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Updated: May 16, 2025

Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
Published on: February 15, 2016
A chiral Si(IV) complex bearing a 1,2,4-triazole-2,2'-diphenol ligand: synthesis, (chiro-)optical properties and
Valerio Giuso1, Thibault Thierry1, Christophe Gourlaouen2
1Institut de Physique et Chimie des Matériaux de Strasbourg UMR 7504 - Université de Strasbourg & CNRS, 23 rue du Loess, 67034 Strasbourg, France. bellemin@unistra.fr.
Abstract:
The reactivity of bis-3,5-phenol 1-phenyl-1,2,4-triazole, a non-symmetrical tridentate O^N^O proligand derived from Deferasirox, towards a Si(IV) precursor is herein studied. The reaction of the proligand (O1NO2)H2 with SiCl4 afforded a highly stable homoleptic hexacoordinate complex, namely Si(O1NO2)2, in high yield. While the emission profile of the proligand - arising from an excited-state intramolecular proton transfer (ESIPT) mechanism - appears featureless and broad, the Si(IV) complex exhibits enhanced photoluminescence in the violet-to-deep-blue region, with a quantum yield of up to 32% in spin-coated thin films. A comprehensive study, combining photophysical methods and (time-dependent) density functional theory (TD-DFT) calculations, has rationalized the emissive behavior of this complex. Due to the non-symmetrical nature of the ligand, the homoleptic Si complex is obtained as a racemate of two Δ/Λ enantiomers that were separated by chiral chromatography and characterized by electronic circular dichroism (ECD). Subsequent TD-DFT calculations enabled the modelling of the ECD spectra and the assignment of the absolute configuration of the resolved enantiomers.
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