Revisiting the quasi-aromaticity in polynuclear metal chalcogenide clusters and their derivative "cluster-assembly" crystalline structures.

ABSTRACT

The concept of aromaticity is primarily invented to account for the high stability of conjugated organic compounds that possess a specific structural and chemical stability with (4n + 2) π electrons. In 1988, quasi-aromaticity was theoretically proposed for the Mo3S44+ core in the Mo3(µ3-S)(µ-S)3(χ-dtp)3(µ-dtp) L compound (χ chelating ligand; dtp (EtO)2PS2-) illustrated by canonical molecular orbitals. However, the origin of the quasi-aromaticity and chemical bonding remains ambiguous, lacking a thorough analysis in terms of stability and quantitative measurement of the aromatic character. Thus, in this work, we systematically reported the electronic structure and aromaticity of a series of polynuclear metal chalcogenide clusters [M3X4(H2O)9]4+ (M = Cr, Mo, W, and Sg; X = O, S, Se, and Te) to explore an efficient tool of NICS index values at specific points to measure the quasi-aromaticity and to figure out the (d-p-d) π three-center bonding as the predominant origin from the arrangement of three Mo atoms and three bridged X atoms. Interestingly, derived from the Mo3⋯S3 quasi-plane, the extended sandwich cluster model of a S3⋯Mo3⋯S3 (Mo3S6) structure can be seen as the seed unit of the popular MoS2 nanomaterials, with the resemblance between both molecular and periodic systems regarding geometries, electronic structures, and chemical bonding. Additionally, the highly symmetric Mo3S4 core in [Mo3X4(H2O)9]4+ can be arranged in a staggered and stacked manner to create the Mo6S82- building block, corresponding to the crystalline structures in BaMo6S8 Chevrel phases, albeit with slight deformations. But the neutral Mo6S8 cluster can be seen as the seed structure for the Mo3S4 periodic materials for the high resemblance in terms of geometry, electronic structures and chemical bonding. Drawing upon the observed similarities between cluster models and materials, we propose a new concept termed "cluster-assembly" materials. This concept involves the expansion from a high-symmetry and/or aromatic stable cluster seed unit to form the corresponding derivative materials, presenting an alternative paradigm for investigating crystals and enriching our comprehension of the stabilities exhibited by both gas-phase clusters and solid-state materials. The concept of "cluster-assembly" materials not only contributes to the formulation of design strategies for novel materials or stable clusters but also provides valuable insights into the extension of periodic aromaticity.