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A spectroscopic, electrochemical and structural study of polarizable, dipolar ruthenium(II) arsine complexes as models for chromophores with large quadratic non-linear optical responses

A spectroscopic, electrochemical and structural study of polarizable, dipolar ruthenium(II) arsine complexes as models for chromophores with large quadratic non-linear optical responses
A spectroscopic, electrochemical and structural study of polarizable, dipolar ruthenium(II) arsine complexes as models for chromophores with large quadratic non-linear optical responses
The new series of complex salts trans-[(RuCl)-Cl-II(pdma)(2)L][PF6](2) [pdma = 1,2-phenylenebis(dimethylarsine); L = N-methyl-4,4'-bipyridinium (MeQ(+)) 2, N-phenyl-4,4'-bipyridinium (PhQ(+)) 3, N-(4-acetylphenyl)-4,4'-bipyridinium (4-AcPhQ(+)) 4, N-(2,4-dinitrophenyl)-4,4'-bipyridinium (2,4-DNPhQ(+)) 5 or N-(2-pyrimidyl)-4,4'-bipyridinium (2-PymQ(+)) 6] have been prepared. The known complex salt trans-[(RuCl)-Cl-II(pdma)(2)(4,4'-bpy)]PF6 (4,4'-bpy = 4,4'-bipyridine) 1 exhibits an intense d(pi)(Ru-II)-->pi*(4,4'-bpy) metal-to-ligand charge-transfer (MLCT) absorption with lambda(max) at 418 nm in acetonitrile, whilst 2-6 display d(pi)(Ru-II)-->pi*(L) MLCT bands with lambda(max) values in the region 486-544 nm. The MLCT energy decreases as the electron-accepting ability of L increases, in the order L = MeQ(+) < PhQ(+) < 4-AcPhQ(+) < 2,4-DNPhQ(+) < 2-PymQ(+). Cyclic voltammetric studies show that within the series 2-6, the energy of the Ru-based HOMO is almost constant, whilst that of the L-based LUMO decreases by ca. 0.4 eV moving from 2 to 6. Single-crystal structures of the complete series 1 . DMF, 2, 3 . MeCN, 4 . Me2CO, 5 . MeCN and 6 have been determined. Analysis of bond lengths and dihedral angles provides no evidence for ground state charge-transfer, despite the strongly dipolar, polarizable nature of these complexes.
hyper-rayleigh scattering, ray crystal-structure, nonlinear optics, organometallic complexes, sigma-acetylides, metal-complexes, hyperpolarizabilities, design, centers
797-803
Coe, B.J.
bcf93592-85df-4a69-a1cf-aea0a9152789
Beyer, T.
c9037d8f-92ab-44fd-afd3-e32199846290
Jeffery, J.C.
938897e2-448b-4840-9013-76fc5fc74b9e
Coles, S.J.
312b6dc7-a929-462c-b4ef-c9af32fcedc1
Gelbrich, T.
6874d813-bf11-4950-b322-dfe77c533f41
Hursthouse, M.B.
427032bc-428c-4396-adb0-b38e87e908e7
Light, M.E.
d04ad463-ba94-4c59-ab35-a64901f32501
Coe, B.J.
bcf93592-85df-4a69-a1cf-aea0a9152789
Beyer, T.
c9037d8f-92ab-44fd-afd3-e32199846290
Jeffery, J.C.
938897e2-448b-4840-9013-76fc5fc74b9e
Coles, S.J.
312b6dc7-a929-462c-b4ef-c9af32fcedc1
Gelbrich, T.
6874d813-bf11-4950-b322-dfe77c533f41
Hursthouse, M.B.
427032bc-428c-4396-adb0-b38e87e908e7
Light, M.E.
d04ad463-ba94-4c59-ab35-a64901f32501

Coe, B.J., Beyer, T., Jeffery, J.C., Coles, S.J., Gelbrich, T., Hursthouse, M.B. and Light, M.E. (2000) A spectroscopic, electrochemical and structural study of polarizable, dipolar ruthenium(II) arsine complexes as models for chromophores with large quadratic non-linear optical responses. Journal of the Chemical Society, Dalton Transactions, (5), 797-803.

Record type: Article

Abstract

The new series of complex salts trans-[(RuCl)-Cl-II(pdma)(2)L][PF6](2) [pdma = 1,2-phenylenebis(dimethylarsine); L = N-methyl-4,4'-bipyridinium (MeQ(+)) 2, N-phenyl-4,4'-bipyridinium (PhQ(+)) 3, N-(4-acetylphenyl)-4,4'-bipyridinium (4-AcPhQ(+)) 4, N-(2,4-dinitrophenyl)-4,4'-bipyridinium (2,4-DNPhQ(+)) 5 or N-(2-pyrimidyl)-4,4'-bipyridinium (2-PymQ(+)) 6] have been prepared. The known complex salt trans-[(RuCl)-Cl-II(pdma)(2)(4,4'-bpy)]PF6 (4,4'-bpy = 4,4'-bipyridine) 1 exhibits an intense d(pi)(Ru-II)-->pi*(4,4'-bpy) metal-to-ligand charge-transfer (MLCT) absorption with lambda(max) at 418 nm in acetonitrile, whilst 2-6 display d(pi)(Ru-II)-->pi*(L) MLCT bands with lambda(max) values in the region 486-544 nm. The MLCT energy decreases as the electron-accepting ability of L increases, in the order L = MeQ(+) < PhQ(+) < 4-AcPhQ(+) < 2,4-DNPhQ(+) < 2-PymQ(+). Cyclic voltammetric studies show that within the series 2-6, the energy of the Ru-based HOMO is almost constant, whilst that of the L-based LUMO decreases by ca. 0.4 eV moving from 2 to 6. Single-crystal structures of the complete series 1 . DMF, 2, 3 . MeCN, 4 . Me2CO, 5 . MeCN and 6 have been determined. Analysis of bond lengths and dihedral angles provides no evidence for ground state charge-transfer, despite the strongly dipolar, polarizable nature of these complexes.

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Published date: 2000
Keywords: hyper-rayleigh scattering, ray crystal-structure, nonlinear optics, organometallic complexes, sigma-acetylides, metal-complexes, hyperpolarizabilities, design, centers

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Local EPrints ID: 39128
URI: http://eprints.soton.ac.uk/id/eprint/39128
PURE UUID: 543cc8d9-b176-418c-80ce-95305b78b8a3

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Date deposited: 17 Jul 2006
Last modified: 15 Jul 2019 19:01

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Contributors

Author: B.J. Coe
Author: T. Beyer
Author: J.C. Jeffery
Author: S.J. Coles
Author: T. Gelbrich
Author: M.B. Hursthouse
Author: M.E. Light

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