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

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.