Rational Design of Supramolecular Gridlike Layers and Zigzag Chains through a Unique Interplay of d10−d10 and π−π Stacking Interactions

Abstract

Six new Cu(II)−M(I) complexes (M = Ag, Au) were synthesized to illustrate the role of the convolution of d10−d10 (aurophilic or argentophilic) and π−π stacking interactions in sustaining supramolecular solid-state architectures. Two types of supramolecular synthons are involved: a rectangular one, based on the aurophilic (argentophilic) interactions between the [M(CN)2]- spacers, and a linear one, relying upon π−π contacts between the aromatic ligands. The reactions between [Cu(acac)(BB)(H2O)](ClO4) complexes and K[M(CN)2] in a 2:1 molar ratio (BB = 2,2‘-bipyridine; 1,10-phenanthroline) lead to the following heterotrinuclear complexes: [{Cu(acac)(bipy)}2{Au(CN)2}](ClO4)·0.5CH3CN (1), [{Cu(acac)(bipy)}2{Ag(CN)2}](ClO4)·0.5CH3CN (2), [{Cu(acac)(phen)}2{Ag(CN)2}](ClO4) (3), and [{Cu(acac)(phen)}2{Au(CN)2}](ClO4) (4). The recrystallization of 4 from acetonitrile affords [{Cu(acac)(phen)}2{Au(CN)2}](ClO4)·0.5CH3CN (5), which is isomorphous with the compounds 1−3. By reacting [Cu(sal)(bipy)]ClO4 with K[Ag(CN)...