Serendipity and Rational Design of One-Dimensional Doubly Stranded Chains with Nanometric Cavities Based on AgI Coordination Chemistry

Abstract

Spontaneous and cooperative self-assembly processes allowed the preparation of two complexes {[AgL12][X]}n [X = CF3SO3, (3a); X = BF4, (3b)] in quantitative yields, identified as 1-D doubly stranded chains. The X-ray molecular structures of 3a,b are reported. Complexes 3a,b are isostructural and crystallize in the triclinic unit cell. The structures of 3a and 3b show the formation of a one-dimensional coordination polymer exhibiting as an outstanding feature the presence of infinite chained metallomacrocycles with nanometric cavities. Interestingly, NMR spectroscopy and electrospray mass spectrometry suggest that the identified elemental sub-unit [AgL12]+ is the key building block which self-assembles to provide the inorganic polymers 3a,b. The effect of weakly coordinating counteranions and the assembling ligand L1 on the supermolecule design are presented and discussed. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)