in which the first metal ion and the second metal ion are alternately linked through the second organic ligand.

Description

Method for manufacturing polymer compounds, polymer compounds, compositions, electrochromic devices, display devices, and dimming devices

The present invention relates to a method for producing a polymer compound, a polymer compound, a composition, an electrochromic element, a display device, and a dimming device.

A polymer compound having a repeating unit formed by a coordinate bond between a metal atom and an organic ligand is known. Such polymer compounds are also referred to as organic / metal hybrid polymers, which have electrical functions and / or electrical functions due to electronic interactions between organic ligands and metals and / or electronic interactions between adjacent metals. Alternatively, it is known that an optical function may be exhibited.

Among them, in an organic / metal hybrid polymer in which different metal ions are alternately bonded, the metal ions interact with each other due to the adjacent metal ions, and each organic / metal ion has a single metal ion in the structure. It is known to have different electrochromic properties from metal hybrid polymers and mixtures thereof, and development is underway.

As such an organometallic hybrid polymer, Patent Document 1 states that "an organometallic hybrid polymer composed of a plurality of organometallic complexes and a plurality of transition metals, wherein the plurality of organometallic complexes are the plurality. Each transition metal of the transition metal is sandwiched in a long chain, and in the organometallic complex, two ligands having a turpyridyl group attach a nitrogen atom at the 1'position of the turpyridyl group to the organometallic complex. _{It is linked by one conjugate having Ru (dppe) 2} and two ethynylene groups so as to face the terminal side of the molecule of the above, and for one of the transition metals, of the plurality of organometallic complexes. An organometallic hybrid characterized in that the plurality of organometallic complexes are linked by alternately sandwiching the plurality of transition metals by coordinating the terpyridyl groups of at least two different organometallic complexes. "Polymer" and its synthesis method are described.

Further, Non-Patent Document 1 describes a heterometallosupramolecular polymer in which Eu (III) and Fe (II) ions are alternately introduced by utilizing the different coordination characteristics of lanthanide ion and transition metal ion, and the supramolecular polymer thereof. The synthesis method is described.

International release 2015/1607010

Sato T; Higuchi M. Chem. Common. 2013, 49, 5256-5258.

According to the synthesis method described in Patent Document 1, an organic / metal hybrid polymer in which different metal ions are alternately introduced can be synthesized, but one ion is Ru, and the obtained polymer compound (organic) is obtained. / Metal hybrid polymer) has a limitation on the combination of metal ions.
Further, according to the synthesis method described in Non-Patent Document 1, one of them was a lanthanide ion, and it was not possible to synthesize an organic / metal hybrid polymer in which different transition metal ions were alternately introduced.

In view of the above-mentioned inconveniences of the prior art, one of the objects of the present invention is the production of a polymer compound capable of more easily synthesizing a polymer compound (organic / metal hybrid polymer) in which different metal ions are alternately introduced. To provide a method.
Another object of the present invention is to provide novel polymer compounds, compositions, electrochromic devices, display devices, and dimming devices.

As a result of diligent studies to achieve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be achieved by the following configuration.

[1].
A method for producing polymer compounds
The first organic ligand is coordinated with a first metal ion to obtain a metal complex, wherein the first organic ligand is one coordinating group capable of coordinating with the first metal ion. It has LIG ¹ and one substituent A that can be involved in the cross-coupling reaction, and the first metal ion has a coordination number n times or more the number of coordination loci of the ^{LIG 1 (where n is 2).} (Ions above) and
It has one substituent B that can participate in the cross-coupling reaction corresponding to the substituent A, and one coordinating group LIGHT ² that can coordinate to a second metal ion different from the first metal ion. The ligand precursor is cross-coupled with the metal complex to obtain a second organic ligand having the ^{LIG 1 coordinated to the LIG 2} and the first metal ion.
The LIG ^2, has the LIG ² coordination sites the number of m times the coordination number of (here m is an integer of 2 or more), the second metal different from the first metal ion A method for producing a polymer compound, which comprises coordinating ions to obtain a polymer compound in which the first metal ion and the second metal ion are alternately linked via the second organic ligand. ..
[2]. The method for producing a polymer compound according to the above [1], wherein the first organic ligand is a compound represented by the formula 1 described later.
[3]. The method for producing a polymer compound according to the above [1] or [2], wherein the ligand precursor is represented by the formula 2 described later.
[4]. The method for producing a polymer compound according to any one of the above [1] to [3], wherein the substituent A is a halogen atom.
[5]. A polymer compound in which two different types of metal ions are coordinated and bonded to an organic ligand, so that the above two types of metal ions are alternately linked via the organic ligand.
[6]. The polymer compound according to the above [5], wherein the organic ligand is a nitrogen-containing ligand.
[7]. The polymer compound according to the above [5], wherein the organic ligand has a residue obtained by removing one or more hydrogen atoms from the pyridine derivative.
[8]. A polymer compound having a repeating unit represented by the formula 3 described later.
[9]. A composition containing the polymer compound according to any one of [5] to [8] and a counterion.
[10]. An electrochromic device having a pair of electrodes and a layer containing the composition according to the above [9] arranged between the electrodes.
[11]. The electrochromic device according to the above [10], which further has an electrolyte layer between at least one of the pair of electrodes and the layer.
[12]. The electrochromic device according to the above [10] or [11], further having a counter electrode layer between at least one of the pair of electrodes and the layer.
[13]. A display device having the electrochromic element according to any one of [10] to [12].
[14]. A dimming device having the electrochromic element according to any one of [10] to [12].

According to one aspect of the present invention, it is possible to provide a method for producing a polymer compound capable of more easily synthesizing an organic / metal hybrid polymer in which different metal ions are alternately introduced.
Further, according to another aspect of the present invention, it is possible to provide a novel polymer compound, a composition, an electrochromic device, a display device, and a dimming device.

It is a schematic sectional view of the electrochromic element which concerns on one non-limiting embodiment of this invention. It is a schematic structure of an electronic book reader having a display device according to one non-limiting embodiment of the present invention. It is a block diagram which shows the structure of the control system in the dimming apparatus which concerns on one Embodiment of this invention. It is a schematic front view which shows the specific structure of the dimmer device of FIG. ^{This is the result of 1 1} H NMR of the metal complex 1. This is the result of MALDI-MS of the metal complex 1. It is the result ^{of 1 1} H NMR of the compound OsL1. It is the result of MALDI-MS of compound OsL1. It is the result of ^{1 1 H NMR of polyFeOs.} It is the result of ^{1 1 H NMR of polyFeOs.} It is the result of cyclic voltammetry of polyFeOs. It is the result of cyclic voltammetry of polyFeOs. It is an ultraviolet-visible absorption spectrum of OsL1 and polyFeOs (0V). This is the result of in situ UV-vis measurement of polyFeOs. It is a photograph which shows the setup of the experiment of the measurement of the electrochromism property. It is a change in the transmitted light intensity of polyFeOs when the applied voltage is changed to 0V, 0.7V, 1.0V (vs. Ag / Ag ^{+) in the measurement of the electrochromism characteristic.} In the measurement of electrochromism characteristics, the change in transmitted light intensity of polyFeOs when the change in applied voltage of ^{0 V (vs. Ag / Ag +} ) and 1.0 V (vs. Ag / Ag ^{+) is repeated 200 times (} Left) and change in current value (right).

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value. In each equation, the broken line represents the coordination bond.

In the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or non-substitution includes those having no substituent and those having a substituent to the extent that the effect of the present invention is not impaired. Is what you do. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). This is synonymous with each compound.

[Manufacturing method of polymer compound]
The method for producing a polymer compound according to an embodiment of the present invention is
The first organic ligand is coordinated with a first metal ion to obtain a metal complex, wherein the first organic ligand is one coordinating group capable of coordinating with the first metal ion. It has LIG ¹ and one substituent A that can be involved in the cross-coupling reaction, and the first metal ion has a coordination number n times or more the number of coordination loci of the ^{LIG 1 (where n is 2).} Having (which is the above integer) (hereinafter referred to as "step a"),
It has one substituent B that can participate in the cross-coupling reaction corresponding to the substituent A, and one coordinating group LIGHT ² that can coordinate to a second metal ion different from the first metal ion. the ligand precursor, the metal complex and by cross-coupling reaction, to obtain a second organic ligand having the LIG ¹ state coordinated to LIG ² and the first metal ion (hereinafter, " Step b ") and

The LIG ^2, has the LIG ² coordination sites the number of m times the coordination number of (here m is an integer of 2 or more), the second metal different from the first metal ion When the ions are coordinated to obtain a polymer compound in which the first metal ion and the second metal ion are alternately linked via the second organic ligand (hereinafter referred to as "step c"). Has.

In the following, each of the above steps will be described in detail.

[Step a]
Since the first organic ligand used in this step ^{has only one LIG 1} in the molecule, the reaction proceeds in a chain reaction when coordinated with the first metal ion. It is suppressed. On the other hand, since the first metal has a coordination number (n is an integer of 2 or more) n times or more the number of coordination ^{constellations of LIGHT 1, the first metal ion of the first metal is a first organic.} Two or more ligands coordinate.
The method for producing a polymer compound according to an embodiment of the present invention is ^{to introduce LIG 2} into the first organic ligand in a state where ^{LIGHT 1} is coordinated to the first metal ion (step b described later). After that, the ^{coordination bond between LIGHT 2} and the second metal ion is included (step c). By doing so, a polymer compound in which the first metal ion and the second metal ion are alternately linked via an organic ligand (a second organic ligand described later) can be obtained.

