Issue 5, 2000
From the journal:

Journal of the Chemical Society, Dalton Transactions

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

Benjamin J. Coe,*a   Tim Beyer,b   John C. Jeffery,b   Simon J. Coles,c   Thomas Gelbrich,c   Michael B. Hursthousec  and  Mark E. Lightc  

* Corresponding authors

a Department of Chemistry, University of Manchester, Oxford Road, Manchester, UK
E-mail: b.coe@man.ac.uk

b Department of Chemistry, University of Bristol, Cantock’s Close, Bristol, UK

c EPSRC X-Ray Crystallography Service, Department of Chemistry, University of Southampton, Highfield, Southampton, UK

Abstract

The new series of complex salts trans-[RuIICl(pdma)2L][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-[RuIICl(pdma)2(4,4′-bpy)]PF6 (4,4′-bpy = 4,4′-bipyridine) 1 exhibits an intense dπ(RuII)→π*(4,4′-bpy) metal-to-ligand charge-transfer (MLCT) absorption with λmax at 418 nm in acetonitrile, whilst 2–6 display dπ(RuII)→π*(L) MLCT bands with λmax 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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Article information

DOI
https://doi.org/10.1039/A909336B
Article type
Paper
Submitted
25 Nov 1999
Accepted
24 Jan 2000
First published
17 Feb 2000

J. Chem. Soc., Dalton Trans., 2000, 797-803

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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

B. J. Coe, T. Beyer, J. C. Jeffery, S. J. Coles, T. Gelbrich, M. B. Hursthouse and M. E. Light, J. Chem. Soc., Dalton Trans., 2000, 797 DOI: 10.1039/A909336B

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