Self-Assembly, Structures, and Solution Dynamics of Emissive Silver Metallacycles and Helices

Reactions of 9,10-bis(diphenylphosphino)anthracene (PAnP) and AgX (X = OTf-, ClO4-, PF6-, and BF4-) led to luminescent Ag−PAnP complexes with rich structural diversity. Helical polymers [Ag(μ-PAnP)(CH3CN)X]n (X = OTf-, ClO4-, and PF6-) and discrete binuclear [Ag2(μ-PAnP)2(CH3CN)4](PF6)2, trinuclear [Ag3(μ-PAnP)3⊃BF4](BF4)2, and tetranuclear [Ag4(μ-PAnP)4⊃(ClO4)2](ClO4)2 metallacycles were isolated from different solvents. The tri- and tetranuclear metallacycles exhibited novel puckered-ring and saddlelike structures. Variable-temperature (VT) 31P{1H}-NMR spectroscopy of the complexes was solvent dependent. The dynamics in CD3CN involve two species, but the exchange processes in CD2Cl2 are more complicated. A ring-opening polymerization was proposed for the exchange mechanism in CD3CN.