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)]·0.875H₂O}_<i>n</i> (<b>1</b>) and {[Cd­(d-cmph)­(dpa)­(Hdpa)]­ClO₄}_<i>n</i> (<b>1a</b>) exhibit one-dimensional (1-D) chains with protonated pendant ligands; <b>1</b> possesses sinusoidal chains with a “wavelength” of over 67 Å. [Zn₂(d-cmph)₂(dpa)­(H₂O)]_<i>n</i> (<b>2</b>) exhibits a two-dimensional (2-D) 3,4-connected binodal net with (5³)₂(5⁴8²) topology. {[Ni­(d-cmph)­(dpa)]·3H₂O}_<i>n</i> (<b>3</b>) and {[M₂(d-cmph)₂(dpa)]·H₂O}_<i>n</i> (M = Co, <b>4</b>; M = Cu, <b>5</b>) manifest three-dimensional (3-D) networks. The nickel derivative has an uncommon 2-fold interpenetrated 4-connected 4²8⁴ <b>lvt</b> topology, while the isostructural cobalt and copper complexes possess 6-connected <b>pcu</b> topologies based on {M₂(OCO)₄} paddlewheel dimers. Complexes <b>1/1a</b> and <b>2</b> undergo visible light emission upon ultraviolet excitation. Variable temperature magnetic susceptibility experiments indicate weak (<i>J</i> = −3.6(2) cm^–1) and strong (<i>J</i> = –202(5) cm^–1) antiferromagnetic coupling for <b>4</b> and <b>5</b>, respectively