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Updated: Jun 19, 2025
Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Mixed-ligand, radical, gold bis(dithiolene) complexes: from single-component conductors to controllable NIR-II
Haia Kharraz1, Pere Alemany2, Enric Canadell3,4
1UnivRennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) 35042 Rennes France marc.fourmigue@univ-rennes.fr dominique.lorcy@univ-rennes.fr.
Abstract:
Neutral radical bis(dithiolene) gold complexes [Au(dt)2]˙ are known to exhibit a strong absorption in the 1400-2000 nm NIR absorption range. Here, we demonstrate that the NIR signature of mixed-ligand bis(dithiolene) gold complexes [Au(dtA)(dtD)]˙ associating two different dithiolene, dtA and dtD, is found at higher energy, out of the range of the homoleptic analogs [Au(dtA)2]˙ and [Au(dtD)2]˙, in the looked-after NIR-II 1000-1400 nm absorption range. An efficient synthetic approach towards precursor mixed-ligand monoanionic gold bis(dithiolene) complexes [Au(dtA)(dtD)]-1 is reported. Using this strategy, no symmetrical complexes are formed and, upon electrocrystallization, no scrambling was observed in solution, allowing for the isolation of radical gold bis(dithiolene) complex such as [Au(bdt)(Et-thiazdt)]˙ (bdt: benzene-1,2-dithiolate; Et-thiazdt: N-ethyl-thiazoline-2-thione-3,4-dithiolate), which behaves as a single-component conductor. It is shown from theoretical calculations that the spin polarization induced by electron repulsions leads to a strong localization of the spin-orbitals, and provides a sound basis to understand, (i) the different ligand-based oxidation potentials, (ii) the NIR optical absorption at notably higher energies and (iii) the larger potential difference of the two redox processes than in the parent symmetric complexes. The solid-state properties of the radical complex [Au(bdt)(Et-thiazdt)]˙ are the consequence of a strongly 1D electronic structure with weakly dimerized chains and electronic localization favoring a semiconducting behavior, stable under pressures up to 18.2 GPa. Altogether, the versatility of the preparation method of [Au(dtA)(dtD)]-1 salts opens the route for a wide library of different mixed-ligand radical complexes [Au(dtA)(dtD)]˙ with simultaneously an adaptable absorption in the NIR-II range and the rich structural chemistry of single-component conductors.
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