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

Abstract

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)]·0.875H2O}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 Å. [Zn2(d-cmph)2(dpa)(H2O)]n (2) exhibits a two-dimensional (2-D) 3,4-connected binodal net with (53)2(5482) topology. {[Ni(d-cmph)(dpa)]·3H2O}n (3) and {[M2(d-cmph)2(dpa)]·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 4284lvt topology, while the isostructural cobalt and copper complexes possess 6-connected pcu topologies based on {M2(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.