The first metal ion is not particularly limited, but the transition metal ion is preferable in that the first metal ion is less likely to be dissociated in the step b described later, in other words, the metal complex described later has more excellent stability.
The coordination number of the first metal ^{is not particularly limited as long as it is n times the number of coordination constellations of LIGHT 1} (n is an integer of 2 or more), but 2 to 12 is preferable, and 4 to 8 is more preferable. It is preferable, 4 to 6 is more preferable.

The transition metal of the first metal is not particularly limited, but chromium (Cr), manganese (Mn), iron (Fe), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Mo ( Molybdenum), Ru (ruthenium), Rh (rhodium), Ag (silver), Sn (tin), W (tungsten), Re (renium), Os (osmium), Ir (iridium), Pt (platinum), and Au (gold) or the like is preferable.

More specifically, as the first metal ion, Cr (II), Cr (III), Cr (IV), Mn (II), Mn (III), Mn (IV), Fe (II), Fe (III). ), Co (II), Co (III), Ni (II), Ni (III), Ni (IV), Cu (I), Cu (II), Mo (III), Mo (IV), Mo (V) ), Ru (II), Ru (III), Rh (IV), W (III), W (IV), W (V), Re (IV), Re (V), Ir (III), Ir (IV) ), Os (II), Os (IV), Os (VIII), Pt (II), Pt (IV) and the like are particularly preferable.
Examples of the first metal other than the usable transition metal include Mg, Al and the like, for example, Mg (II), Al (III) and the like.

LIG ¹ is not particularly limited as long as it is a coordinating group capable of coordinating with the first metal ion, in other words, a group capable of forming a coordination bond with the first metal ion.
The number of coordination loci of LIG ¹ is not particularly limited, but 1 to 6 is preferable, and 2 to 4 is more preferable. The number of coordination loci of LIG ¹ is related to the coordination number with the first metal so that one first metal ion and two or more first organic ligands can form a coordination bond. It may be selected as.

As LIG ¹ , a group having a nitrogen-containing heterocycle is preferable because the obtained metal complex has more excellent stability. The group having a nitrogen-containing heterocycle is not particularly limited, but a monocycle of a 3- to 7-membered ring having a nitrogen atom and a condensed ring thereof (collectively referred to as "nitrogen-containing ligand") are used. Examples thereof include a monovalent residue excluding one hydrogen atom having. The number of carbon atoms in the ring may be one or two or more.

Examples of the nitrogen-containing ligand include pyrol, imidazole, pyrazole, oxazole, isooxazole, thiazole, isothiazole, 1,2,3-triazole, 1,2,4-triazole, 1,3,4-thiazazole, tetrazole, Pyridine, pyrazine, pyrimidine, pyridazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, 1,2,4,5-tetrazine, azepine, azonin, quinoline, isoquinoline, Aclysin, phenanthridine, indole, isoindole, carbazole, benzimidazole, 1,8-naphthylidine, purine, pteridine, benzotriazole, quinoline, quinazoline, perimidine, cinnoline, phthalazine, 1,10-phenanthlorin, phenoxazine, Phenothiazine, phenazine, 8-hydroxyquinoline, 8-mercaptoquinoline, 2,2'-bipyridine, 2,2'-dipyridylamine, di (2-picorylamine), 2,2', 2''-terpyridine, porphyrin, Examples thereof include phthalocyanine and derivatives thereof.

Pyrrole, imidazole, pyrazole, oxazole, thiazole, pyridine, 2,2', 2''-terpyridine, and these, as nitrogen-containing ligands, in that the resulting metal complex has better stability. Derivatives and the like are preferred.

The specific structure of the nitrogen-containing ligand is shown below. Any substituent may be bonded to these compounds (monovalent residues obtained by removing one hydrogen atom from them). In the following formula, p represents an integer of 2 or more, and is not particularly limited, but 20 or less is preferable, 10 or less is more preferable, and 6 or less is further preferable.

・ Pyridine derivative

In addition, examples of the nitrogen-containing ligand include the following compounds (monovalent residues obtained by removing one hydrogen atom from the following compounds).

The nitrogen-containing ligand may be purchased and used as a commercially available product, or may be used by a known method (CH Weidl, AA Precup, C. Eschbaumer, US Schubert, Polymeric Materials: Science). And Engineering, 84,649 (2001). Etc.) may be used for synthesis and use.

In addition to ^{the above, LIG 1} includes a hydroxy group, an alkoxy group, an acyl group, an alkoxy-carbonyl group, an acetylacetonato group, a benzylideneacetylacetonato group, a cycloalkazienyl group (cyclopentadienyl group, and a cyclopentadienyl group, and A group having a cyclooctadienyl group, etc.), a benzylidene group, a cyano group, a nitro group, an amino group, a phosphino group, and a group combining these groups can also be used.

(Substituent A)
Substituent A is a substituent that can participate in the cross-coupling reaction between the metal complex and the ligand precursor described later. The substituent A is not particularly limited, and examples thereof include a halogen atom, a boronic acid group, a boronic acid derivative group, a metal halide group, a trifluoromethanesulfonyloxy group (* -Otf), and a trialkyltin group.

The cross-coupling reaction is not particularly limited, and examples thereof include known cross-coupling reactions such as Mizorogi / Heck reaction, Negishi coupling, Sonogashira coupling, and Suzuki / Miyaura coupling. The substituent A may be a substituent capable of cross-coupling reaction between the metal complex and the ligand precursor in relation to the substituent B described later.

The halogen atom is not particularly limited, and examples thereof include a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of reactivity, a chlorine atom or a bromine atom is preferable.

The boronic acid derivative group is not particularly limited, but a dimethylborane group, a diethylborane group, a diphenylborane group, a pinacholylborane group, a catecholborane group, a 9-borabicyclo [3,3,1] nonyl group, a trifluoroborone group and the like. Can be mentioned.

The metal halide group is not particularly limited, and examples thereof include a magnesium chloride group, a magnesium bromide group, a magnesium iodide group, a zinc chloride group, a zinc bromide group, and a zinc iodide group.
The trialkyltin group is not particularly limited, and examples thereof include a trimethyltin group, a triethyltin group, and a tributyltin group.

Substituent A and substituent B, which will be described later, constitute a combination of substituents necessary for a cross-coupling reaction between a metal complex and a ligand precursor. For example, when the substituent A is a halogen atom or a trifluoromethanesulfonyloxy group, the substituent B is preferably a boronic acid group, a boronic acid derivative group, a metal halide group, and a trialkyltin group. .. When the substituent A is a boronic acid group, a boronic acid derivative group, a metal halide group, and a trialkyltin group, the substituent B is preferably a halogen atom or a trifluoromethanesulfonyloxy group.
Among them, the halogen as the substituent A is in that the obtained metal complex has more excellent stability and the reaction can be easily proceeded under the condition that the first metal ion is more difficult to dissociate in the step b described later. It is preferably an atom.

The first organic ligand has one coordinating group LIGHT ¹ capable of coordinating to the first metal ion and one substituent A described above. The structure of the first organic ligand is not particularly limited, but the compound represented by the following formula 1 is preferable in that the reaction is easier.

In formula 1, L ¹ represents a single bond or an arylene group, a heteroarylene group, an alkenylene group, an alkynylene group, or a group in which these are combined, and L ² represents a single bond or a divalent group. , X represent the substituent A, and LIG ^{1 represents the coordinating group LIG 1} capable of coordinating with the first metal ion.

The arylene group of L ¹ is not particularly limited, but an arylene group having 6 to 20 carbon atoms is preferable. As the arylene group, for example, 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 1,8-naphthylene group, 1,2-anthrylene group, 2,3-anthrylene group, 1, Examples thereof include a 2-phenanthrylene group, a 3,4-phenanthrylene group, and a 9,10-phenanthrylene group.

The heteroarylene group of L ¹ is not particularly limited, but furan, thiophene, pyrrole, oxazole, isooxazole, thiazole, thiadiazol, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, Bonds to carbon atoms from aromatic heterocyclic compounds such as indol, isoindole, indridin, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxalin. Examples thereof include divalent residues excluding the two hydrogen atoms.

The alkynylene group of L ¹ is not particularly limited, and examples thereof include a group having one or two or more carbon-carbon triple bonds in the group. The number of carbon atoms of the alkynylene group is not particularly limited, but is 2 or more, preferably 20 or less, more preferably 15 or less, further preferably 8 or less, and particularly preferably 4 or less.

The alkynylene group having 2 to 15 carbon atoms includes an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, a hexynylene group, a heptinylene group, an octinilen group, a nonignylene group, a decinilen group, an undecynylene group, a dodecinylene group, a tridecylene group, and a tetradecylene group. , Pentadecinylene groups, and isomers thereof are preferred.

The alkynylene group having 2 to 8 carbon atoms includes an ethynylene group, a propynylene group, a butynylene group, a butaziinylene group, a pentynylene group, a pentadiinylene group, a hexynylene group, a hexadiinylene group, a heptinylene group, a heptadienylene group, an octidineylene group, and an octadiylene group. preferable.

As the alkynylene group having 2 to 4 carbon atoms, an ethynylene group, a propynylene group, and a butenylene group are preferable.

The alkenylene group of L ¹ is not particularly limited, and examples thereof include a group having one or two or more carbon-carbon double bonds in the group. The number of carbon atoms of the alkenylene group is not particularly limited, but is 2 or more, preferably 20 or less, more preferably 15 or less, further preferably 8 or less, and particularly preferably 4 or less.

