Exploring the Differences in Self‐Assembly Behavior, Structure, and Properties of Two Novel Pentanuclear Zinc (II) Salamo‐Type Complexes Possessing Solvent Effect

Abstract

ABSTRACTA salamo‐type biscompartmental ligand was successfully prepared. On this basis, two novel pentanuclear zinc (II) salamo‐type complexes possessing solvent effect were self‐assembled successfully with different zinc (II) salts: [Zn5(L)2(μ‐OAc)2(CH3COCH3)] (1) and [Zn5(L)2(μ‐OAc)2(CH3CN)] (2). Complex 1 contains two fully deprotonated (L)4− units, five Zn(II) atoms, two coordinating acetate anions, and one coordinating acetone molecule. The zinc (II) atoms are all in a slightly distorted triangular bipyramidal geometrical configurations. Complex 2 consists of two fully deprotonated (L)4− units, five zinc (II) atoms, two coordinating acetate anions and a coordinating acetonitrile molecule. The different structures of the self‐assembling complexes may be attributed to various solvent effects applied in the self‐assembly. As a result, the acetate anions are involved in bridging coordination, thereby expanding the distance between secondary building units (SBUs). In addition, polar nonprotonic solvents, especially acetonitrile and acetone molecules, were involved in the coordination process. Finally, the reaction sites and intermolecular interactions were further discussed by MEP, IRI, and Hirshfeld surfaces, and their fluorescence properties were explored.