Introducing Benzene-1,3,5-tri(dithiocarboxylate) as a Multidentate Linker in Coordination Chemistry

Benzene-1,3,5-tri(dithiocarboxylate) (BTDTC^3–), the sulfur-donor analogue of trimesate (BTC^3–, benzene-1,3,5-tricarboxylate), is introduced, and its potential as a multidentate, electronically bridging ligand in coordination chemistry is evaluated. For this, the sodium salt Na₃BTDTC has been synthesized, characterized, and compared with the sodium salt of the related ditopic benzene-1,4-di(dithiocarboxylate) (Na₂BDDTC). Single-crystal X-ray diffraction of the respective tetrahydrofuran (THF) solvates reveals that such multitopic aromatic dithiocarboxylate linkers can form both discrete metal complexes (Na₃BTDTC·9THF) and (two-dimensional) coordination polymers (Na₂BDDTC·4THF). Additionally, the versatile coordination behavior of the novel BTDTC^3– ligand is demonstrated by successful synthesis and characterization of trinuclear Cu(I) and hexanuclear Mo(II)₂ paddlewheel complexes. The electronic structure and molecular orbitals of both dithiocarboxylate ligands as well as their carboxylate counterparts are investigated by density functional theory computational methods. Electrochemical investigations suggest that BTDTC^3– enables electronic communication between the coordinated metal ions, rendering it a promising tritopic linker for functional coordination polymers.