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

Benjamin J. Coe; Naomi R M Curati; Emma C. Fitzgerald; Simon J. Coles; Peter N. Horton; Mark E. Light; Michael B. Hursthouse

doi:10.1021/om070042x

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

Benjamin J. Coe, Naomi R M Curati, Emma C. Fitzgerald, Simon J. Coles, Peter N. Horton, Mark E. Light, Michael B. Hursthouse

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Abstract

We have prepared a family of six new bimetallic complexes containing electron-donating trans-[RuII-Cl(pdma)2}+ [pdma = 1,2-phenylenebis(dimethylarsine)] centers linked to trans-[Ru IICl(pdma)(2,2′-bpy)-(NO)] (bpy = bipyridyl) or fac-{Re I(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) → πr*(4,4′-bpy/bpe) metal-to-ligand charge-transfer (MLCT) bands and d(ReI) → π*(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-[Re I(biq)-(CO)3(MeCN)]CF3SO3· CHCl3, /ac-[ReI(biq)(CO)3(4-BrCH 2C5H4N)]PF6, fac-[Re I(biq)(CO)3(4-HCO2-CH2C 5H4N)]PF6·Me2CO, fac-[Re I(biq)(CO)3(ISNE)]CF3SO3 (ISNE = ethylisonicotinate), and fac-[ReI(biq)(CO)3(NC 5H4CO2)]2·HPF 6·3MeCN. 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. © 2007 American Chemical Society.

Original language	English
Pages (from-to)	2318-2329
Number of pages	11
Journal	Organometallics
Volume	26
Issue number	9
DOIs	https://doi.org/10.1021/om070042x
Publication status	Published - 23 Apr 2007

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10.1021/om070042x

CCDC 649780: Experimental Crystal Structure Determination
Coe, B. (Contributor), Curati, N. R. M. (Contributor), Fitzgerald, E. C. (Contributor), Coles, S. J. (Contributor), Horton, P. N. (Contributor), Light, M. E. (Contributor) & Hursthouse, M. B. (Contributor), Cambridge Crystallographic Data Centre, 6 Jun 2007
DOI: 10.5517/ccpt4n8, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccpt4n8&sid=DataCite
Dataset
CCDC 649781: Experimental Crystal Structure Determination
Coe, B. (Contributor), Curati, N. R. M. (Contributor), Fitzgerald, E. C. (Contributor), Coles, S. J. (Contributor), Horton, P. N. (Contributor), Light, M. E. (Contributor) & Hursthouse, M. B. (Contributor), Cambridge Crystallographic Data Centre, 6 Jun 2007
DOI: 10.5517/ccpt4p9, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccpt4p9&sid=DataCite
Dataset
CCDC 649784: Experimental Crystal Structure Determination
Coe, B. (Contributor), Curati, N. R. M. (Contributor), Fitzgerald, E. C. (Contributor), Coles, S. J. (Contributor), Horton, P. N. (Contributor), Light, M. E. (Contributor) & Hursthouse, M. B. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2007
DOI: 10.5517/ccpt4sd, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccpt4sd&sid=DataCite
Dataset

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@article{4337062b3c3b4c3eb4b54da8a2532fc9,

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

abstract = "We have prepared a family of six new bimetallic complexes containing electron-donating trans-[RuII-Cl(pdma)2}+ [pdma = 1,2-phenylenebis(dimethylarsine)] centers linked to trans-[Ru IICl(pdma)(2,2′-bpy)-(NO)] (bpy = bipyridyl) or fac-{Re I(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) → πr*(4,4′-bpy/bpe) metal-to-ligand charge-transfer (MLCT) bands and d(ReI) → π*(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-[Re I(biq)-(CO)3(MeCN)]CF3SO3· CHCl3, /ac-[ReI(biq)(CO)3(4-BrCH 2C5H4N)]PF6, fac-[Re I(biq)(CO)3(4-HCO2-CH2C 5H4N)]PF6·Me2CO, fac-[Re I(biq)(CO)3(ISNE)]CF3SO3 (ISNE = ethylisonicotinate), and fac-[ReI(biq)(CO)3(NC 5H4CO2)]2·HPF 6·3MeCN. 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. {\textcopyright} 2007 American Chemical Society.",

author = "Coe, {Benjamin J.} and Curati, {Naomi R M} and Fitzgerald, {Emma C.} and Coles, {Simon J.} and Horton, {Peter N.} and Light, {Mark E.} and Hursthouse, {Michael B.}",

year = "2007",

month = apr,

day = "23",

doi = "10.1021/om070042x",

language = "English",

volume = "26",

pages = "2318--2329",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "9",

}

TY - JOUR

T1 - Syntheses and properties of bimetallic chromophore-quencher assemblies containing ruthenium(II) and rhenium(I) centers

AU - Coe, Benjamin J.

AU - Curati, Naomi R M

AU - Fitzgerald, Emma C.

AU - Coles, Simon J.

AU - Horton, Peter N.

AU - Light, Mark E.

AU - Hursthouse, Michael B.

PY - 2007/4/23

Y1 - 2007/4/23

N2 - We have prepared a family of six new bimetallic complexes containing electron-donating trans-[RuII-Cl(pdma)2}+ [pdma = 1,2-phenylenebis(dimethylarsine)] centers linked to trans-[Ru IICl(pdma)(2,2′-bpy)-(NO)] (bpy = bipyridyl) or fac-{Re I(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) → πr*(4,4′-bpy/bpe) metal-to-ligand charge-transfer (MLCT) bands and d(ReI) → π*(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-[Re I(biq)-(CO)3(MeCN)]CF3SO3· CHCl3, /ac-[ReI(biq)(CO)3(4-BrCH 2C5H4N)]PF6, fac-[Re I(biq)(CO)3(4-HCO2-CH2C 5H4N)]PF6·Me2CO, fac-[Re I(biq)(CO)3(ISNE)]CF3SO3 (ISNE = ethylisonicotinate), and fac-[ReI(biq)(CO)3(NC 5H4CO2)]2·HPF 6·3MeCN. 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. © 2007 American Chemical Society.

AB - We have prepared a family of six new bimetallic complexes containing electron-donating trans-[RuII-Cl(pdma)2}+ [pdma = 1,2-phenylenebis(dimethylarsine)] centers linked to trans-[Ru IICl(pdma)(2,2′-bpy)-(NO)] (bpy = bipyridyl) or fac-{Re I(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) → πr*(4,4′-bpy/bpe) metal-to-ligand charge-transfer (MLCT) bands and d(ReI) → π*(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-[Re I(biq)-(CO)3(MeCN)]CF3SO3· CHCl3, /ac-[ReI(biq)(CO)3(4-BrCH 2C5H4N)]PF6, fac-[Re I(biq)(CO)3(4-HCO2-CH2C 5H4N)]PF6·Me2CO, fac-[Re I(biq)(CO)3(ISNE)]CF3SO3 (ISNE = ethylisonicotinate), and fac-[ReI(biq)(CO)3(NC 5H4CO2)]2·HPF 6·3MeCN. 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. © 2007 American Chemical Society.

U2 - 10.1021/om070042x

DO - 10.1021/om070042x

M3 - Article

VL - 26

SP - 2318

EP - 2329

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 9

ER -

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

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CCDC 649780: Experimental Crystal Structure Determination

CCDC 649781: Experimental Crystal Structure Determination

CCDC 649784: Experimental Crystal Structure Determination

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