Coordination Copolymerization Mediated by Zn4O(CO2R)6 Metal Clusters: a Balancing Act between Statistics and Geometry

Isolated successes of coordination copolymerization for the production of microporous coordination polymers (MCPs) have been reported recently; the logic for this synthetic approach has not been established nor have the key features of the synthetic conditions needed to generalize the method. Here, we establish guidelines for application of the copolymerization technique by exploring coordination modes and report, in addition to details on two previous coordination copolymers with exceptional properties, three new MCPs: UMCM-3 (Zn4O(2,5-thiophenedicaboxylate)(1.2)(1,3,5-tris(4-carboxyphenyl)benzene)(1.2)), UMCM-4 (Zn4O(1,4-benzenedicarboxylate)(3/2)(4,4',4 ''-tricarboxytriphenylamine)), and UMCM-5 (Zn4O(1,4-naphthalenedicarboxylate)(1,3,5-tris(4-carboxyphenyl)benzene)(4/3)). The MCPs prepared by the copolymerization technique demonstrate Brunauer-Emmett-Teller (BET) surface areas between 3500-5200 m(2)/g and high pore volumes (1.64-2.37 cm(3)/g). In addition, the alignment of poly(3-hexylthiophene) within mesoporous channels of UMCM-1 is reported as a demonstration of the unique properties of these hosts.