Self-assembly, structures, and solution dynamics of emissive silver metallacycles and helices

Abstract

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 PF 6 -) and discrete binuclear [Ag2(μ-PAnP) 2(CH3CN)4](PF6)2, trinuclear [Ag3(μ-PAnP)3⊃BF4]-(BF 4)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. © 2006 American Chemical Society.