The alkenylene group having 2 to 15 carbon atoms includes an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, a noneneylene group, a desenylene group, an undecenylene group, a dodeceneylene group, and a tridecenylene group. Groups, pentadecenylene groups, and isomers thereof are preferred.

Examples of the alkenylene group having 2 to 8 carbon atoms include a group having one or two or more double bonds in the group. Examples thereof include an ethenylene group, a propenylene group, a butenylene group, a butazienylene group, a pentenylene group, a pentadienylene group, a hexenylene group, a hexadienylene group, a heptenylene group, a heptadienylene group, an octenylene group, and an octadienylene group.

As the alkenylene group having 2 to 4 carbon atoms, ethenylene, propenylene, and butenylene groups are preferable.

Among them, in terms of reaction proceeds more efficiently, as the L ^1, except a single bond, an arylene group, or, preferably heteroarylene group, an arylene group is more preferable.

Specific examples of L ¹ are not particularly limited, and examples thereof include groups represented by the following formulas. In the following formula, * means the bonding position.

The ^{divalent group of L 2} is not particularly limited, but ^{the group of groups already described as L 1} , -C (O)-, -C (O) O-, -OC (O)-, -O-, -S-, -NR ^2- (R ² represents a hydrogen atom or a monovalent organic group), an alkylene group (preferably 1 to 20 carbon atoms), a cycloalkylene group (preferably 3 to 20 carbon atoms). , Alkenylene group (preferably having 2 to 20 carbon atoms), alkynylene group (preferably having 2 to 20 carbon atoms), arylene group, heteroarylene group, and a group combining these groups.

For example, examples of the ^{group represented by −L 1} − L ² − include a group represented by the following formula. In the following formula, * means the coupling position.

The first organic ligand represented by the formula 1 may be a commercially available product, or may be synthesized by a known method as described in paragraph 0135 of International Publication No. 2016/208554.

In this step, the first organic ligand is coordinated with the first metal ion. The method for coordinating (coordinating) the first organic ligand to the first metal ion is not particularly limited, and a known method can be used. For example, there is a method of preparing a reaction solution containing a first organic ligand, a first metal ion (typically a salt containing the first metal ion), and a solvent, and applying energy (for example, heating). Can be mentioned.

The solvent is not particularly limited, and examples thereof include water, an organic solvent, and a mixture thereof.
The organic solvent is not particularly limited, and examples thereof include ethylene glycol, ethanol, methanol, chloroform, NMP (N-methyl-2-pyrrolidone), dimethylformamide, and dimethyl sulfoxide.
The reaction temperature is not particularly limited, but is usually 50 ° C. to 250 ° C., preferably 60 to 200 ° C.
The reaction time is not particularly limited, but is usually 5 to 50 hours, preferably 6 to 36 hours.

For example, the first organic ligand is a compound represented by Formula 1 (typically a terpyridine derivative), the number of coordination constellations is 3, and the coordination number of the first metal is 6 (eg, Os ^2+). ), The metal complex represented by the following formula 1A is synthesized by this step. In the following formula, M ¹ represents the first metal ion, and each symbol (X, L ¹ , and L ² ) has the same meaning as each symbol in the formula 1.

As described above, since the first organic ligand has ^{only one} coordinating group LIGHT 1 capable of coordinating with the first metal ion, the first organic ligand and the first metal ion The chain reaction of the binding reaction is suppressed. Further, due to the relationship between the number of coordination numbers of the first organic ligand and the coordination number of the first metal, two first organic ligands are coordinated to the first metal ion.
Therefore, a polymer compound in which the first metal ion and the second metal ion are alternately linked via a ligand can be obtained through the steps b and c described later.

In the above, the example in which the number of coordination numbers of the first organic ligand is 3 and the number of coordination numbers of the first metal is 6, but the present invention is not limited to this. For example, the first metal ion is a metal ion of a metal having a coordination number of 4, such as Pd (II) and Zn (II), and the first organic ligand is a 2,2'-bipyridine derivative or the like. Even in the case of a bidentate ligand, the synthesis reaction of the metal complex represented by the above formula 1A proceeds.

Further, in the formula 1A, two first organic ligands are coordinated to one first metal ion, but the metal complex obtained in this step is not limited to the above.
The first metal ions are Mg (II), Al (III), Cr (III), Mn (II), Mn (III), Fe (II), Fe (III), Co (III), and Pt ( When it is a metal ion of a metal having a coordination number of 6 such as IV) and LIG ¹ is a coordination group of two loci (in other words, the number of coordination loci of the first organic ligand is 2). If there is), a metal complex represented by the following formula 1B is obtained. In addition, M ¹ in the formula 1B represents the first metal ion, and each symbol has the same meaning as each symbol in the formula 1.
Assuming that the metal complex has a form represented by the following formula 1B, the polymer compound obtained through the steps (b) and (c) described later has a two-dimensional crosslinked structure with the first metal ion as a crosslinked point.

Further, the first metal ion is a metal ion of a metal such as Co (II) and Ni (II) having a coordination number of 4 or 6, and LIG ¹ is a bidentate coordination. When it is a sex group, both 1A and 1B metal complexes can be synthesized. In this case, the polymer compound obtained through the steps (b) and (c) described later has both a linear structure and a two-dimensional crosslinked structure.

In any of the above cases, the reaction between the first metal ion and the first organic ligand does not proceed in a chain reaction, so that the first metal ion and the first metal ion go through the steps (b) and (c) described later. A polymer compound in which the second metal ion is alternately linked via a ligand is obtained.

When the first metal ion is reacted with the first organic ligand, the method of supplying the first metal ion into the reaction system is not particularly limited, but a method of adding the first metal ion as a metal salt to the reaction solution is preferable. Examples of the metal salt include a salt composed of a first metal ion and a counter anion.
The counter anion is not particularly limited, but is not particularly limited, but is a halide ion such as chloride ion, hydroxide ion, acetate ion, perchlorate ion, carbonate ion, boron tetrafluoride ion, hexafluorophosphate ion, trifluoromethanesulfonic acid. _{ions, (CF 3 SO 2) 2} N ions, polyoxyethylene metalate, and, combinations thereof and the like.

The amount ratio of the first metal ion added to the solvent to the first organic ligand is not particularly limited, and the coordination number of the first metal ion and the coordination number of the first organic ligand are not particularly limited. It may be determined as appropriate according to the number.
For example, when the first metal ion is Os ²⁺ (coordination number 6) and the first organic ligand is a terpyridine derivative (3 loci), the first organic is relative to the content ^{of Os 2+ in the reaction solution.} It is preferable that the content molar ratio of the ligand content is adjusted to be 1.9 to 3.0.

In addition, this step may further have a step of purifying the obtained metal complex. A step described later by purifying the metal complex and removing excess first metal ions and / or first organic ligands that did not contribute to the reaction from the reaction solution after the reaction. It is possible to further suppress the progress of an unintended reaction (for example, the reaction ^{between LIGHT 2 and the first metal ion) in b and step c.} The purification method is not particularly limited, and known methods (filtration and washing) and the like can be used.

[Step b]
In step b, one substituent B corresponding to the substituent A and capable of participating in the cross-coupling reaction, and one coordinating group capable of coordinating with a second metal ion different from the first metal ion. In the step of cross-coupling a ligand precursor having ^{LIG 2} with the metal complex to obtain a second organic ligand having ^{LIG 1} in a state of being coordinated with ^{LIG 2 and the first metal ion.} is there.

(Second metal ion)
The second metal ion may be a metal ion different from the first metal ion, and its form is not particularly limited. As the second metal ion, for example, the metal ion already described as the first metal ion can be used, and the form thereof is also the same.
In the present specification, different metal ions mean that the types of elements are different (for example, Os and Fe) and that the valences are different (for example, Cr (II) and Cr having the same element but different valences). It means either or both of (including cases such as (III)). It is preferable that at least the types of elements differ between the first metal ion and the second metal ion.

The second metal ion is not particularly limited, but a transition metal ion is preferable.
The transition metal ion is not particularly limited, and chromium (Cr), manganese (Mn), iron (Fe), Ni (nickel), Co (cobalt), Cu (copper), Zn (zinc), Mo (molybdenum), Ru (ruthenium), Rh (rhodium), Ag (silver), Sn (tin), W (tungsten), Re (renium), Os (osmium), Ir (iridium), Pt (platinum), and Au (gold) ) And other metal ions are preferred.

More specifically, as the second metal ion, Cr (II), Cr (III), Cr (IV), Mn (II), Mn (III), Mn (IV), Fe (II), Fe (III). ), Co (II), Co (III), Ni (II), Ni (III), Ni (IV), Cu (I), Cu (II), Mo (III), Mo (IV), Mo (V) ), Ru (II), Rh (III), Rh (IV), W (III), W (IV), W (V), Re (IV), Re (V), Ir (III), Ir (IV) ), Os (II), Os (IV), Os (VIII), Pt (II), Pt (IV) and the like are particularly preferable.
Examples of the second metal other than the usable transition metal include Mg, Al and the like, for example, Mg (II), Al (III) and the like.

Substituent B is one of a set of substituents capable of undergoing a cross-coupling reaction between a metal complex and a ligand precursor in combination with substituent A. In other words, it is a substituent that can be involved in the cross-coupling reaction in correspondence with the substituent A. The substituent B is not particularly limited, and examples thereof include the same substituents as the substituent A. Specific examples thereof include a halogen atom, a boronic acid group, a boronic acid derivative group, a metal halide group, and a trifluoromethanesulfonyloxy group. (* -Otf), a trialkyltin group and the like are preferable. Substituent B can be selected in combination with Substituent A.
Of these, a boronic acid group and a boronic acid derivative group are preferable as the substituent B in that the reaction proceeds more efficiently. The form of each substituent is the same as that of the substituent A.

