Structural Diversity in Luminescent Three-Dimensional Cadmium Aliphatic Dicarboxylate Coordination Polymers Incorporating 4,4 '-Dipyridylamine: Interpenetrated, Non-Interpenetrated, and Self-Penetrated Networks

摘要

Three cadmium coordination polymers incorporating both a flexible aliphatic alpha,omega-dicarboxylate and the hydrogen-bonding capable diimine 4,4'-dipyridylamine (dpa) have been prepared and structurally characterized. {[Cd(adp)(dpa)]}(n) (1, adp = adipate) adopts a doubly interpenetrated decorated primitive cubic three-dimensional (3D) coordination polymer network. {[Cd-7(pim)(6)(dpa)(6)(H2O)(2)](ClO4)(2) center dot 6H(2)O}(n) (2, pim = pimelate) exhibits a complex (8,10)-connected binodal self-penetrated cationic 3D network with (3(8)4(14)5(4)6(2))(3(10)4(18)5(14)6(3)) topology constructed from the linkage of oligomeric {Cd-7(dpa)(6)(H2O)(2)}(14+) secondary building units through pimelate ligands with different conformations. To the best of our knowledge, this is the highest-connected binodal self-penetrated lattice reported to date. Extending the length of the alpha,omega-dicarboxylate resulted in a CdSO4-type (6(5)8 topology) 4-connected 3D network in {[Cd(sub)(dpa)] center dot 2H(2)O}(n) (3, sub = suberate). The length of the polymethylene unit within the dicarboxylate ligand, the coordination preferences at cadmium and anion inclusion, to-ether with dpa-mediated hydrogen bonding, exert a cooperative structure directing effect in this system. All three coordination polymers undergo blue-violet luminescence under ultraviolet irradiation.