Electrochemical, spectroelectrochemical, and molecular quadratic and cubic nonlinear optical properties of alkynylruthenium dendrimers

Cifuentes, MP; Powell, CE; Morrall, JP; McDonagh, AM; Lucas, NT; Humphrey, MG; Samoc, M; Houbrechts, S; Asselberghs, I; Clays, K; Persoons, A; Isoshima, T

Electrochemical, spectroelectrochemical, and molecular quadratic and cubic nonlinear optical properties of alkynylruthenium dendrimers

Cifuentes, MP Powell, CE Morrall, JP McDonagh, AM

Lucas, NT Humphrey, MG Samoc, M Houbrechts, S Asselberghs, I Clays, K Persoons, A Isoshima, T

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Publication Type:: Journal Article
Citation:: Journal of the American Chemical Society, 2006, 128 (33), pp. 10819 - 10832
Issue Date:: 2006-08-23

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Field	Value	Language
dc.contributor.author	Cifuentes, MP	en_US
dc.contributor.author	Powell, CE	en_US
dc.contributor.author	Morrall, JP	en_US
dc.contributor.author	McDonagh, AM https://orcid.org/0000-0002-9502-1175	en_US
dc.contributor.author	Lucas, NT	en_US
dc.contributor.author	Humphrey, MG	en_US
dc.contributor.author	Samoc, M	en_US
dc.contributor.author	Houbrechts, S	en_US
dc.contributor.author	Asselberghs, I	en_US
dc.contributor.author	Clays, K	en_US
dc.contributor.author	Persoons, A	en_US
dc.contributor.author	Isoshima, T	en_US
dc.date.issued	2006-08-23	en_US
dc.identifier.citation	Journal of the American Chemical Society, 2006, 128 (33), pp. 10819 - 10832	en_US
dc.identifier.issn	0002-7863	en_US
dc.identifier.uri	http://hdl.handle.net/10453/583
dc.description.abstract	A combination of cyclic voltammetry (CV), UV-vis-NIR spectroscopy and spectroelectrochemistry, hyper-Rayleigh scattering (HRS) [including depolarization studies], Z-scan and degenerate four-wave mixing (DFWM) [including studies employing an optically transparent thin-layer electrochemical (OTTLE) cell to effect electrochemical switching of nonlinearity], pump-probe, and electroabsorption (EA) measurements have been used to comprehensively investigate the electronic, linear optical, and nonlinear optical (NLO) properties of nanoscopic π-delocalizable electron-rich alkynylruthenium dendrimers, their precursor dendrons, and their linear analogues. CV, UV-vis-NIR spectroscopy, and UV-vis-NIR spectroelectrochemistry reveal that the reversible metal-centered oxidation processes in these complexes are accompanied by strong linear optical changes, "switching on" low-energy absorption bands, the frequency of which is tunable by ligand replacement. HRS studies at 1064 nm employing nanosecond pulses reveal large nonlinearities for these formally octupolar dendrimers; depolarization measurements are consistent with lack of coplanarity upon π-framework extension through the metal. EA studies at 350-800 nm in a poly(methyl methacrylate) matrix are consistent with the important transitions having a charge-transfer exciton character that increases markedly on introduction of peripheral polarizing substituent. Time-resolved pump-probe studies employing 55 ps, 527 nm pulses reveal absorption saturation, the longest excited-state lifetime being observed for the dendrimer. Z-scan studies at 800 nm employing femtosecond pulses reveal strong two-photon absorption that increases significantly on progression from linear complex to zero- and then first-generation dendrimer with no loss of optical transparency. Both refractive and absorptive nonlinearity for selected alkynylruthenium dendrimers have been reversibly "switched" by employing the Z-scan technique at 800 and 1180 nm and 100-150 fs pulses, together with a specially modified OTTLE cell, complementary femtosecond time-resolved DFWM and transient absorption studies at 800 nm suggesting that the NLO effects originate in picosecond time scale processes. © 2006 American Chemical Society.	en_US
dc.relation.ispartof	Journal of the American Chemical Society	en_US
dc.relation.isbasedon	10.1021/ja062246v	en_US
dc.subject.classification	General Chemistry	en_US
dc.title	Electrochemical, spectroelectrochemical, and molecular quadratic and cubic nonlinear optical properties of alkynylruthenium dendrimers	en_US
dc.type	Journal Article
utslib.citation.volume	33	en_US
utslib.citation.volume	128	en_US
utslib.for	0306 Physical Chemistry (incl. Structural)	en_US
utslib.for	03 Chemical Sciences	en_US
pubs.embargo.period	Not known	en_US
pubs.organisational-group	/University of Technology Sydney
pubs.organisational-group	/University of Technology Sydney/Faculty of Science
pubs.organisational-group	/University of Technology Sydney/Faculty of Science/School of Mathematical and Physical Sciences
pubs.organisational-group	/University of Technology Sydney/Strength - CCET - Centre for Clean Energy Technology
utslib.copyright.status	closed_access
pubs.issue	33	en_US
pubs.publication-status	Published	en_US
pubs.volume	128	en_US

Abstract:

A combination of cyclic voltammetry (CV), UV-vis-NIR spectroscopy and spectroelectrochemistry, hyper-Rayleigh scattering (HRS) [including depolarization studies], Z-scan and degenerate four-wave mixing (DFWM) [including studies employing an optically transparent thin-layer electrochemical (OTTLE) cell to effect electrochemical switching of nonlinearity], pump-probe, and electroabsorption (EA) measurements have been used to comprehensively investigate the electronic, linear optical, and nonlinear optical (NLO) properties of nanoscopic π-delocalizable electron-rich alkynylruthenium dendrimers, their precursor dendrons, and their linear analogues. CV, UV-vis-NIR spectroscopy, and UV-vis-NIR spectroelectrochemistry reveal that the reversible metal-centered oxidation processes in these complexes are accompanied by strong linear optical changes, "switching on" low-energy absorption bands, the frequency of which is tunable by ligand replacement. HRS studies at 1064 nm employing nanosecond pulses reveal large nonlinearities for these formally octupolar dendrimers; depolarization measurements are consistent with lack of coplanarity upon π-framework extension through the metal. EA studies at 350-800 nm in a poly(methyl methacrylate) matrix are consistent with the important transitions having a charge-transfer exciton character that increases markedly on introduction of peripheral polarizing substituent. Time-resolved pump-probe studies employing 55 ps, 527 nm pulses reveal absorption saturation, the longest excited-state lifetime being observed for the dendrimer. Z-scan studies at 800 nm employing femtosecond pulses reveal strong two-photon absorption that increases significantly on progression from linear complex to zero- and then first-generation dendrimer with no loss of optical transparency. Both refractive and absorptive nonlinearity for selected alkynylruthenium dendrimers have been reversibly "switched" by employing the Z-scan technique at 800 and 1180 nm and 100-150 fs pulses, together with a specially modified OTTLE cell, complementary femtosecond time-resolved DFWM and transient absorption studies at 800 nm suggesting that the NLO effects originate in picosecond time scale processes. © 2006 American Chemical Society.

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