Coordination frameworks containing the pyrimidin-4-olate ligand.: Synthesis, thermal, magnetic, and ab initio XRPD structural characterization of nickel and zinc derivatives

被引:20
作者
Barea, E
Navarro, JAR
Salas, JM
Masclocchi, N
Galli, S
Sironi, A
机构
[1] Univ Granada, Dept Quim Inorgan, E-18071 Granada, Spain
[2] Ist Nazl Fis Mat, I-20133 Milan, Italy
[3] CNR, Ist Sci & Tecnol Mol, I-20133 Milan, Italy
[4] Univ Milan, Dipartimento Chim Strutturale & Stereochim Inorga, I-20133 Milan, Italy
[5] Univ Insubria, Dipartimento Sci Chim Fis & Matemat, I-22100 Como, Italy
关键词
D O I
10.1021/ic0351287
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Extended coordination frameworks containing the pyrimidin-4-olate ligand (4-pymo) and Zn(II) and Ni(II) metal ions have been obtained by solid state reactions and have been fully characterized by spectroscopic, thermal, and magnetic measurements and by ab initio XRPD. The reaction of ZnO and 4-Hpymo at 140 degreesC gives a solid microcrystalline phase, Zn(4-PYMO)(2) (1). Its 3D framework contains Zn(II) centers linked by 4-pymo ligands acting in two different coordination modes, namely, the N,N'- and the N,O-exo-bidentate ones, which result in a pseuclotetrahedral ZnN3O chromophore. Thermal treatment of the "molecular' Ni(4-pymo)(2)(H2O)(4) complex (2) above 140 degreesC gives an anhydrous amorphous material analyzing as Ni(4-PYMO)(2) (3a). Further heating of this material above 388 degreesC results in the formation of the microcrystalline layered Ni(4-PYMO)(2) species (3b), in which Ni(II) centers are bridged by N,O-exo-bidentate 4-pymo ligands (assisted by longer Ni...N contacts). The thermal dependence of the magnetic susceptibility has been studied for the paramagnetic species 2 and 3a. 2 shows a weak antiferromagnetic interaction [J = -0.313(5) cm(-1)] transmitted through the multiple H-bonding interactions between the exocyclic pyrimidine and water oxygen atoms coordinated to the metal centers. 3a behaves as a 2D Heisenberg antiferromagnet with J = -4.11(3) cm(-1).
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页码:473 / 481
页数:9
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