Highly unusual effects of π-conjugation extension on the molecular linear and quadratic nonlinear optical properties of ruthenium(II) ammine complexes

Benjamin J. Coe; Lathe A. Jones; James A. Harris; Bruce S. Brunschwig; Inge Asselberghs; Koen Clays; André Persoons

doi:10.1021/ja028897i

Highly unusual effects of π-conjugation extension on the molecular linear and quadratic nonlinear optical properties of ruthenium(II) ammine complexes

Benjamin J. Coe, Lathe A. Jones, James A. Harris, Bruce S. Brunschwig, Inge Asselberghs, Koen Clays, André Persoons

Research output: Contribution to journal › Article › peer-review

Abstract

We have used several techniques, including hyper-Rayleigh scattering and Stark spectroscopy, to investigate the effects of polyene chain length on the optical properties of complexes containing ruthenium(II) electron donor groups and pyridinium electron acceptors. In marked contrast with all other known donor-acceptor polyenes, conjugation extension beyond a single double bond in the dipolar complexes studied leads to blue-shifting of the intramolecular charge-transfer absorptions. Furthermore, the static first hyperpolarizabilities β0 become maximized with trans-1,3-butadienyl linkages and then decrease in complexes with three CH=CH bonds. Our results clearly demonstrate that the molecular engineering criteria for metal-containing nonlinear optical chromophores can differ dramatically from those for purely organic compounds. Copyright © 2003 American Chemical Society.

Original language	English
Pages (from-to)	862-863
Number of pages	1
Journal	Journal of the American Chemical Society
Volume	125
Issue number	4
DOIs	https://doi.org/10.1021/ja028897i
Publication status	Published - 29 Jan 2003

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title = "Highly unusual effects of π-conjugation extension on the molecular linear and quadratic nonlinear optical properties of ruthenium(II) ammine complexes",

abstract = "We have used several techniques, including hyper-Rayleigh scattering and Stark spectroscopy, to investigate the effects of polyene chain length on the optical properties of complexes containing ruthenium(II) electron donor groups and pyridinium electron acceptors. In marked contrast with all other known donor-acceptor polyenes, conjugation extension beyond a single double bond in the dipolar complexes studied leads to blue-shifting of the intramolecular charge-transfer absorptions. Furthermore, the static first hyperpolarizabilities β0 become maximized with trans-1,3-butadienyl linkages and then decrease in complexes with three CH=CH bonds. Our results clearly demonstrate that the molecular engineering criteria for metal-containing nonlinear optical chromophores can differ dramatically from those for purely organic compounds. Copyright {\textcopyright} 2003 American Chemical Society.",

author = "Coe, {Benjamin J.} and Jones, {Lathe A.} and Harris, {James A.} and Brunschwig, {Bruce S.} and Inge Asselberghs and Koen Clays and Andr{\'e} Persoons",

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TY - JOUR

T1 - Highly unusual effects of π-conjugation extension on the molecular linear and quadratic nonlinear optical properties of ruthenium(II) ammine complexes

AU - Coe, Benjamin J.

AU - Jones, Lathe A.

AU - Harris, James A.

AU - Brunschwig, Bruce S.

AU - Asselberghs, Inge

AU - Clays, Koen

AU - Persoons, André

PY - 2003/1/29

Y1 - 2003/1/29

N2 - We have used several techniques, including hyper-Rayleigh scattering and Stark spectroscopy, to investigate the effects of polyene chain length on the optical properties of complexes containing ruthenium(II) electron donor groups and pyridinium electron acceptors. In marked contrast with all other known donor-acceptor polyenes, conjugation extension beyond a single double bond in the dipolar complexes studied leads to blue-shifting of the intramolecular charge-transfer absorptions. Furthermore, the static first hyperpolarizabilities β0 become maximized with trans-1,3-butadienyl linkages and then decrease in complexes with three CH=CH bonds. Our results clearly demonstrate that the molecular engineering criteria for metal-containing nonlinear optical chromophores can differ dramatically from those for purely organic compounds. Copyright © 2003 American Chemical Society.

AB - We have used several techniques, including hyper-Rayleigh scattering and Stark spectroscopy, to investigate the effects of polyene chain length on the optical properties of complexes containing ruthenium(II) electron donor groups and pyridinium electron acceptors. In marked contrast with all other known donor-acceptor polyenes, conjugation extension beyond a single double bond in the dipolar complexes studied leads to blue-shifting of the intramolecular charge-transfer absorptions. Furthermore, the static first hyperpolarizabilities β0 become maximized with trans-1,3-butadienyl linkages and then decrease in complexes with three CH=CH bonds. Our results clearly demonstrate that the molecular engineering criteria for metal-containing nonlinear optical chromophores can differ dramatically from those for purely organic compounds. Copyright © 2003 American Chemical Society.

U2 - 10.1021/ja028897i

DO - 10.1021/ja028897i

M3 - Article

SN - 0002-7863

VL - 125

SP - 862

EP - 863

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 4

ER -

Highly unusual effects of π-conjugation extension on the molecular linear and quadratic nonlinear optical properties of ruthenium(II) ammine complexes

Abstract

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