The ligand precursor has one substituent B and one coordinating group LIGHT ² capable of coordinating to the second metal ion. The structure of the ligand precursor is not particularly limited, but for example, a compound represented by the following formula 2 is preferable.

In formula 2, Y represents the substituent B, L ⁴ represents a single bond or an arylene group, a heteroarylene group, an alkenylene group, an alkynylene group, or a combination thereof, and LIGHT ² represents a second metal. A coordinating group capable of coordinating to an ion is represented, and L ³ represents a single bond or a divalent group.

Arylene group L ^4, heteroarylene, alkenylene, and, as a form of an alkynylene group, an arylene group of L ¹ in Formula 1, heteroarylene, alkenylene, and, similar to that described as an alkynylene group The groups are mentioned, and the preferred forms are the same.
Further, as the divalent group of ^{L 3 , the same group as described as the divalent group of L 2 in} the formula 1 can be mentioned, and the preferred form is also the same.

Further, in the formula 2, the LIG ² is a coordinating group capable of coordinating to the second metal ion, ^{and the substituent described as the LIG 1} in the formula 1 can be mentioned, and the preferred form is also the same. LIG ² may be appropriately selected in relation to the second metal ion, and may be the same as or different from ^{LIG 1.}

The method of the cross-coupling reaction between the metal complex and the ligand precursor is not particularly limited, and a known method can be used.
Although not particularly limited, the cross-coupling reaction includes Pd (PPh ₃ ) ₄ , Pd (PPh ₃ ) ₂ Cl ₂ , NiCl ₂ (dppe), Pd (OAc) ₂ , Pd ₂ (dba) ₃ , Cu (OAc). ) ₂ and transition metal catalysts such as CuI can be used.

Further, although not particularly limited _{, bases such as K 2} CO ₃ , K ₃ PO ₄ , Cs ₂ CO ₃ , EtsN, and pyridine can be used in combination.
Further, ligands such as BINAP, di-tert-butylphosphinebiphenyl, dicyclohexylphosphinobiphenyl, tritert-butylphosphine, XANTPHOS, and triphenylarsine may be added.

The reaction can be carried out in a solvent such as toluene, DME, DMSO, dioxane, THF, water, and mixtures thereof. The reaction system may be kept at 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., for usually 1 to 48 hours, preferably 5 to 40 hours. The reaction may be homogeneous or heterogeneous.
As a specific method, for example, Miyaura, N. et al. Suzuki, A. et al. Chem. Rev. 1995, 95, 2457-2483, Dai, C.I. Fu, G. C. J. Am. Chem. Soc. , 2001, 123, 2719-2724, Littke, A. et al. F. Fu, G. C. Angew. Chem. Int. Ed. The description of 1999, 38, 6, 2411-2413 and the like can be referred to.

By this step, a second organic ligand in which a group having ^{LIGHT 2} is introduced into the first organic ligand in a state coordinated with the first metal ion is obtained.
As reaction examples in this step, coordinated manner coordinated number first organic ligand are two in the first metal ion M ^1, and, if the number of coordination sites are selected, the following equation 2A The reaction represented proceeds.

According to the above, the ^{second organic ligand in a state coordinated to the first metal ion M 1} (that is, the second organic ligand is "LIG ^2- L ^3- L ^4- L ^1- L ^2- LIG ¹ ". Means.) Is obtained. Each of the second organic ligand, the LIG ¹ one example of the formula 2A, and the LIG ² have one, LIG ¹ is in a state of being coordinated to the first metal ion. Therefore, when the second organic ligand is coordinated with the second metal ion in the step c described later, the height in which the first metal ion and the second metal ion are alternately bonded via the second organic ligand. A molecular compound is obtained.

The reaction in Formula 2A is an example. In addition to this example, the number of coordination as the first organic ligand has three coordinating the first metal ion M ^1, and, if the number of coordination sites is selected, the formula: 2B Reaction progresses.

In the above formula 2B, each symbol has the same meaning as the same symbol in the formulas 1 and 2, and the preferred form is also the same. In addition, M ¹ represents a first metal ion.

By this step, one of the ligands (LIG ¹⁾ in the state of fixing the first metal ion side (coordinate bonding state), while allowing coordinated to the second metal ion coordinating groups (LIG ² ) Is formed. Therefore, as a result of undergoing the step c described later, a polymer compound in which the first metal ion and the second metal ion are alternately linked via the second organic ligand is obtained.

[Step c]
Step c is in the LIG ^2, the LIG ² coordination sites the number of m times the coordination number of (here m are an integer of 2 or more), different from the first metal ion This is a step of coordinating the second metal ion to obtain a polymer compound in which the first metal ion and the second metal ion are alternately linked via a second organic ligand.

In this step, the second metal ion is coordinate-bonded to the coordinating ^{group LIGHT 2} possessed by the second organic ligand obtained in step b already described.
^{The method of coordinating the LIGHT 2} possessed by the second organic ligand to the second metal ion is not particularly limited, but the method of coordinating the ^{LIGHT 1} possessed by the first organic ligand to the first metal ion in step a. The same methods and conditions as in can be used. Specifically, the second metal ion and the second organic ligand can be mixed in a solvent and stirred at room temperature or under heating conditions. As the solvent, a polar solvent such as acetic acid, methanol, methylene chloride, chloroform, DMSO, or a mixture thereof can be used. As the reaction temperature, the temperature at which the coordination bond proceeds can be selected in the temperature range from room temperature to the boiling point temperature of the solvent used.

The polymer compound obtained by this step is not particularly limited, but it is preferable to have a repeating unit represented by the following formula 3. The molecular weight of this polymer compound varies greatly depending on the strength of the coordination bond between ^{LIG 2 and the second metal ion in step c, and may be several hundred to several million.} Although not limited, the molecular weight (weight average molecular weight: Mw) can be confirmed by, for example, polystyrene-equivalent GPC (gel exclusion chromatography) measurement or RALS (light scattering) measurement. For example, its weight average molecular weight range may be from about 200 to less than 10,000,000.

In Equation 3, M ¹ represents a first metal ion, M ² represents a second metal ion different from M ^{1 , LI G 1} represents a coordinating group LIGHT ¹ that can be coordinated to M ¹ , and LIG. ² represents a coordinating group LIGHT ² that can be coordinated to M ² , and LIG ¹ and LIG ² may be the same or different, respectively, and L ¹ and L ⁴ are independently single-bonded, or an arylene group or a hetero. It represents an arylene group, an alkenylene group, an alkynylene group, or a group obtained by combining these groups, and may be the same or different from each other. L ² and L ³ each independently represent a single bond or a divalent group and are the same as each other. But it may be different.
LIG ¹ , M ¹ , M ² , LIG ² , L ¹ , L ² , L ³ , and L ⁴ are synonymous with the symbols in Equations 1 and 2, and the preferred forms are also the same.

The repeating unit contained in the polymer compound is not particularly limited, and examples thereof include repeating units represented by the following formulas 3A to 3D.

In formula 3A, M ¹⁶ represents the first metal ion. As M ¹⁶ , a metal ion of a metal having a coordination number of 6 and a metal ion of a metal having a coordination number of 4 or 6 can be used. A metal ion of a metal having a coordination number of 6 is preferable.
As the metal having a coordination number of 6, for example, Mg, Al, Cr, Mn, Fe, and the like can be used. More specifically, as this metal ion, Mg (II), Al (III), Cr (III), Mn (II), Mn (III), Fe (II), Fe (III), and Examples thereof include Os (II) and Os (III).

Examples of the metal having a coordination number of 4 or 6 include Cu, Co, Pt, and the like. More specific examples of this metal ion include Cu (I), Cu (II), Co (II), Co (III), Pt (II), and Pt (IV).

Further, in the formula 3A, M ²⁶ represents a second metal ion. As M ²⁶ , if it is a metal ion different from M ^{16 , the metal ion listed as M 16} can be used. As M ²⁶ , a metal ion of a metal having a coordination number of 6 is preferable.

In formula 3A, L ¹ , L ² , L ³ and L ⁴ are synonymous with the same symbols in formulas 1 and 2, respectively, and the preferred forms are also the same. ^{Among them, L 1} and L ⁴ are each independently selected from the group consisting of the following formula (3AA) in that the polymer compound has more excellent electrochromic properties. preferable. Note that L ¹ and L ⁴ may be the same or different.

In formula 3A, L ² and L ³ have the same meanings as the same symbols in formulas 1 and 2, respectively, and the preferred forms are also the same. ^{Among them, L 2} and L ³ are independent of each other in that the polymer compound has more excellent electrochromic properties, and C (O)-, -C (O) O-,-other than a single bond. OC (O)-, -O-, ^{-S-, -NR 2- (R 2} represents a hydrogen atom or a monovalent organic group), an alkylene group (preferably 1 to 10 carbon atoms, 2 to 8 carbon atoms) (Preferably), cycloalkylene group (preferably 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms), alkenylene group (preferably 2 to 10 carbon atoms), alkynylene group (2 to 10 carbon atoms are preferable). (Preferably), an arylene group, a heteroarylene group, and a group combining these groups can be mentioned. L ² and L ³ more preferably contain —O—.

