Electron-Rich Arene–Ruthenium Metalla-architectures Incorporating Tetrapyridyl–Tetrathiafulvene Donor Moieties

Abstract

A series of arene ruthenium architectures have been prepared from coordination-driven self-assembly using dinuclear <i>p</i>-cymene ruthenium acceptors and π-donating tetratopic tetrapyridyl–tetrathiafulvalene donor ligands. The synthetic strategy, based on a geometric interaction approach, leads to four electroactive metalla-assemblies, <b>1</b>–<b>4</b> (one molecular cube and three metallaplates), that were characterized by NMR, ESI-MS, X-ray diffraction, and cyclic voltammetry. Rationalization of their formation discrepancy was completed by DFT calculations supported by structural features of their constituting TTF and Ru-complex components. Metalla-architectures possessing electron-rich cores (<b>3</b>, <i>cis-</i><b>4</b>, and <i>trans</i>-<b>4</b>) interact strongly with picric acid (PA) to yield cocrystallized products, PA + metalla-assemblies, confirmed by single-crystal X-ray structure analyses