Organic/heterometallic hybrid polymer, process for producing same, film of organic/heterometallic hybrid polymer, organic/multimetallic hybrid polymer, process for producing same, and film of organic/multimetallic hybrid polymer

Patent metadata

Field	Value
Publication number	US-10118995-B2
Application number	US-201515307037-A
Country	US
Kind code	B2
Filing date	May 1, 2015
Priority date	May 2, 2014
Publication date	Nov 6, 2018
Grant date	Nov 6, 2018

Abstract

The present invention relates to an organic/heterometallic hybrid polymer including a plurality of organometal complexes and a plurality of transition metals, the organic/heterometallic hybrid polymer, wherein
the plurality of organometal complexes are linked in a linear manner by sandwiching each of the plurality of transition metals therebetween, the organometal complexes include two ligands each having a terpyridyl group and one connector having Ru(dppe) 2 and two ethynylene groups, and the two ligands are linked by the connector, so that a nitrogen atom at position 1′ of the terpyridyl group is directed toward the terminal side of the molecule of the organometal complex, and the terpyridyl groups of at least two different organometal complexes of the plurality of organometal complexes are bound to one of the transition metals through a coordinate bond, thereby linking the plurality of organometal complexes while sandwiching the plurality of transition metals alternately therebetween.

First claim

The invention claimed is:

1. An organic/heterometallic hybrid polymer comprising a plurality of organometal complexes and a plurality of transition metals,
wherein said plurality of organometal complexes are linked in a linear manner by sandwiching each of said plurality of transition metals therebetween,
said organometal complexes include two ligands each having a terpyridyl group and one connector having Ru(dppe) 2 and two ethynylene groups, and the two ligands are linked by the connector, so that a nitrogen atom at position 1′ of said terpyridyl group is directed toward a terminal side of a molecule of said organometal complex, and
the terpyridyl groups of at least two different organometal complexes of said plurality of organometal complexes are bound to one of said transition metals through a coordinate bond, thereby linking said plurality of organometal complexes while sandwiching said plurality of transition metals alternately therebetween.

2. The organic/heterometallic hybrid polymer according to claim 1 , wherein said transition metal is any one of Ru, Fe or Zn.

3. The organic/heterometallic hybrid polymer according to claim 1 , wherein a molecular weight M W is at least 10.5×10 4 and not more than 29.2×10 4 .

4. An organic/heterometallic hybrid polymer film comprising the organic/heterometallic hybrid polymer according to claim 1 .

5. The organic/heterometallic hybrid polymer film according to claim 4 , wherein a film thickness is at least 100 nm and not more than 1 mm.

6. The organic/heterometallic hybrid polymer film according to claim 4 , wherein a transition metal contained in said organic/heterometallic hybrid polymer is either Fe or Zn.

7. An organic/multimetallic hybrid polymer comprising a plurality of organometal ligands and a plurality of transition metals,
wherein a linear portion in which said plurality of organometal ligands are linked in a linear manner by sandwiching each of said plurality of transition metals therebetween is included,
said organometal ligand is formed by linking two ligands to one connector,
said connector is formed with a benzene ring at the center by linking two Ru(dppe) 2 via two ethynylene groups bonded to the benzene ring, while connecting two phenyl groups to said two Ru(dppe) 2 via other two ethynylene groups,
said ligands are terpyridyl groups and are formed by being connected respectively to said two phenyl groups of said connector, and
said terpyridyl groups of at least two different organometal ligands of said plurality of organometal ligands are bound to one of said transition metals through a coordinate bond, thereby linking said plurality of organometal ligands while alternately sandwiching said plurality of transition metals therebetween.

8. The organic/multimetallic hybrid polymer according to claim 7 , wherein said transition metal is Fe, Zn, Co or Ru.

9. The organic/multimetallic hybrid polymer according to claim 7 which is linear.

10. The organic/multimetallic hybrid polymer according to claim 7 which is branched.

11. The organic/multimetallic hybrid polymer according to claim 10 comprising a branched portion composed of 1,3,5-Tris[4-(2,2′:6′,2″-terpyridin-4′-yl)phenyl]benzene.