In formula 3B, M ¹⁴ represents the first metal ion. As M ¹⁴ , a metal ion of a metal having a coordination number of 4 and a metal ion of a metal having a coordination number of 4 or 6 can be used. A metal ion of a metal having a coordination number of 4 is preferable.

Examples of the metal having a coordination number of 4 include Pd, Au, Zn, and the like. More specific examples of this metal ion include Pd (II), Au (III), Zn (II) and the like.
As the metal coordination number can take any of the 4 and 6 are as previously described as a metal M ¹⁶ in the formula 3A.
Further, L ¹ to L ⁴ in the formula 3B have the same meaning as the same symbols in the formula 3A, and the preferred forms are also the same.

Further, in the formula 3B, M ²⁴ represents a second metal ion. As M ²⁴ , if it is a metal ion different from M ^{14 , the same metal ion as M 14} can be used.

In formula 3C, M ¹⁶ represents the first metal ion. As M ¹⁶ , a metal ion of a metal having a coordination number of 6 and a metal ion of a metal having a coordination number of 4 or 6 can be used. A metal ion of a metal having a coordination number of 6 is preferable.
Metal coordination number is 6, and, as the metal coordination number can take any of the 4 and 6 are as previously described as a metal M ¹⁶ of formula 3A. Examples of the metal having a coordination number of 6 include Mg, Al, Cr, Mn, Fe, and the like. More specifically, as this metal ion, Mg (II), Al (III), Cr (III), Mn (II), Mn (III), Fe (II), Fe (III), and Examples thereof include Os (II) and Os (III).
Moreover, it has already been described as M ¹⁶ also metal coordination number can take any of the 4 and 6.
^{Further, L 1} to L ⁴ in the formula 3C have the same meanings as the same symbols in the formula 3A, and the preferred forms are also the same.

In formula 3C, M ²⁴ represents a second metal ion. As M ²⁴ , a metal ion of a metal having a coordination number of 4 and a metal ion of a metal having a coordination number of 4 or 6 can be used. A metal ion of a metal having a coordination number of 4 is preferable. The form of M ^24, are as previously described as ^{M 24} in the formula 3B, ^i.e., if the different metal ions and ^{M 14,} the same metal ions as the above ^{M 14} can be used.

In formula 3D, M ¹⁴ represents the first metal ion and M ²⁶ represents the second metal ion. These forms are ^{synonymous with M 14 in} the formula 3B and M ²⁶ in the formula 3A, and the preferred forms are also the same. Further, L ¹ to L ⁴ have the same meaning as each symbol in the formula 3A, and the preferred form is also the same.

Further, the polymer compound may have a partial structure represented by the following formulas 3E to 3H.

In formula 3E, M ¹⁴ represents the first metal ion. The ^{M 14} has the same meaning as ^{M 14} of formula 3B, it is preferable forms are also similar. Further, M ²⁶ represents a second metal ion. The ^{M 26} has the same meaning as ^{M 26} in the formula 3A, it is preferable forms are also similar. ^Further, L 1 ~ ^{L 4} has the same meaning as ^L 1 ~ ^{L 4} in the formula 3A, it is preferable forms are also similar. Note that * represents the bonding position.

　式３Ｆ中、Ｍ^１４は第１金属イオンを表す。このＭ^１４は、式３Ｂ中のＭ^１４と同義であり、好適形態も同様である。また、Ｍ^２４は第２金属イオンを表す。このＭ^２４は、式３Ｂ中のＭ^２４と同義であり、好適形態も同様である。また、Ｌ^１～Ｌ^４は、式３Ａ中のＬ^１～Ｌ^４と同義であり、好適形態も同様である。なお、＊は結合位置を表す。

In the formula 3F, M ¹⁴ represents the first metal ion. The ^{M 14} has the same meaning as ^{M 14} of formula 3B, it is preferable forms are also similar. Further, M ²⁴ represents a second metal ion. The ^{M 24} has the same meaning as ^{M 24} of formula 3B, it is preferable forms are also similar. ^Further, L 1 ~ ^{L 4} has the same meaning as ^L 1 ~ ^{L 4} in the formula 3A, it is preferable forms are also similar. Note that * represents the bonding position.

In formula 3G, M ¹⁴ represents the first metal ion. The ^{M 14} has the same meaning as ^{M 14} of formula 3B, it is preferable forms are also similar. Further, M ²⁶ represents a second metal ion. The ^{M 26} has the same meaning as ^{M 26} in the formula 3A, it is preferable forms are also similar. ^Further, L 1 ~ ^{L 4} has the same meaning as ^L 1 ~ ^{L 4} in the formula 3A, it is preferable forms are also similar. Note that * represents the bonding position.

In formula 3H, M ¹⁶ represents the first metal ion. The ^{M 16} has the same meaning as ^{M 16} of formula 3A, it is preferable forms are also similar. Further, M ²⁶ represents a second metal ion. The ^{M 26} has the same meaning as ^{M 26} in the formula 3A, it is preferable forms are also similar. ^Further, L 1 ~ ^{L 4} has the same meaning as ^L 1 ~ ^{L 4} in the formula 3A, it is preferable forms are also similar. Note that * represents the bonding position.

Different metal ions are alternately introduced into the polymer compound according to the embodiment of the present invention. As a result, since two different types of metal ions are adjacent to each other, the metal ions interact with each other. Therefore, as shown in Examples described later, they have different electrochromic properties from organic / metal hybrid polymers having individual metal ions in their structures and mixtures thereof.
The polymer compound in which different metal ions according to an embodiment of the present invention are alternately introduced can be suitably used for various electrochromic devices, display devices, dimming devices, and the like due to their characteristics. ..

The configuration of such an electrochromic device is not particularly limited, and examples thereof include the devices described in JP-A-2018-205523, International Publication No. 2017/159221, and International Publication No. 2012/093547.

[Composition]
The composition according to one embodiment of the present invention is a composition containing the polymer compound already described and a counterion.
The counterion is not particularly limited, but in the method for producing a polymer compound already described, the counterion when the first metal ion in step a is added as a salt to the reaction system and / or the second metal ion is salted. Examples include counter ions when added to the reaction system.

The counterion is not particularly limited, and examples thereof include acetate ion, phosphate ion, chlorine ion, phosphorus hexafluoride ion, boron tetrafluoride ion, perchlorate ion, triflate ion, and polyoxometallate.

Since this composition contains a polymer compound and a counterion, it tends to be electrically neutral and has more excellent stability. The pH of the composition can be adjusted to usually be in the range of 6-8, preferably in the range of 6.5-7.7, more preferably about 7. The molar ratio of the polymer compound to the counterion in the present composition is not particularly limited, but the pH of the present composition is usually in the range of 6 to 8, preferably in the range of 6.5 to 7.7, more preferably. Can be adjusted as appropriate so as to be about 7.
The molar ratio of the polymer compound to the counterion in the present composition is, for example, in the range of 2: 1 to 1: 2, preferably in the range of 1.5: 1 to 1: 1.5, more preferably about. It may be 1: 1.
The present composition may contain a solvent or the like in addition to the above. The solvent is not particularly limited, and examples thereof include water and / or an organic solvent. The amount of solid content in the composition can be appropriately adjusted according to the intended use.

[Electrochromic element]
An electrochromic device according to an embodiment of the present invention is an electrochromic device having a pair of electrodes and a layer containing the above composition arranged between the electrodes (hereinafter, also referred to as “electrochromic layer”). Is.
FIG. 1 is a schematic cross-sectional view of a non-limiting embodiment of the electrochromic device according to the embodiment of the present invention.

The electrochromic element 100 of FIG. 1 has a first electrode 101, an electrochromic layer 102 arranged on the first electrode 101, an electrolyte layer 103 arranged on the electrochromic layer 102, and an electrolyte layer 103. The counter electrode layer 104 arranged on the counter electrode layer 104 and the second electrode 105 arranged on the counter electrode layer 104 have a structure sandwiched between the supporting substrates 106 and 107 facing each other. Here, the electrochromic layer 102 contains the polymer compound already described.

At least one of the first electrode 101 and the second electrode 105 is preferably an arbitrary transparent electrode. The electrode material is not particularly limited, but a SnO ₂ film, an In ₂ O ₃ film, or an ITO (Indium Tin Oxide) film is preferable. The first electrode 101 and the second electrode 105 are made of a transparent electrode material such as ITO by an arbitrary physical vapor deposition method or chemical vapor deposition method, and are made of a resin substrate such as plastic and glass. It is obtained by forming it on a transparent substrate such as a substrate.

The electrochromic layer 102 contains a composition containing the above-described polymer compound (hereinafter, also referred to as “specific polymer compound”) and a counterion. The polymer compound and the counterion are as described above, and the description thereof will be omitted.
The electrochromic layer 102 may be formed only of the above polymer compound and counterions.

The electrolyte layer 103 is not particularly limited, but is a polymer compound capable of forming a gel (a polymer compound different from a specific polymer compound constituting the electrochromic layer, and is hereinafter also referred to as a “gelled polymer compound”. ) And a supporting salt. The electrolyte layer 130 contains, for example, at least one plasticizer selected from the group consisting of propylene carbonate (PC), ethylene carbonate, dimethyl carbonate, diethylene carbonate, γ-butyrolactone, succinonitrile, and ionic liquids. You may.
Here, the ionic liquid is not particularly limited, but is at least one selected from the group consisting of tetrafluoroborate, hexafluorophosphate, bis (trifluoromethanesulfonyl) imide, and bis (pentafluoroethylsulfonyl) imide. Examples include combinations of anions with at least one cation selected from the group consisting of imidazolium, pyrrolidinium, and tetraalkylammonium.
A flexible electrochromic device can be provided by forming the gel-like electrolyte layer 130 by further adding a supporting salt and optionally a plasticizer to the network of gelled polymer compounds.

