This item still needs to be validated !
Title: Unusual frequency dispersion effects of the nonlinear optical response in highly conjugated (polypyridyl)metal-(porphinato)zinc(II) chromophores
Authors: Uyeda, HT ×
Zhao, YX
Wostyn, Kurt
Asselberghs, Inge
Clays, Koen
Persoons, Andre
Therien, MJ #
Issue Date: Jan-2002
Publisher: Amer chemical soc
Series Title: Journal of the American Chemical Society vol:124 issue:46 pages:13806-13813
Abstract: The syntheses and electrooptic properties of a new family of nonlinear optical chromophores are reported. These species feature an ethyne-elaborated, highly polarizable porphyrinic component and metal polypyridyl complexes that serve as integral donor and acceptor elements. Examples of this structural motif include ruthenium(II) [5-(4'-ethynyl-(2,2';6',2"-terpyridinyl))-10,20-bis(2',6'-bis(3,3-di-methyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2';6',2"-terpyridine)(2+) bis-hexafluorophosphate (Ru-PZn); osmium(II) [5-(4'-ethynyl-(2,2';6',2"-terpyridinyl))-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2';6',2"-terpyridine)(2+) bis-hexafluorophosphate (Os-PZn); ruthenium(II) [5-(4'-ethynyl-(2,2';6',2"-terpyridinyl))-15-(4'-nitrophenyl)ethynyl-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2';6',2"-terpyridine)(2+) bis-hexafluorophosphate (Ru-PZn-A); osmium(II) [5-(4'-ethynyl-(2,2';6',2"-terpyridinyl))-15-(4'-nitrophenyl)ethynyl-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(ii)-(2,2';6',2"-terpyridine)(2+) bis-hexafluorophosphate (Os-PZn-A); and ruthenium(II) [5-(4'-ethynyl-(2,2';6',2"-terpyridinyl))osmium(II)-15-(4'-ethynyl-(2,2';6',2"-terpyridinyl))-10,20-bis (2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-bis(2,2';6',2"-terpyridine)(4+) tetrakis-hexafluorophosphate (Ru-PZn-Os). The frequency dependence of the dynamic hyperpolarizability of these compounds was determined from hyperRayleigh light scattering (HRS) measurements carried out at fundamental incident irradiation wavelengths (lambda(inc)) of 800, 1064, and 1300 nm. These data show that (i) coupled oscillator photophysics and metal-mediated cross-coupling can be exploited to elaborate high beta(0) supermolecules that exhibit significant excited-state electronic communication between their respective pigment building blocks; (ii) high-stability metal polypyridyl compounds constitute an attractive alternative to electron releasing dialkyl- and diarylamino groups, the most commonly used donor moieties in a wide range of established nonlinear optical dyes; (iii) this design strategy enables ready elaboration of chromophores having extraordinarily large dynamic hyperpolarizabilities (beta(i) values) at telecommunication relevant wavelengths; and (iv) porphyrin B- and Q-state-derived static hyperpolarizabilities (beta(0) values) can be designed to have the same or opposite sign in these species, thus providing a new means to regulate the magnitude Of lambda(inc)-specific dynamic hyperpolarizabilities.
ISSN: 0002-7863
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Molecular Imaging and Photonics
× corresponding author
# (joint) last author

Files in This Item:

There are no files associated with this item.

Request a copy


All items in Lirias are protected by copyright, with all rights reserved.

© Web of science