12. The organic/multimetallic hybrid polymer according to claim 10 , wherein a content of said branched portion is at least 10 molar parts and not more than 30 molar parts, relative to the total number of moles of linear portions and branched portions constituting the organic/multimetallic hybrid polymer.

13. An organic/multimetallic hybrid polymer film comprising the organic/multimetallic hybrid polymer according to claim 7 .

14. The organic/multimetallic hybrid polymer film according to claim 13 , wherein a film thickness is at least 100 nm and not more than 1 mm.

15. A method of producing an organic/heterometallic hybrid polymer, the method comprising:
a step of synthesizing an organometal complex having Ru(dppe) 2 and a terminal terpyridyl group by reacting a terpyridine compound having an ethynyl group and a terpyridyl group with a compound containing Ru(dppe) 2 in an organic solvent; and
a step of synthesizing the organic/heterometallic hybrid polymer by reacting said organic metal complex and a transition metal compound in an organic solvent.

16. The method of producing an organic/heterometallic hybrid polymer according to claim 15 , wherein 1.0 molar equivalent or more of the transition metal compound is reacted with respect to said organometal complex.

17. The method of producing an organic/heterometallic hybrid polymer according to claim 15 , wherein said transition metal compound is any one of RuCl 2 , Fe(BF 4 ) 2 , or Zn(NTf 2 ) 2 .

18. The method of producing an organic/heterometallic hybrid polymer according to claim 15 , wherein a reaction time of said organic metal complex and said transition metal compound is equal to or more than 12 hours.

19. A method of synthesizing an organic/multimetallic hybrid polymer, the method comprising:
a step of synthesizing a binuclear organometallic site comprising two Ru(dppe) 2 by reacting 1 molar equivalent of diethynylbenzene and 2 molar equivalents of Ru(dppe) 2 Cl(OTf) in an organic solvent;
a step of synthesizing an organometal ligand having a terpyridyl group at the terminal and two Ru(dppe) 2 by reacting 2 molar equivalents of a terpyridine compound having an ethynyl group and a terpyridyl group with one molar equivalent of a binuclear organometallic site in an organic solvent; and
a step of synthesizing a linear organic/multimetallic hybrid polymer by reacting said organometal ligand and a transition metal compound in an organic solvent.

20. The method of synthesizing an organic/multimetallic hybrid polymer according to claim 19 , wherein a branched organic/multimetallic hybrid polymer is synthesized by reacting said linear organic/multimetallic hybrid polymer, a branched compound branched into three or more directions with a branch element at the center and having a ligand at a branched molecule end, and a transition metal compound.

21. The method of synthesizing an organic/multimetallic hybrid polymer according to claim 20 , wherein said branched compound is 1,3,5-Tris[4-(2,2′:6′,2″-terpyridin-4′-yl)phenyl]benzene.

22. The method of synthesizing an organic/multimetallic hybrid polymer according to claim 20 , wherein a mixing amount of said branched compound is at least 10 molar parts and not more than 30 molar parts, relative to the combined total of 100 molar parts of linear portions constituting the linear organic/multimetallic hybrid polymer.

23. The method of synthesizing an organic/multimetallic hybrid polymer according to claim 19 , wherein 1.0 molar equivalent or more of the transition metal compound is reacted with respect to said organometal ligand.

24. The method of synthesizing an organic/multimetallic hybrid polymer according to claim 19 , wherein said transition metal compound is Fe(BF 4 ) 2 or Zn(NTf 2 ) 2 .

25. The method of synthesizing an organic/multimetallic hybrid polymer according to claim 19 , wherein a reaction time of said organometal ligand and said transition metal compound is equal to or more than 6 hours.

Assignees

• Nat Inst Materials Science
• Nat Institute Of Materials Science

Inventors

• Higuchi Masayoshi
• Sato Takashi

Classifications

• C08G79/00

  Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon {with or without the latter elements in the main chain of the macromolecule} · CPC title

• G01N27/04

  by investigating resistance · CPC title

• H01M8/02

  Details (electrodes H01M4/86 - H01M4/98) · CPC title

• C08G79/14 Primary

  a linkage containing two or more elements other than carbon, oxygen, nitrogen, sulfur and silicon · CPC title

• H01B1/06

  mainly consisting of other non-metallic substances · CPC title