Studies on the solvatochromic effect and NLO response in new symmetric bimetallic Rhenium compounds
Date
Authors
SANHUEZA FRIGOLETT, JUAN MANUEL
González, Iván Alonzo
Cortés-Arriagada, Diego
Dreyse, Paulina A.
Sanhueza, Luís Manuel
Crivelli, Irma G.
Ngo, Hoang Minh
Ledoux-Rak, Isabelle
Toro-Labbé, Alejandro
Maze, Jerónimo R.
Loeb, Bárbara L.
González, Iván Alonzo
Cortés-Arriagada, Diego
Dreyse, Paulina A.
Sanhueza, Luís Manuel
Crivelli, Irma G.
Ngo, Hoang Minh
Ledoux-Rak, Isabelle
Toro-Labbé, Alejandro
Maze, Jerónimo R.
Loeb, Bárbara L.
Authors
Date
Datos de publicación:
10.1016/j.poly.2020.114679
Keywords
Bridging Ligand - Metal To Ligand Charge Transfer - Nonlinear Optics - Rhenium Complexes - Solvatochromic Effect - Absorption Spectroscopy - Charge Transfer - Chlorine Compounds - Ligands - Rhenium Compounds - Bimetallic Complexes - Bimetallics - Bridging Ligands - Coordination Complex - Metal To Ligand Charge Transfers - Non-linear Optical Activity - Polypyridines - Rhenium Complexes - Solvatochromic Effects - Symmetrics - Nonlinear Optics
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Abstract
In the search of novel coordination complexes with enhanced nonlinear optical activity, symmetrical bimetallic Rhenium complexes incorporating polypyridine plane bridging ligands are reported. The complexes studied were of the type (Re(CO)<inf>3</inf>Cl)<inf>2</inf>?-N^N, with N?N 2,3-Dicarboxypyrazino[2,3-f][4,7]phenanthrolinedicarboxylic (L1), or 2,3-Diethoxycarbonylypyrazino[2,3-f][4,7]phenanthroline (L2). Specifically, the physicochemical, solvatochromic, and nonlinear optical behaviour of the complexes were measured. DFT calculations were also performed, in order to improve the understanding of the observed phenomena. Spectroscopic characterization shows absorption bands at low energy associated to a charge transfer that involves the electronic transition from the Rhenium center and Chloride ligand towards the bridging ligand (Re(d) + Cl(n) ? L1(?*); Re(d) + Cl(n) ? L2(?*)) in both complexes. These bands are strongly dependent on the polarity of the solvent. This behaviour indicates a redistribution of the electronic density, mainly observed in the complex with L1. As expected, a relationship between solvatochromic effect and NLO response of the analyzed complexes was observed. The bimetallic complexes show a high NLO response, that is a noteworthy effect considering the symmetrical arrangement of the bimetallic complexes herein reported, the non-centro symmetry of these molecules being due to the carboxylic and ester groups only. © 2024 Elsevier B.V., All rights reserved.
Description
Keywords
Bridging Ligand , Metal To Ligand Charge Transfer , Nonlinear Optics , Rhenium Complexes , Solvatochromic Effect , Absorption Spectroscopy , Charge Transfer , Chlorine Compounds , Ligands , Rhenium Compounds , Bimetallic Complexes , Bimetallics , Bridging Ligands , Coordination Complex , Metal To Ligand Charge Transfers , Non-linear Optical Activity , Polypyridines , Rhenium Complexes , Solvatochromic Effects , Symmetrics , Nonlinear Optics
Citation
10.1016/j.poly.2020.114679