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Extended dipolar nonlinear optical chromophores based on trans-bis[1,2-phenylenebis(dimethylarsine)]chlororuthenium(II) centers

Extended dipolar nonlinear optical chromophores based on trans-bis[1,2-phenylenebis(dimethylarsine)]chlororuthenium(II) centers
Extended dipolar nonlinear optical chromophores based on trans-bis[1,2-phenylenebis(dimethylarsine)]chlororuthenium(II) centers
Four new complex salts trans-[(RuCl)-Cl-II(pdma)(2)L-A][PF6](n) [pdma = 1,2-phenylenebis(dimethylarsine); L-A =1,4-bis[E-2-(4-pyridyl)ethenyl]benzene (bpvb), n = 1, 1; L-A = N-methyl-1,4-bis(E-2-(4-pyridyl)ethenyl)benzene (Mebpvb(+)), n = 2, 2; L-A = N-phenyl-1,4-bis(E-2-(4-pyridyl)ethenyl)benzene (Phbpvb(+)), n = 2, 3; L-A = N-(2-pyrimidyl)-1,4-bis(E-2-(4-pyridyl) ethenyl) benzene (Pymbpvb(+)), n) 2, 4] have been prepared. The electronic absorption spectra of 1-4 display intense, visible metal-to-ligand charge-transfer (MLCT) bands, with lambda(max) values in the range 432-474 nm in acetonitrile. Intense intraligand charge-transfer (ILCT) bands due to LA are also observed, with lambda(max) values in the range 350-416 nm. Cyclic voltammetric studies in acetonitrile reveal reversible Ru-III/II waves with E-1/2 values of ca. 1.05 V vs Ag/AgCl, together with L-A-based reduction processes that are irreversible with the exception of 1. Salts 1-4 have been investigated by using Stark (electroabsorption) spectroscopy in butyronitrile glasses at 77 K. These studies have afforded dipole moment changes, Delta mu(12), for the MLCT and ILCT transitions which have been used to calculate molecular static first hyperpolarizabilities, beta(0), according to the two-state equation, beta(0) = 3 Delta mu(12)-(mu(12))(2)/(E-max)(2) (mu(12) = transition dipole moment, E-max = MLCT/ILCT energy). In contrast with related Ru-II ammine complexes, replacement of a central E-ethylene bond with a 1,4-phenylene unit does not appear to be an especially effective strategy for combating the NLO transparency-efficiency tradeoff in these pdma complexes. Single-crystal X-ray studies with the complex salts 2 and 3 and also with the pro-ligand salt [Phbpvb(+)]PF6(.)0.5HPF(6) show that these materials all adopt centrosymmetric packing structures.
hyper-rayleigh scattering, transition-metal complexes, bond-length alternation, ruthenium(ii) complexes, charge-transfer, stark spectroscopy, quadratic hyperpolarizabilities, 1st hyperpolarizabilities, organometallic complexes, electron-acceptors
0020-1669
11019-11029
Coe, Benjamin J.
a31c652b-47a8-4478-8c4c-298a252e6d91
Harries, Josephine L.
ee93b1df-53b6-4eba-87d0-a26c0721a7db
Harris, James A.
9cb0084b-5141-4ff4-a69c-3ce4a6d8f5fb
Brunschwig, Bruce S.
9963c670-c36f-476b-83e8-7bba982cbdc6
Horton, Peter N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Coe, Benjamin J.
a31c652b-47a8-4478-8c4c-298a252e6d91
Harries, Josephine L.
ee93b1df-53b6-4eba-87d0-a26c0721a7db
Harris, James A.
9cb0084b-5141-4ff4-a69c-3ce4a6d8f5fb
Brunschwig, Bruce S.
9963c670-c36f-476b-83e8-7bba982cbdc6
Horton, Peter N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da

Coe, Benjamin J., Harries, Josephine L., Harris, James A., Brunschwig, Bruce S., Horton, Peter N. and Hursthouse, Michael B. (2006) Extended dipolar nonlinear optical chromophores based on trans-bis[1,2-phenylenebis(dimethylarsine)]chlororuthenium(II) centers. Inorganic Chemistry, 45 (26), 11019-11029. (doi:10.1021/ic061659u).

Record type: Article

Abstract

Four new complex salts trans-[(RuCl)-Cl-II(pdma)(2)L-A][PF6](n) [pdma = 1,2-phenylenebis(dimethylarsine); L-A =1,4-bis[E-2-(4-pyridyl)ethenyl]benzene (bpvb), n = 1, 1; L-A = N-methyl-1,4-bis(E-2-(4-pyridyl)ethenyl)benzene (Mebpvb(+)), n = 2, 2; L-A = N-phenyl-1,4-bis(E-2-(4-pyridyl)ethenyl)benzene (Phbpvb(+)), n = 2, 3; L-A = N-(2-pyrimidyl)-1,4-bis(E-2-(4-pyridyl) ethenyl) benzene (Pymbpvb(+)), n) 2, 4] have been prepared. The electronic absorption spectra of 1-4 display intense, visible metal-to-ligand charge-transfer (MLCT) bands, with lambda(max) values in the range 432-474 nm in acetonitrile. Intense intraligand charge-transfer (ILCT) bands due to LA are also observed, with lambda(max) values in the range 350-416 nm. Cyclic voltammetric studies in acetonitrile reveal reversible Ru-III/II waves with E-1/2 values of ca. 1.05 V vs Ag/AgCl, together with L-A-based reduction processes that are irreversible with the exception of 1. Salts 1-4 have been investigated by using Stark (electroabsorption) spectroscopy in butyronitrile glasses at 77 K. These studies have afforded dipole moment changes, Delta mu(12), for the MLCT and ILCT transitions which have been used to calculate molecular static first hyperpolarizabilities, beta(0), according to the two-state equation, beta(0) = 3 Delta mu(12)-(mu(12))(2)/(E-max)(2) (mu(12) = transition dipole moment, E-max = MLCT/ILCT energy). In contrast with related Ru-II ammine complexes, replacement of a central E-ethylene bond with a 1,4-phenylene unit does not appear to be an especially effective strategy for combating the NLO transparency-efficiency tradeoff in these pdma complexes. Single-crystal X-ray studies with the complex salts 2 and 3 and also with the pro-ligand salt [Phbpvb(+)]PF6(.)0.5HPF(6) show that these materials all adopt centrosymmetric packing structures.

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Published date: 2006
Keywords: hyper-rayleigh scattering, transition-metal complexes, bond-length alternation, ruthenium(ii) complexes, charge-transfer, stark spectroscopy, quadratic hyperpolarizabilities, 1st hyperpolarizabilities, organometallic complexes, electron-acceptors

Identifiers

Local EPrints ID: 44576
URI: http://eprints.soton.ac.uk/id/eprint/44576
ISSN: 0020-1669
PURE UUID: 96f35b35-f530-4d24-b2de-bd14c55b5975
ORCID for Peter N. Horton: ORCID iD orcid.org/0000-0001-8886-2016

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Date deposited: 05 Mar 2007
Last modified: 29 Aug 2019 00:47

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Author: Benjamin J. Coe
Author: Josephine L. Harries
Author: James A. Harris
Author: Bruce S. Brunschwig
Author: Peter N. Horton ORCID iD

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