Abstract
A pair of three-dimensional divalent copper pyromellitate (1,2,4,5-benzene-tetracarboxylate, pyro) coordination polymers containing 4,4′-dipyridylamine (dpa) was hydrothermally prepared and structurally characterized by single-crystal X-ray diffraction. The higher-temperature phase {[H2dpa][Cu3(pyro)2(H2O)3]·2.5H2O}n (1) displays an acentric 3-D 4,4,6-connected anionic network with (445.6)(5482)(44546374) topology, featuring {Cu2(OCO)4} paddlewheel dimers and isolated copper ions. Charge-balancing H2dpa cations are embedded in incipient voids. Prepared at lower temperature, {[Cu3(pyro)2(dpa)2(dpaH)2]·3H2O}n (2) manifests a 3-D 4,4,4-connected neutral network with uncommon (4264)4(6482) frl topology based on {Cu3(OCO)2} linear trimers. Antiferromagnetic coupling (J=–82(5)cm–1) was observed within the {Cu2(OCO)4} dimeric units in 1, while weak ferromagnetic coupling (J=1.0(4)cm–1) was evident for the {Cu3(OCO)2} linear trimers in 2. Thermal degradation behavior of these new materials is also presented.
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