title: N-heterocyclic amine-directed structures and properties of two Cu(II) diphosphonates.
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, [Cu(3)(HL)(2)(Hpyterpy)(2)]·2H(2)O 1 and [Cu(4)(HL)(2)(4,4'-bipy)(H(2)O)(5)] 2 based on 1-hydroxyethylidenediphosphonic acid (H(5)L = CH(3)C(OH)(PO(3)H(2))(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 [Cu(3)(HL)(2)(2-)](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 [Cu(4)O(10)] via 4,4'-bipy linkage. The results of electrochemical measurements indicate half-wave potential of 1 (E(1/2)(1) = 1.01 V) is less than that of 2 (E(1/2)(2) = 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 (λ(ex) = 233 nm). Magnetism data indicate that compound 1 exhibits ferrimagnetic interactions between metal centers, while compound 2 has antiferromagnetic property.
authors.affiliation: Jiangsu Key Laboratory for Chemistry of Low-dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huaian, PR China. kuirongma@163.com
authors.forename: Kui-Rong
authors.initials: KR
authors.lastname: Ma
authors.forename: Feng
authors.initials: F
authors.lastname: Ma
authors.forename: Yu-Lan
authors.initials: YL
authors.lastname: Zhu
authors.forename: Lin-Juan
authors.initials: LJ
authors.lastname: Yu
authors.forename: Xiao-Min
authors.initials: XM
authors.lastname: Zhao
authors.forename: Yin
authors.initials: Y
authors.lastname: Yang
authors.forename: Wei-He
authors.initials: WH
authors.lastname: Duan
mesh_terms: D000588:Amines / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004164:Diphosphonates / Q000737:chemistry*; D004563:Electrochemistry; D006571:Heterocyclic Compounds / Q000737:chemistry*; D008024:Ligands; D008280:Magnetics; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013696:Temperature
chemical_list: D000588:Amines; D004164:Diphosphonates; D006571:Heterocyclic Compounds; D008024:Ligands; D009942:Organometallic Compounds; D003300:Copper