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Syntheses and properties of bimetallic chromophore-quencher assemblies containing ruthenium(II) and rhenium(I) centers

Syntheses and properties of bimetallic chromophore-quencher assemblies containing ruthenium(II) and rhenium(I) centers
Syntheses and properties of bimetallic chromophore-quencher assemblies containing ruthenium(II) and rhenium(I) centers
We have prepared a family of six new bimetallic complexes containing electron-donating trans-{RuIICl(pdma)2}+ [pdma = 1,2-phenylenebis(dimethylarsine)] centers linked to trans-[RuIICl(pdma)(2,2'-bpy)(NO)] (bpy = bipyridyl) or fac-{ReI(biq)(CO)3}+-based (biq = 2,2'-biquinolinyl) electron acceptors. The extended bridging units are based on 4,4'-bpy or bpe [E-1,2-bis(4-pyridyl)ethylene] ligands, and these assemblies are designed to display long-lived photoinduced charge-separated states. A number of new monometallic precursor complexes have also been synthesized and fully characterized. The electronic absorption spectra of the bimetallic species are dominated by intense, visible d(RuII) *(4,4'-bpy/bpe) metal-to-ligand charge-transfer (MLCT) bands and d(ReI) *(biq) absorptions in the near-UV region. Cyclic voltammetric studies show both metal-based oxidation and ligand-based reduction processes and provide evidence that these assemblies contain thermodynamic driving forces for charge separation. Single-crystal X-ray structures have been determined for the monometallic complex salts fac-[ReI(biq)(CO)3(MeCN)]CF3SO3·CHCl3, fac-[ReI(biq)(CO)3(4-BrCH2C5H4N)]PF6, fac-[ReI(biq)(CO)3(4-HCO2CH2C5H4N)]PF6·Me2CO, fac-[ReI(biq)(CO)3(ISNE)]CF3SO3 (ISNE = ethylisonicotinate), and fac-[ReI(biq)(CO)3(NC5H4CO2)]2·HPF6·3MeCN. Ultrafast time-resolved infrared and Raman spectroscopic measurements will be employed to investigate the photoexcitation properties of the bimetallic species and of monometallic reference complexes.
ir, charge-separated-state, room-temperature, photosynthesis, resolved, artificial, transfer excited-states, molecular assemblies, resonance raman, metal-complexes, photoinduced electron-transfer, absorption, infrared-spectroscopy
0276-7333
2318-2329
Coe, B.J.
bcf93592-85df-4a69-a1cf-aea0a9152789
Curati, N.R.M.
c4c0f9d2-8b4f-4253-aeba-4720b5738d54
Fitzgerald, E.C.
8ac84e2d-fc1d-41c4-9f93-7201a5d79b7a
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Horton, P.N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Light, M.E.
cf57314e-6856-491b-a8d2-2dffc452e161
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Coe, B.J.
bcf93592-85df-4a69-a1cf-aea0a9152789
Curati, N.R.M.
c4c0f9d2-8b4f-4253-aeba-4720b5738d54
Fitzgerald, E.C.
8ac84e2d-fc1d-41c4-9f93-7201a5d79b7a
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Horton, P.N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Light, M.E.
cf57314e-6856-491b-a8d2-2dffc452e161
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da

Coe, B.J., Curati, N.R.M., Fitzgerald, E.C., Coles, S.J., Horton, P.N., Light, M.E. and Hursthouse, M.B. (2007) Syntheses and properties of bimetallic chromophore-quencher assemblies containing ruthenium(II) and rhenium(I) centers. Organometallics, 26 (9), 2318-2329. (doi:10.1021/om070042x).

Record type: Article

Abstract

We have prepared a family of six new bimetallic complexes containing electron-donating trans-{RuIICl(pdma)2}+ [pdma = 1,2-phenylenebis(dimethylarsine)] centers linked to trans-[RuIICl(pdma)(2,2'-bpy)(NO)] (bpy = bipyridyl) or fac-{ReI(biq)(CO)3}+-based (biq = 2,2'-biquinolinyl) electron acceptors. The extended bridging units are based on 4,4'-bpy or bpe [E-1,2-bis(4-pyridyl)ethylene] ligands, and these assemblies are designed to display long-lived photoinduced charge-separated states. A number of new monometallic precursor complexes have also been synthesized and fully characterized. The electronic absorption spectra of the bimetallic species are dominated by intense, visible d(RuII) *(4,4'-bpy/bpe) metal-to-ligand charge-transfer (MLCT) bands and d(ReI) *(biq) absorptions in the near-UV region. Cyclic voltammetric studies show both metal-based oxidation and ligand-based reduction processes and provide evidence that these assemblies contain thermodynamic driving forces for charge separation. Single-crystal X-ray structures have been determined for the monometallic complex salts fac-[ReI(biq)(CO)3(MeCN)]CF3SO3·CHCl3, fac-[ReI(biq)(CO)3(4-BrCH2C5H4N)]PF6, fac-[ReI(biq)(CO)3(4-HCO2CH2C5H4N)]PF6·Me2CO, fac-[ReI(biq)(CO)3(ISNE)]CF3SO3 (ISNE = ethylisonicotinate), and fac-[ReI(biq)(CO)3(NC5H4CO2)]2·HPF6·3MeCN. Ultrafast time-resolved infrared and Raman spectroscopic measurements will be employed to investigate the photoexcitation properties of the bimetallic species and of monometallic reference complexes.

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More information

Published date: 2007
Keywords: ir, charge-separated-state, room-temperature, photosynthesis, resolved, artificial, transfer excited-states, molecular assemblies, resonance raman, metal-complexes, photoinduced electron-transfer, absorption, infrared-spectroscopy

Identifiers

Local EPrints ID: 54270
URI: https://eprints.soton.ac.uk/id/eprint/54270
ISSN: 0276-7333
PURE UUID: d049d663-92c0-4324-a4a5-afff428fcb05
ORCID for S.J. Coles: ORCID iD orcid.org/0000-0001-8414-9272
ORCID for P.N. Horton: ORCID iD orcid.org/0000-0001-8886-2016
ORCID for M.E. Light: ORCID iD orcid.org/0000-0002-0585-0843

Catalogue record

Date deposited: 31 Jul 2008
Last modified: 20 Jul 2019 01:10

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