Packing motifs and magneto-structural correlations in crystal structures of metallo-tetrakis(1,2,5-thiadiazole)porphyrazine series, MTTDPz (M=H2, Fe, Co, Ni, Cu, Zn).
Packing motifs and magneto-structural correlations in crystal structures of metallo-tetrakis(1,2,5-thiadiazole)porphyrazine series, MTTDPz (M=H2, Fe, Co, Ni, Cu, Zn).
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DOI：
10.1002/chem.200400394
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发表时间：
2004-10
期刊：
影响因子：
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通讯作者：
Yosuke Suzuki;M. Fujimori;Hirofumi Yoshikawa;K. Awaga
中科院分区：
文献类型：
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作者：
Yosuke Suzuki;M. Fujimori;Hirofumi Yoshikawa;K. Awaga
用减压升华法生长了四(噻二唑)卟嗪及其相应的金属(II)衍生物MTTDPz(M=H2、Fe、Co、Ni、Cu、Zn)单晶。X-射线晶体分析表明，它们的结构明显依赖于中心金属离子，并且M=Ni和Cu的衍生物表现出多晶性。它们可以分为三种形式，阿尔法、贝塔和伽马。α晶型(M=H2、Ni和Cu)由两个噻二唑环之间的并排接触形成的二维六方紧密堆积组成，而β晶型(M=Fe、Co和Zn)结晶成一维配位聚合物。伽马晶型(M=Ni和Cu)由pi堆积和噻二唑环之间的并排接触形成的梯形结构组成，类似于酞菁的β晶型。虽然MTTDPz系列的晶体结构显示出多维网络结构，但磁性测量显示交换作用相对较弱，可能反映了金属离子之间的较长距离。
Single crystals of tetrakis(thiadiazole)porphyrazine and the corresponding metal(II) derivatives, MTTDPz (M=H2, Fe, Co, Ni, Cu, and Zn) were grown by sublimation under reduced pressure with continuous N2 gas flow. Their structures, obtained by X-ray crystallographic analysis, depend significantly on the central metal ion, and the M=Ni and Cu derivatives exhibit polymorphism. They can be classified into three forms, alpha, beta, and gamma. The alpha form (M=H2, Ni, and Cu) is composed of two-dimensional hexagonal close packing formed by side-by-side contacts between thiadiazole rings, whereas the beta form (M=Fe, Co, and Zn) crystallizes into a one-dimensional coordination polymer. The gamma form (M=Ni and Cu) consists of a ladder structure caused by pi stacking, similar to the beta form of phthalocyanine, and by side-by-side contacts between thiadiazole rings. Although the crystal structures of the MTTDPz series exhibited multi-dimensional network structures, magnetic measurements revealed relatively weak exchange interactions, probably reflecting the long distances between the metal ions.