The electrolyte layer 103 is cast by dissolving the gelled polymer compound and the supporting salt (and optionally a plasticizer) in at least one solvent selected from the group consisting of acetonitrile, acetone, and tetrahydrofuran. It can be produced by removing the solvent.
By constructing an electrolyte layer in which the gelled polymer compound, the supporting salt, and optionally the plasticizer are uniformly dispersed, the electrochromic device characteristics are advantageously improved and stabilized. be able to.

The gelled polymer compound is not particularly limited, and for example, polymethylmethacrylate (PMMA), polyethylene oxide (PEO), poly (vinylidene fluoride-co-hexafluoroisopropyl) (PVdF-co-PHFP), and the like. Examples thereof include polypropylene carbonate (PPC), polycarbonate, and polyacrylonitrile. These gelled polymer compounds are advantageous in the composition of the electrolyte layer.

The supporting salt is not particularly limited, but is, for example, LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ COO, lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), LiCH ₃ COO, perchloric acid. Examples thereof include tetrabutylammonium acid acid, tetraethylammonium perchlorate, KCl, NaClO ₃ , NaCl, NaBF ₄ , NaSCN, KBF ₄ , Mg (ClO ₄ ) ₂ , and Mg (BF ₄ ) _2. These supporting salts can also function as counterions of specific polymer compounds constituting the electrochromic layer.

The electrolyte layer 103 may further contain a viologen and an ion storage material such as N, N, N', N'-tetramethyl-p-phenylenediamine. As a result, it is possible to suppress the accumulation of electric charges between the first electrode 101 and the electrochromic layer 102, so that the physical damage to the first electrode 101 caused by the accumulation of electric charges can be suppressed.
Further, as the ion storage material, ferrocene, Prussian blue, porphyrin and the like can also be used.

The counter electrode layer 104 means an electrochemically active layer that does not undergo a large color change.
The counter electrode layer 104 has an effect of stabilizing each electrochemical reaction by reacting with the electrochromic layer 102, for example, and reducing the potential difference required for the electrochromic reaction.
For example, when the electrochromic layer 102 is an oxidative color-developing type, the counter electrode layer 104 is preferably a material capable of a reduction reaction.

The material used for the counter electrode layer is not particularly limited as long as it is a material capable of reversely reacting with the electrochromic layer 102, and an inorganic compound and / or an organic compound may be used.
As the counter electrode layer, an electrochromic material in which the change in the light absorption band in the visible light region due to the redox reaction is small (the color change is small) can also be used. Examples of the inorganic compound that imparts such a function include antimony oxide, fluorine-doped tin oxide, nickel oxide, titanium oxide, zinc oxide, and tin oxide.
As the counter electrode _{material, K 3 Fe (CN) 6} , and ferrocene and the like may be used. These may be used alone or in combination of two or more.

Examples of the organic compound having the above function include a bipyridine derivative represented by the following formula 4. The bipyridine derivative can also be molecularly designed so that an absorption band is not expressed in the visible light region by adjusting the conjugate length of A in the formula 4.

In the formula 4, R1 and R2 represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 8 carbon atoms, each of which may have a substituent independently, and R1 and R2 and At least one of R2 has a substituent selected from the group consisting of COOH, PO (OH) ₂ , and Si (OC _k H _{2k + 1} ) _{3 (k is an integer greater than or equal to 1).} X represents a monovalent anion. n, m, and l independently represent 0, 1, or 2, respectively. A, B, and C may each have an independent substituent, such as an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heterocyclic group having 3 to 20 carbon atoms. Represents.

A bipyridine derivative can also be used to form an organic film on the second electrode 105 on the support substrate 107. As the bipyridine derivative, a structure supported on at least one of conductive particles and semiconductor particles can also be used.
The conductive particles and the semiconductor particles are not particularly limited, and for example, metal oxides can be used.

Examples of metal oxides include titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, yttrium oxide, boron oxide, magnesium oxide, strontium titanate, potassium titanate, barium titanate, calcium titanate, and calcium oxide. , Ferrite, Hafnium Oxide, Indium Oxide, Tungsten Oxide, Iron Oxide, Copper Oxide, Nickel Oxide, Cobalt Oxide, Barium Oxide, Strontium Oxide, Vanadium Oxide, Aluminosilicate, Calcium Phosphate, and Metal Oxide Things can be mentioned. These may be used alone or in combination of two or more.

The method for forming the counter electrode layer is not particularly limited, and examples thereof include a vacuum deposition method, a sputtering method, and an ion plating method. Further, as long as the material of the counter electrode layer can be applied and formed, for example, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, and a dip coating method. , Slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, and various printing methods such as inkjet printing method can also be used. Is.

The support substrates 106 and 107 are preferably made of a material provided to protect each layer and having excellent light transmittance. Examples of the materials of the support substrates 106 and 107 include glass, resin, and the like.

The electrochromic element 100 according to the embodiment of the present invention may be hermetically sealed with a sealing agent such as an epoxy resin and / or a silicone resin. As a result, the barrier property of the electrochromic element 100 against oxygen, water, and the like is improved.

The electrochromic element 100 according to the embodiment of the present invention operates as follows. The first electrode 101 and the second electrode 105 are connected to a power source (not shown), and a predetermined voltage is applied to the electrochromic layer 102, the electrolyte layer 103, and the counter electrode layer 104. Thereby, the redox of the electrochromic layer 102 can be controlled. That is, the redox of the metal ion of the specific polymer compound according to the embodiment of the present invention constituting the electrochromic layer 102 is controlled, and the electrochromic property can be exhibited.

Here, since the electrochromic layer 102 contains the polymer compound according to the embodiment of the present invention, it has different electrochromic properties from conventional electrochromic devices, for example, different color development and / or light transmission. Can be demonstrated.

The electrochromic element of the above embodiment has a counter electrode layer 104, a support substrate 106, and a support substrate 107, but the electrochromic element of the present invention is not limited to the above, and the counter electrode layer 104 and a support It is not necessary to have any one or more of the substrate 106 and the support substrate 107.
Further, a plurality of electrochromic elements 100 may be combined and arranged in a matrix for use.

The method for manufacturing the electrochromic device according to the embodiment of the present invention is not particularly limited, but it is preferable to have the following steps in that the electrochromic device can be manufactured more easily.

-Step of applying the above composition onto the electrode to form a composition layer This step forms a composition layer on the electrode, and the above composition layer functions as the electrochromic layer already described.
The method of forming the composition layer on the electrode is not particularly limited, but the method of applying the composition on the electrode, the method of attaching the film-like composition layer on the electrode, and the composition on the temporary substrate. Examples thereof include a method of arranging a material layer and transferring the composition layer onto the electrodes.
Among them, in this step, a method of applying the composition on the electrode to form the composition layer is preferable. If necessary, the composition layer may be further dried to remove the solvent and the like.

The method of applying the composition onto the electrode is not particularly limited, but when the composition is liquid, for example, a method of applying the composition onto the electrode, a method of immersing the electrode in the composition, and a method of immersing the electrode in the composition are used. Examples include a method of spraying.

The thickness of the obtained composition layer (electrochromic layer) is not particularly limited, but the thickness after drying is generally preferably 10 nm to 10 μm.
When the thickness of the composition layer is within the above range, a sufficient amount of the polymer compound according to the embodiment of the present invention is contained in the composition layer, so that higher electrochromic properties are likely to be exhibited.

-Step of laminating the electrolyte layer on the composition layer This step is a step of laminating the electrolyte layer on the composition layer formed in the previous step. The method of laminating the electrolyte layer on the composition layer is not particularly limited, but a composition for forming an electrolyte layer (containing a gelled polymer compound, a supporting salt, a solvent, etc.) is applied onto the composition layer. A method of forming an electrolyte layer, a composition for forming an electrolyte layer is applied onto the other electrode (an optional electrode layer is formed) to form an electrolyte layer, and then one having the composition layer. Examples thereof include a method in which the electrode and the other electrode having the electrolyte layer are laminated so that the composition layer and the electrolyte layer face each other.

The method of forming the electrolyte layer with the composition for forming the electrolyte layer is not particularly limited, but the method of applying on the composition layer or the electrode, the method of immersing the composition layer or the electrode in the composition layer for forming the electrolyte layer, and , A method of spraying the composition for forming an electrolyte layer onto the composition layer or the electrode can be used.
The thickness of the electrolyte layer is not particularly limited, but is generally preferably 10 nm to 10 mm.

[Display device]
The display device according to the embodiment of the present invention is a display device having the electrochromic element described above. FIG. 2 shows a schematic structure according to a non-limiting form of an electronic book reader as a device having the display device.

The electronic book reader 200 has a display device 201, a main controller 202, a ROM (Read Only Memory) 203, a RAM (Random Access Memory) 204, a flash memory 205, a character generator 206, and an interface 207.
The display device 201 includes a display panel 211 with a touch panel, a touch panel driver 212, a display controller 213, and a VRAM (Video RAM) 214.

Although the electronic book reader 200 is provided with the character generator 206 outside the display device 201, the character generator 206 may be provided inside the display device 201.
Further, the display panel 211 does not have to be provided with a touch panel. If there is another input means other than the touch panel, the display panel 211 may be provided with the other input means. If the display panel 211 does not have a touch panel, the touch panel driver 212 is not required.

