Diverse Topologies in Chiral Divalent Metal Camphorate Coordination Polymers Containing 4,4′-Dipyridylamine

Hydrothermal synthesis has afforded six chiral divalent metal coordination polymers containing D-camphorate (D-cmph) and 4,4'-dipyridylamine (dpa) ligands, whose topologies depend largely on metal coordination geometry preference. Both cadmium derivatives {[Cd(dpa)(D-cmphH)(2)(H2O)]center dot 0.875H(2)O}(n) (1) and {[Cd(D-cmph)(dpa)(Hdpa)]ClO4}(n) (1a) exhibit one-dimensional (1-D) chains with protonated pendant ligands; 1 possesses sinusoidal chains with a "wavelength" of over 67 angstrom. [Zn-2(D-cmph)(2)(dpa)(H2O)] (2) exhibits a two-dimensional (2-D) 3,4-connected binodal net with (5(3))(2)(5(4)8(2)) topology. {[Ni(D-cmph)(dpa)]center dot 3H(2)O}(n) (3) and {[M-2(D-cmph)(2)(dpa)]center dot H2O}(n) (M = Co, 4; M = Cu, 5) manifest three-dimensional (3-D) networks. The nickel derivative has an uncommon 2-fold interpenetrated 4-connected 4(2)8(4) lvt topology, while the isostructural cobalt and copper complexes possess 6-connected pcu topologies based on {M-2(OCO)(4)} paddlewheel dimers. Complexes 1/1a and 2 undergo visible light emission upon ultraviolet excitation. Variable temperature magnetic susceptibility experiments indicate weak (J = -3.6(2) cm(-1)) and strong (J = -202(5) cm(-1)) antiferromagnetic coupling for 4 and 5, respectively.