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首页> 外文期刊>Bulletin of the Chemical Society of Japan >Multi-Dimensional Crystal Structures and Unique Solid-State Properties of Heterocyclic Thiazyl Radicals and Related Materials
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Multi-Dimensional Crystal Structures and Unique Solid-State Properties of Heterocyclic Thiazyl Radicals and Related Materials

机译：杂环噻唑基和相关材料的多维晶体结构和独特的固态性质

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摘要

The crystal structures and magnetic properties of heterocyclic thiazyl radicals and related materials have been examined.TTTA (=1,3,5-trithia-2,4,6-triazapentalenyl) exhibited a first-order phase transition between a paramagnetic high-temperature (HT) phase and a diamagnetic low-temperature (LT) phase,with a wide thermal hysteresis loop over the temperature range 230-305 K.The phase control of TTTA was achieved by pressure and by light irradiation.BDTA (=1,3,2-benzodithiazolyl) also exhibited a diamagnetic-paramagnetic phase transition above room temperature.However,fresh samples always exhibited a superheating of the LT phase that resulted in a double melting (melt-recrystal-lization-melt process) and supercooling of the HT phase,which in turn led to an antiferromagnetic ordering at 11 K.The molecular compounds of thiazyl radicals were prepared;TTTA formed a coordination polymer structure in the TTTA centre dot [Cu(hfac)_2 (=bis(hexafluoroacetylacetonato)-copper(II))] crystal,where a ferromagnetic coupling was found between the organic and inorganic species.The cation radical salts,[BBDTA (=benzo[1,2-d:4,5-d']bis[1,3,2]dithiazole)]centre dot MCl_4 (M = Ga and Fe),exhibited ferromagnetic ordering at 7 K and ferrimagnetic ordering at 44 K after evaporation of crystal solvents.We also grew crystals of M-TTDPz (TTDPz = tetrakis(thiadiazole)porphyrazine and M = H_2,Fe,Co,Ni,Cu,and Zn) and performed their structural analyses.Their crystal structures were found to depend strongly on the central metal ion and could be classified into three forms:alpha,beta,and gamma.
机译：研究了杂环噻唑基和相关材料的晶体结构和磁性，TTTA（= 1,3,5-trithia-2,4,6-triazapentalenyl）在顺磁高温（ HT）相和抗磁性低温（LT）相，在230-305 K的温度范围内具有宽的热滞回线.TTTA的相控是通过压力和光照射实现的.BDTA（= 1,3， 2-苯并二噻唑基）在室温以上也表现出反磁性-顺磁性相变，但是新鲜样品总是表现出LT相的过热，从而导致双重熔化（熔融-重结晶-熔化-熔融过程）和HT相的过冷制备了噻唑基自由基的分子化合物; TTTA在TTTA中心点[Cu（hfac）_2（=双（六氟乙酰丙酮））-铜（II）上形成配位聚合物结构）]晶体，其中在有机物和无机物之间发现了铁磁耦合。阳离子自由基盐，[BBDTA（=苯并[1,2-d：4,5-d']双[1,3,2]二噻唑）]中心点MCl_4（ M = Ga和Fe），在结晶溶剂蒸发后表现出7 K的铁磁有序和44 K的亚铁磁有序。我们还生长了M-TTDPz（TTDPz =四（噻二唑）卟啉和M = H_2，Fe，Co， Ni，Cu和Zn）并进行结构分析。发现它们的晶体结构强烈依赖于中心金属离子，可以分为三种形式：α，β和γ。

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