The display panel 211 with a touch panel includes the electrochromic element and its drive circuit. The display panel 211 drives a drive element corresponding to the selected pixel based on the pixel selection signal output from the display controller 213, and applies a predetermined voltage to the selected pixel. The pixel selection signal is a signal that specifies the vertical position and the horizontal position of the selected pixel. Further, the display panel 211 applies a predetermined voltage to the corresponding display electrodes according to the designated color based on the color designation signal output from the display controller 213. The display panel 211 displays a moving image, a still image, or the like based on a signal such as a pixel selection signal or a color designation signal.

Further, when the user touches the touch panel, the display panel 211 outputs a signal based on the touch position to the touch panel driver 212.

The VRAM 214 stores display data for displaying a moving image or a still image on the display panel 211. The display data individually corresponds to a plurality of pixels included in the display panel 211. Therefore, the display data includes display color information corresponding to each pixel.
The display controller 213 reads out the display data stored in the VRAM 214 at predetermined timings, and individually controls the display colors of the plurality of pixels included in the display panel 211 according to the display data. The display controller 213 outputs a pixel selection signal for specifying the pixel to be colored and a color designation signal for specifying the color to the display panel 211.

The touch panel driver 212 outputs the position information corresponding to the position touched by the user on the display panel 211 to the main controller 202.
The main controller 202 comprehensively controls each part such as the RAM 204, the flash memory 205, the character generator 206, the interface 207, and the VRAM 214 according to the program stored in the ROM 203.

For example, when the power is turned on by the user, the main controller 202 reads the initial menu screen data from the ROM 203, refers to the character generator 206, converts the initial menu screen data into dot data, and converts the dot data into dot data. Transfer to VRAM 214. From this, the initial menu screen is displayed on the display panel 211. At this time, a list of contents stored in the flash memory 205 is displayed on the display panel 211. When one of the menus on the display panel 211 is selected by the user and the display portion is touched, the main controller 202 acquires the user's selection contents based on the position information from the touch panel driver 212.

When the user specifies the content and requests to view the content, the main controller 202 reads the electronic data of the content from the flash memory 205, refers to the character generator 206, converts the electronic data into dot data, and converts the electronic data into dot data. The dot data is transferred to the VRAM 214.
Further, when the user requests the purchase of the content via the Internet, the main controller 202 connects to a predetermined purchase site via the interface 207 and functions as a normal browser.

Information from the purchase site is displayed on the display panel 211, and when the user purchases the content, the electronic data of the content is downloaded. The main controller 202 stores the electronic data of the contents in the flash memory 205.

The ROM 203 stores various programs written in a code that can be deciphered by the main controller 202, and various data necessary for executing the programs.
The RAM 204 is a working memory.
The flash memory 205 stores electronic data and the like of books as contents. The character generator 206 stores dot data corresponding to various character data.
Interface 207 controls the connection with an external device. The interface 207 can be connected to a memory card, a personal computer, and a public line. It should be noted that the connection to the personal computer and the public line can be either wired or wireless.

[Dimmer]
The dimming device according to the embodiment of the present invention is a dimming device having the electrochromic element described above.
FIG. 3 is a block diagram showing a configuration of a control system in the dimming device according to the embodiment of the present invention.
In FIG. 3, the outdoor illuminance measuring unit 301, the indoor illuminance measuring unit 302, and the incident angle measuring unit 303 are connected to the calculation unit 304. The outdoor illuminance measuring unit 301 measures the outdoor illuminance, the indoor illuminance measuring unit 302 measures the indoor illuminance, the incident angle measuring unit 303 measures the incident angle of the sun, and the calculation units are based on these information S1 to S3. At 304, the optimum transmittance of each electrochromic element is calculated based on the calculation program.

The control unit 305 connected to the calculation unit 304 is connected to the DC power supply unit 306 and the electrochromic elements 307a to 307z. The control unit 305 is supplied with the DC voltage required for driving from the DC power supply unit 306, and the transmittance of the electrochromic elements 307a to 307z is independently changed according to the calculation result from the calculation unit 304 to determine the amount of incident light. Control the adjustment of. As described above, the dimming device 300 is configured.

FIG. 4 is a schematic front view showing a specific configuration of the dimming device of FIG. In FIGS. 3 and 4, the dimming device 300 has a dimming surface composed of 26 electrochromic elements 307a to 307z. These electrochromic elements 307a to 307z are configured so that the transmittance can be changed independently by applying a DC voltage supplied from the DC power supply unit 306.

The calculation result from the calculation unit 304 is input to the control unit 305, and the control unit 305 outputs the control signals S4 to S29 based on the calculation result. The control signal S4 changes the transmittance of the electrochromic element 307a, and the control signal S5 changes the transmittance of the electrochromic element 307b. Hereinafter, the transmittance up to the electrochromic element 307z is changed in the same manner. On the other hand, these transmittances can also be manually operated by the operation unit 401, and in this case, the control unit 305 similarly outputs the control signals S4 to S29 based on the manual operation.

Therefore, the control unit 305 can separately control the transmittance of the electrochromic elements 307a to 307z based on the arithmetic program and the manual operation. For example, by reducing the transmittance of the lower electrochromic element and increasing the transmittance of the upper electrochromic element, it is possible to avoid reflection of light due to strong sunlight on the desk surface, etc., and to make daylight deeper indoors than the upper part. It can be incorporated, which makes it possible to realize a comfortable visual environment that efficiently uses daylight.

In addition, daylight can be automatically controlled more efficiently by sensing the ever-changing indoor and outdoor light environment and / or the incident angle of the sun, which in turn can contribute to energy saving.
Further, by reducing the transmittance of the electrochromic element up to the height of the height, the line of sight can be blocked from the outside of the window when changing clothes. It is also possible to imitate a blind device by setting the high and low transmittance in a striped pattern.

As described above, according to this dimming device, the amount of incident light can be set independently depending on the location by configuring the dimming surface with electrochromic elements whose transmittance can be changed independently for each of a plurality of parts. Therefore, a comfortable viewing environment can be realized in the daytime and contribute to energy saving.
In addition, the user does not need to judge the indoor condition and set the transmittance, and the daylight can be automatically controlled more efficiently by sensing the ever-changing indoor / outdoor light environment and the incident angle of the sun. ..

The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.
Further, in the following examples and drawings, the unit "V" means "V, vs. Ag / Ag ⁺ " unless otherwise specified.

(Synthesis of metal complex 1)
4'-Bromo-2,2': 6', 2''-terpyridine (825 mg, 2.64 mmol) and (NH ₄ ) ₂ O ₅ Cl ₆ (528 mg, 1. 2 mmol) was placed in a nitrogen atmosphere. After adding dehydrated and degassed ethylene glycol (12 mL), the mixture was stirred at 180 ° C. for 6 hours.
After the reaction, the mixture was cooled to room temperature and excess THF was added to form a precipitate. The precipitate was then filtered to give a black powder which was purified by column chromatography (eluted with DCM / MeOH (5: 1) on a column packed with _{Al 2} O _3).
The metal complex 1 [Os (4-Brtpy) ₂ ] Cl ₂ was obtained as a black solid (930 mg, 87% yield). The reaction formula is shown below.

^{1 1} H NMR (CD ₃ OD, 300 MHz, ppm): δ9.26 (d, 4H),
8.72 (d, 4H), 7.86 (t, 4H), 7.43 (d, 4H), 7.21 (t, 4H). ^{The result of 1} H NMR of the metal complex 1 is shown in FIG.

MALDI-MS (m / z) : 814.49 [1-2Cl -] + ( calculated m / z = 814.57), 849.72 [1-Cl -] + ( calcd been m / z = 850.02), 884.91 [1] ⁺ (calculated m / z = 885.47). The result of MALDI-MS of the metal complex 1 is shown in FIG.

(Synthesis of a second organic ligand bound to a first metal ion)
Metal complex 1 (204 mg, 0.23 mmol), compound 2 (500.6 mg, 1.15), and K ₂ CO ₃ (80.2 mg, 0.58 mmol) synthesized above were placed in a 50 mL two-necked round bottom flask. The reaction mixture was prepared by dissolving in 20 mL of DMSO (dimethyl sulfoxide, anhydrous) under nitrogen.
Next, Pd (PPh ₃ ) ₄ (40 mg, 0.034 mmol, 15%) was added to the reaction mixture and heated at 100 ° C. for 36 hours.
Next, DMSO was removed under vacuum and the resulting solid was purified by column chromatography (eluting with DCM / MeOH (4: 1, vol / vol) in a column packed with _{SiO 2).} The reaction formula is shown below.

The obtained compound OsL1 (having a first metal ion of the first metal and a second organic ligand bound to the first metal ion) was a black solid (228.5 mg, 74% yield). Met.

^{1 1} H NMR (CD ₂ Cl ₂ / CD ₃ OD [1: 1, vol / vol], 300 MHz, ppm) δ9.34 (s, 4H), 8.93-8.90 (m, 8H), 8. 85 to 8.82 (m, 8H), 8.51 to 8.40 (m, 8H), 8.16 (t, 4H). 7.96 (t, 4H), 7.62 (t, 4H), 7.43 (d, 4H), 7.30 (t, 4H). ^{The results of 1} H NMR of compound OsL1 are shown in FIG.

MALDI-MS (m / z) : 1271.63 [OsL1-2Cl -] + ( calculated m / z = 1271.49). The results of MALDI-MS of compound OsL1 are shown in FIG.

