Hierarchical symmetry transfer and flexible charge matching in five [M(phen)3]2+ directed iodoargentates with 1 to 3D frameworks

Abstract

Charge compensated by D₃-symmetric [M(phen)₃]²⁺, five iodoargentates, 1D [Co(phen)₃](Ag₃I₅)·2CH₃CN (1), 2D [M(phen)₃]₂Ag₁₁I₁₅·H₂O (M = Co for 2, Cu for 3), and 3D [M(phen)₃]₂Ag₁₃I₁₇ (M = Co for 4, Cd for 5, phen = 1,10-phenanthroline), have been synthesized by changing the molar ratios of AgI : phen and the solvent systems. The 1D anionic chain in 1 is built up from Ag₃I₇ building units and the 2D anionic layers with a (6,3) topology in 2–3 are constructed from C₃-symmetric Ag₆I₁₀ and Ag₆I₁₁/Ag₃I₉ building units, which all correspond to alternatively aggregated enantiomeric [M(phen)₃]²⁺ supramolecular layers with a (6,3) network. Distinctively, the 3D open frameworks in 4–5 are constructed from C₃-symmetric Ag₆I₁₃ and Ag₇I₁₃ building units and enantiopure [M(phen)₃]²⁺ aggregates into rare homochiral 3D supramolecular networks, both of which feature a complementary chiral (10,3) network. Remarkable structural correlations reveal hierarchical symmetry transfer attributed to the unique structural directing effect of [M(phen)₃]²⁺ in the iodoargentate hybrids, while exceptional interruption in 1 is likely due to the encumbrance effect of large lattice solvent molecules. Meanwhile, the occurrence of connection disorder for the inorganic moieties in 2–3 and similar Ag₆I₁₃/Ag₇I₁₃ building units in 4–5 display flexible framework constructions and charge matching of the iodoargentates. Moreover, photodegradation of Rhodamine B catalyzed by 1–5 exhibits good structure–property correlativity.