Solvent-Dependent Photophysical Properties of a Semiconducting One-Dimensional Silver Cluster-Assembled Material
Anish Kumar Das, Sourav Biswas, Surya Sekhar Manna, Biswarup Pathak, Sukhendu Mandal
Abstract
Unraveling the total structure of the atom-precise silver cluster-assembled materials (CAMs) is extremely significant to elucidating the structure–property correlation, but it is a very challenging task. Herein, a new silver CAM is synthesized by a facile synthetic pathway with a unique distorted elongated square-bipyramid-based Ag11 core geometry. The core is protected by two different kinds of the surface protecting ligands (adamantanethiolate and trifluoroacetate) and connected through a bidentate organic linker. The crystallographic data show that this material embraces a one-dimensional periodic structure that orchestrates by various noncovalent interactions to build a thermally stable supramolecular assembly. Further characterization confirms its n-type semiconducting property with an optical band gap of 1.98 eV. The impact of an adamantanethiol-protected silver core on the optical properties of this type of periodic framework is analyzed by the UV–vis absorbance and emission phenomena. Theoretical calculations predicted that the occupied states are majorly contributed by Ag–S. Solvent-dependent photoluminescence studies proved that a polar solvent can significantly perturb the metal thiolate and thiolate-centered frontier molecular orbitals that are involved in the electronic transitions.