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Syntheses, spectroscopic and molecular quadratic nonlinear optical properties of dipolar ruthenium(II) complexes of the ligand 1,2-phenylenebis(dimethylarsine)

Syntheses, spectroscopic and molecular quadratic nonlinear optical properties of dipolar ruthenium(II) complexes of the ligand 1,2-phenylenebis(dimethylarsine)
Syntheses, spectroscopic and molecular quadratic nonlinear optical properties of dipolar ruthenium(II) complexes of the ligand 1,2-phenylenebis(dimethylarsine)
Six new complex salts trans-[(Ru(II)Cl)(pdma)(2)L][PF6](n) [pdma=1,2-phenylenebis(dimethylarsine); L=(E,E,E)-1,6-bis(4-pyridyl) hexa-1,3,5-triene (bph), n=1, 5; L=N-methyl-4-[(E)-2-(4-pyridyl) ethenyl]pyridinium (Mebpe(+)), n=2, 7; L=N-methyl-4-[(E,E)-4-(4-pyridyl)buta-1,3-dienyl]pyridinium (Mebpb(+)), n=2, 8; L=N-methyl-4-{(E,E,E)-6-(4-pyridyl)hexa-1,3,5-trienyl} pyridinium (Mebph(+)), n=2, 9; L=bis(4-pyridyl) acetylene (bpa), n=1, 10; L=N-methyl-4-[2-(4-pyridyl)ethynyl] pyridinium (Mebpa(+)), n=2, 11] have been prepared. The electronic absorption spectra of 5 and 7-11 display intense, visible metal-to-ligand charge-transfer (MLCT) bands, with ?(max) values in the range 434-492 nm in acetonitrile. Cyclic voltammetric studies reveal reversible Ru-III/II waves with E-1/2 values in the range 1.06-1.15 V vs. Ag-AgCl, together with irreversible L-based reduction processes. Along with a number of previously reported related compounds (B. J. Coe et al., J. Chem. Soc., Dalton Trans., 1996, 3917; 1997, 591; 2000, 797), salts 5 and 7-11 have been investigated by using Stark (electroabsorption) spectroscopy in butyronitrile glasses at 77 K. These studies have afforded dipole moment changes ??(12) for the MLCT transitions which have been used to calculate molecular static first hyperpolarizabilities ?(0) according to the two-state equation ?(0)=3 ??(12)(?(12))(2)/(E-max)(2) (?(12)=transition dipole moment, E-max=MLCT energy). MLCT absorption and electrochemical data show that a trans-[(Ru(II)Cl)(pdma)(2)](+) centre is considerably less electron-rich than a {Ru-II(NH3)(5)}(2+) unit. Although the ?(0) responses of the pdma complexes are only a little smaller than those of their {Ru-II(NH3)(5)}(2+) analogues, this result is partly attributable to unexpected changes in the relative ?(12) values on freezing. Thus, substantial increases in ?(12) for the arsine compounds act to partially offset the ?(0)-decreasing influence of their higher E-max values when compared with the analogous pentaammine species. Single crystal X-ray structures have been obtained for the salts 1.2.5MeCN, 4.2MeCN, 7 and 11, but only 1.2.5MeCN adopts a non-centrosymmetric space group (Fdd2) such as may show bulk NLO effects.
hyper-rayleigh scattering, transition-metal complexes, bond-length alternation, trans-tetraammineruthenium(ii) complexes, pentaammineruthenium complexes, organometallic complexes, stark spectroscopy, ammine complexes, electron-donor, hyperpolarizabilities
1477-9226
2935-2942
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
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
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
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da

Coe, Benjamin J., Harries, Josephine L., Harris, James A., Brunschwig, Bruce S., Coles, Simon J., Light, Mark E. and Hursthouse, Michael B. (2004) Syntheses, spectroscopic and molecular quadratic nonlinear optical properties of dipolar ruthenium(II) complexes of the ligand 1,2-phenylenebis(dimethylarsine). Dalton Transactions, (18), 2935-2942. (doi:10.1039/B409432H).

Record type: Article

Abstract

Six new complex salts trans-[(Ru(II)Cl)(pdma)(2)L][PF6](n) [pdma=1,2-phenylenebis(dimethylarsine); L=(E,E,E)-1,6-bis(4-pyridyl) hexa-1,3,5-triene (bph), n=1, 5; L=N-methyl-4-[(E)-2-(4-pyridyl) ethenyl]pyridinium (Mebpe(+)), n=2, 7; L=N-methyl-4-[(E,E)-4-(4-pyridyl)buta-1,3-dienyl]pyridinium (Mebpb(+)), n=2, 8; L=N-methyl-4-{(E,E,E)-6-(4-pyridyl)hexa-1,3,5-trienyl} pyridinium (Mebph(+)), n=2, 9; L=bis(4-pyridyl) acetylene (bpa), n=1, 10; L=N-methyl-4-[2-(4-pyridyl)ethynyl] pyridinium (Mebpa(+)), n=2, 11] have been prepared. The electronic absorption spectra of 5 and 7-11 display intense, visible metal-to-ligand charge-transfer (MLCT) bands, with ?(max) values in the range 434-492 nm in acetonitrile. Cyclic voltammetric studies reveal reversible Ru-III/II waves with E-1/2 values in the range 1.06-1.15 V vs. Ag-AgCl, together with irreversible L-based reduction processes. Along with a number of previously reported related compounds (B. J. Coe et al., J. Chem. Soc., Dalton Trans., 1996, 3917; 1997, 591; 2000, 797), salts 5 and 7-11 have been investigated by using Stark (electroabsorption) spectroscopy in butyronitrile glasses at 77 K. These studies have afforded dipole moment changes ??(12) for the MLCT transitions which have been used to calculate molecular static first hyperpolarizabilities ?(0) according to the two-state equation ?(0)=3 ??(12)(?(12))(2)/(E-max)(2) (?(12)=transition dipole moment, E-max=MLCT energy). MLCT absorption and electrochemical data show that a trans-[(Ru(II)Cl)(pdma)(2)](+) centre is considerably less electron-rich than a {Ru-II(NH3)(5)}(2+) unit. Although the ?(0) responses of the pdma complexes are only a little smaller than those of their {Ru-II(NH3)(5)}(2+) analogues, this result is partly attributable to unexpected changes in the relative ?(12) values on freezing. Thus, substantial increases in ?(12) for the arsine compounds act to partially offset the ?(0)-decreasing influence of their higher E-max values when compared with the analogous pentaammine species. Single crystal X-ray structures have been obtained for the salts 1.2.5MeCN, 4.2MeCN, 7 and 11, but only 1.2.5MeCN adopts a non-centrosymmetric space group (Fdd2) such as may show bulk NLO effects.

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More information

Published date: 2004
Keywords: hyper-rayleigh scattering, transition-metal complexes, bond-length alternation, trans-tetraammineruthenium(ii) complexes, pentaammineruthenium complexes, organometallic complexes, stark spectroscopy, ammine complexes, electron-donor, hyperpolarizabilities

Identifiers

Local EPrints ID: 39101
URI: https://eprints.soton.ac.uk/id/eprint/39101
ISSN: 1477-9226
PURE UUID: 76a264f4-06b0-4b05-81d0-f803fc17e994
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272
ORCID for Mark E. Light: ORCID iD orcid.org/0000-0002-0585-0843

Catalogue record

Date deposited: 20 Jun 2006
Last modified: 15 Jul 2019 19:02

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