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 p -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, 1 – 4 (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 ( 3, cis- 4, and trans - 4 ) interact strongly with picric acid (PA) to yield cocrystallized products, PA + metalla-assemblies, confirmed by single-crystal X-ray structure analyses.