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Microwave-Assisted Synthesis and Photophysical Properties of Poly-Imine Ambipolar Ligands and Their Rhenium(I) Carbonyl Complexes

The phenomenon luminescence rigidochromism has been reported since the 1970s in tricarbonyldiimine complexes with a general formula [R(CO)3LX] using conventional unipolar diimine ligands such as 2,2;-bipyridine or 1,10-phenanthroline as L, and halogens or simple solvents as X. As a major part of this dissertation, microwave-assisted synthesis, purification, characterization and detailed photoluminescence studies of the complex fac-[ReCl(CO)3L], 1, where L = 4-[4,6-bis(3,5-dimethyl-1H-pyrazol-1-yl]-N,N-diethylbenzenamine are reported. The employment of microwaves in the preparation of 1 decreased the reaction time from 48 to 2 hours compared to the conventional reflux method. Stoichiometry variations allows for selective preparation of either a mononuclear, 1, or binuclear, fac-[Re2Cl2(CO)6], 2, complex. The photophysical properties of 1 were analyzed finding that it possesses significant luminescence rigidochromism. The steady state photoluminescence emission spectra of 1 in solution shift from 550 nm in frozen media to 610 nm when the matrix becomes fluid. Moreover, a very sensitive emission spectral analysis of 0.1 K temperatures steps shows a smooth transition through the glass transition temperature of the solvent host. Furthermore, synthetic modifications to L have attained a family of ambipolar compounds that have tunable photophysical, thermophysical and other material properties that render them promising candidates for potential applications in organic electronics and/or sensors - either as is or for their future complexes with various transition metals and lanthanides.

Identiferoai:union.ndltd.org:unt.edu/info:ark/67531/metadc1011818
Date08 1900
CreatorsSalazar Garza, Gustavo Adolfo
ContributorsOmary, Mohammad A. 1969-, Richmond, Michael G., D'Souza, Francis, Reidy, Richard F., 1960-
PublisherUniversity of North Texas
Source SetsUniversity of North Texas
LanguageEnglish
Detected LanguageEnglish
TypeThesis or Dissertation
Formatxi, 93 pages, Text
RightsPublic, Salazar Garza, Gustavo Adolfo, Copyright, Copyright is held by the author, unless otherwise noted. All rights Reserved.

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