(Synthesis of polymer compounds)
_{In a 25 mL round bottom flask, add 10 mL of CHCl 3} / MeOH / acetic acid (1: 1: 6, vol / vol /) with OsL1 (30 mg, 0.023 mmol) and Fe (OAc) ₂ (4 mg, 0.023 mmol). It was dissolved in vol) to obtain a reaction mixture. The reaction mixture was then refluxed for 24 hours. The reaction mixture was then cooled to 25 ° C. and subsequently filtered. The filtrate was then collected and the solvent evaporated to give polyFeOs as a dark purple solid (31.2 mg, 92% yield). The RALS (light scattering) measurements, a molecular weight in a solution dissolved in methanol polyFeOs was 1.37 × ¹⁰ 6 Da. The reaction formula is shown below.

^{1 1} H NMR (CD ₃ OD, 300 MHz, ppm) δ9.70 to 9.57 (m, 4H), 9.02 to 8.53 (m, 8H), 8.08 to 7.99 (m, 4H) , 7.57 to 7.33 (m, 8H). The results of ¹ H NMR of polyFeOs are shown in FIGS. 9 and 10.

[Sample preparation for evaluation of electronic properties]
A sample for evaluating the electrochromic properties of polyFeOs obtained above was prepared by the following procedure. First, polyFeOs was dissolved in methanol to prepare a 4 mg / mL solution. Next, the prepared solution was spray-coated on an ITO substrate to obtain a film having an area of 1.5 cm × 1.5 cm.

[Cyclic voltammetry]
Cyclic voltammetry (CV) was measured using an ALS / CHI electrochemical workstation (manufactured by CH Instruments).
For the CV measurement, a conventional 3-electrode system using _{0.1M LiClO 4} / CH _{3 CN as the supporting electrolyte was adopted.} The three electrodes are a working electrode (WE; working electrode), a platinum electrode (platinum flag) as a counter electrode, and Ag / in acetonitrile containing _{0.1 M TBAP + 0.01 M AgNO 3 with a polymer arranged on ITO.} The Ag ⁺ electrode was used as the reference electrode.
The range of applied voltage was 0 to + 1.1 V at a scanning speed of 50 mV / s. The results of cyclic voltammetry of polyFeOs are shown in FIGS. 11 and 12.

In FIG. 11, when swept from 0V to + 1.1V, the peak observed at 0.60V is the peak of iron ion oxidation, and the peak observed at 0.77V is the peak of Os ion oxidation. Further, when swept from + 1.1 V to 0 V, the peak observed at 0.69 V is the peak of reduction of Os ions, and the peak observed at 0.54 V is the peak of oxidation of Fe ions. Each potential is summarized in FIG. From FIG. 11, it was found that the above redox occurred reversibly.

[In situ UV-vis measurement]
In situ UV-vis measurement was performed with the same experimental settings as CV measurement. Used for. Absorption of the polymer film on ITO was recorded in the applied potential range of 0.6 to + 1.2 V in increments of 0 V and 0.1 V. The results are shown in FIGS. 13 to 14.

FIG. 13 is an ultraviolet-visible absorption spectrum of OsL1 and polyFeOs (0V). From the results shown in FIG. 13, in polyFeOs, absorption of 577 nm and 672 nm, which was not seen in OsL1, was observed, suggesting that Fe and Os were complexed.
The OsL1 solution was brown and transparent, and the polyFeOs solution was lilac and transparent.

FIG. 14 shows the results (absorbance) of in situ UV-vis measurement of polyFeOs.
In the photograph shown in FIG. 14, when the applied voltage changes from 0.0V to + 1.2V, the purple color gradually fades from 0.0V purple to 0.9V, and 1.0V to 1.2V. It shows how the color changes from gray to bluish beige. In addition, the change in absorbance was also a result consistent with the above change in color.

[Measurement of electrochromism characteristics]
Electrochromism (EC) measurements of polyFeOs were performed by monitoring changes in transmitted light intensity of the film on ITO during chronoamperometry measurements with an Ocean Optics modular spectrometer. Three different voltages, 0V, 0.7V, and 1V, were applied by CV and the corresponding changes in transmitted light intensity of the polymer film were recorded. Finally, the EC durability of the polymer film was measured by applying 0V and + 1V to measure the change in the transmittance spectrum.

FIG. 15 is a photograph showing the setup of the above experiment. The applied voltages are 0V, 0.7V, and 1.0V from the left in FIG. When the applied voltage was 0 V, the sample was purple transparent (Fig. 15, left). When the applied voltage was 0.7 V, the sample (center of FIG. 15) was light purple (more reddish, more bluish, and lighter as a whole) and transparent. When the applied voltage was 1.0 V, the sample (Fig. 15, right) was light yellow-green (more bluish, more yellowish, and lighter overall).

FIG. 16 shows the change in transmitted light intensity when the applied voltage is changed to 0V, 0.7V, and 1.0V. The change in transmitted light intensity showed the same tendency as the visual change in color.

FIG. 17 shows a change in transmitted light intensity (left) and a change in current value (right) when changes in applied voltage of 0 V and 1.0 V were repeated 200 times. According to the above, it was found that the transmitted light intensity, the current value, and the response speed did not change even if the color development was repeatedly changed, and the material had excellent durability (excellent fatigue characteristics).

100: Electrochromic element 101: First electrode 102: Electrochromic layer 103: Electrolyte layer 104: Counter electrode layer 105: Second electrode 106: Support substrate 107: Support substrate 200: Electronic book reader 201: Display device 202: Main Controller 203: ROM
204: RAM
205: Flash memory 206: Character generator 207: Interface 211: Display panel 212: Touch panel driver 213: Display controller 214: VRAM
300: Dimmer 301: Outdoor illuminance measurement unit 302: Indoor illuminance measurement unit 303: Incident angle measurement unit 304: Calculation unit 305: Control unit 306: DC power supply unit 307a: Electrochromic element 307b: Electrochromic element 307z: Electrochromic Element 401: Operation unit

Claims (14)

A method for producing polymer compounds
The first organic ligand is coordinated with a first metal ion to obtain a metal complex, wherein the first organic ligand is one coordinating group capable of coordinating with the first metal ion. It has LIG ¹ and one substituent A that can be involved in the cross-coupling reaction, and the first metal ion has a coordination number n times or more the number of coordination loci of the ^{LIG 1 (where n is 2).} (Ions above) and
It has one substituent B that can participate in the cross-coupling reaction corresponding to the substituent A, and one coordinating group LIGHT ² that can coordinate to a second metal ion different from the first metal ion. The ligand precursor is cross-coupled with the metal complex to obtain a second organic ligand having the ^{LIG 1 coordinated to the LIG 2} and the first metal ion.
The LIG ^2, has the LIG ² coordination sites the number of m times the coordination number of (here m is an integer of 2 or more), the second metal different from the first metal ion A method for producing a polymer compound, which comprises coordinating ions to obtain a polymer compound in which the first metal ion and the second metal ion are alternately linked via the second organic ligand. .. The method for producing a polymer compound according to claim 1, wherein the first organic ligand is a compound represented by the following formula 1.

(In Formula 1, L ¹ represents a single bond or an arylene group, a heteroarylene group, an alkenylene group, an alkynylene group, or a combination thereof, and L ² represents a single bond or a divalent group. Represented, X represents the substituent A, and LIGHT ^{1 represents the coordinating group LIGHT 1} that can be coordinated to the first metal ion.) The method for producing a polymer compound according to claim 1 or 2, wherein the ligand precursor is represented by the following formula 2.

(In Formula 2, Y represents the substituent B, L ⁴ represents a single bond or an arylene group, a heteroarylene group, an alkenylene group, an alkynylene group, or a combination thereof, and LIGHT ² represents the first group. ^{Represents the coordinating group LIGHT 2} capable of coordinating with two metal ions, and L ³ represents a single bond or a divalent group. The method for producing a polymer compound according to any one of claims 1 to 3, wherein the substituent A is a halogen atom. A polymer compound in which two different types of metal ions are coordinated and bonded to an organic ligand, so that the two types of metal ions are alternately linked via the organic ligand. The polymer compound according to claim 5, wherein the organic ligand is a nitrogen-containing ligand. The polymer compound according to claim 5, wherein the organic ligand has a residue obtained by removing one or more hydrogen atoms from a pyridine derivative. A polymer compound having a repeating unit represented by the following formula 3.

(In Equation 3, M ¹ represents a first metal ion, M ² represents a second metal ion different from M ^{1 , LI G 1} represents a coordinating group that can be coordinated to M ^{1 , and LIG 2} Represents a coordinating group that can be coordinated to M ^{2 , and LIG 1} and LIG ² may be the same or different, respectively, and L ¹ and L ⁴ are independently single-bonded or an arylene group or a heteroarylene group. alkenylene group, alkynylene group, or represents a group comprising a combination thereof, may be the same or different, L ² and L ³ are each independently a single bond or a divalent group, are identical to or different from each other May be good.) A composition containing the polymer compound according to any one of claims 5 to 8 and a counterion. An electrochromic device having a pair of electrodes and a layer containing the composition according to claim 9 arranged between the electrodes. The electrochromic device according to claim 10, further comprising an electrolyte layer between at least one of the pair of electrodes and the layer. The electrochromic device according to claim 10 or 11, further comprising a counter electrode layer between at least one of the pair of electrodes and the layer. A display device having the electrochromic element according to any one of claims 10 to 12. A dimming device having the electrochromic element according to any one of claims 10 to 12.

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