960化工网
N-heterocyclic amine-directed structures and properties of two Cu(ii) diphosphonates†
Kui-Rong Ma,Feng Ma,Yu-Lan Zhu,Lin-Juan Yu,Xiao-Min Zhao,Yin Yang,Wei-He Duan
Dalton Transactions Pub Date : 08/25/2011 00:00:00 , DOI:10.1039/C1DT10528K
Abstract

By introducing the second organic N-heterocyclic ligands 4′-(4-pyridyl)-4,2′:6′,4′′-terpyridine (pyterpy) and 4,4′-bipyridyl (4,4′-bipy), two examples of Cu(II)-diphosphonates, [Cu3(HL)2(Hpyterpy)2]·2H2O 1 and [Cu4(HL)2(4,4′-bipy)(H2O)5] 2 based on 1-hydroxyethylidenediphosphonic acid (H5L = CH3C(OH)(PO3H2)2), have been hydrothermally obtained and characterized by powder X-ray diffraction, elemental analysis, IR, TG-DSC. The single-crystal X-ray diffractions reveal that compound 1 has a one-dimensional fishbone-like chain constructed by anions [Cu3(HL)22−]n while simultaneously organic cations [Hpyterpy+]n suspending both sides, and compound 2 exhibits two-dimensional inorganic-organic alternate arrangement layer built from 1-D ladder-like inorganic chain with tetranuclear cluster [Cu4O10] via4,4′-bipy linkage. The results of electrochemical measurements indicate half-wave potential of 1 (E1/21 = 1.01 V) is less than that of 2 (E1/22 = 1.20 V), indicating a good D-A system in ICT for 1. Moreover fluorescent measurements reveal that emission intensity of 1 centered at 422 nm is larger than that of 2 emitted at 420 nm, caused by intraligand π*–π emission state of organic N-heterocyclic amine (λex = 233 nm). Magnetism data indicate that compound 1 exhibits ferrimagnetic interactions between metal centers, while compound 2 has antiferromagnetic property.

Graphical abstract: N-heterocyclic amine-directed structures and properties of two Cu(ii) diphosphonates
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