Solvent-Dependent Photophysical Properties of a Semiconducting One-Dimensional Silver Cluster-Assembled Material

Abstract

Unraveling the total structure of the atom-precise silver clusterassembled 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 Ag 11 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.

An atomically precise silver nanocluster for artificial light-harvesting system through supramolecular functionalization

“…S2 †) which indicates the reality of the nonbonding argentophilic interaction. 53,54 The geometry of the distorted Ag 16 core comprises eight triangular facets and ten square facets (Fig. S3 †).…”

Template-assisted alloying of atom-precise silver nanoclusters: a new approach to generate cluster functionality

“…S1), where the twenty Ag(I) atoms are held together by the argentophilic interactions. 42,43 The Bader's charge analysis between the two adjacent Ag atoms in each Ag 20 core indicates the reality of non-covalent argentophilic interaction (Fig. S2).…”

Role of Non-covalent Interaction toward Conductivity in a One-Dimensional Tube-like Silver-Thiolate Structure

“…Interestingly, we observed the presence of the C–H···H–C interaction between the neighboring isobutyl thiol molecules in the one-dimensional chains as well as in-between the chains (Table S4, Figures S4,S5). These H···H interactions appeared as crucial to arrange each individual chain in a three-dimensional supramolecular fashion …”

“…The progress in the synthesis, structural evolution, functionalization, and application of ligand-stabilized atom-precise metal nanoclusters unfolded several opportunities to use these cluster building blocks for designing a cluster-based architecture for tunable properties. − Therefore, the stability of these building blocks appears challenging for practical applications as this depends on several factors: nanocluster size, core structure, surface ligand architecture, ligand nature, and supramolecular assembly of the nanocluster being a few of these. − However, the progressing research interest has led to a solution where the network structure of cluster-building blocks has been proven to provide ultimate stability. − In most cases, organic linker molecules were used to assemble cluster units through coordination bonds. ,, The incorporation of foreign linker molecules into the cluster building blocks, however, further complicates the understanding of the structure–property relationship. This is because the organic linkers that added to the clusters, contribute to the frontier molecular orbitals, which makes it difficult to attribute the newly arising properties of the assembled clusters to its structural framework alone.…”