1－苯基－3－甲基－4－（6－氢－4－氨基－5－硫杂－2，3－吡嗪）－吡唑啉酮光致变色超分子化合物的合成、结构与性能

通过1－苯基－3－甲基－4－氯乙酰基－吡唑啉酮－5（PMCP）和氨基硫脲（ TSC）缩合，形成了一种含NNS六元杂环的光致变色化合物（PMCP－TSC）。利用元 素分析，MS，”1H NMR，IR和UV光谱进行了表征。通过紫外可见光谱对它的光致 变色性质进行了研究，测出了光致变色反应的动力学常数。并用X线单晶衍射仪测 定了PMCP－TSC变色后的晶体结构，该晶体属单斜晶系，具有P2_1/c空间群，a = 0.105 10(2) nm, b = 0.150 61(3) nm, c = 0.993 70(10) nm, β = 107.890 (10)°, V = 1.496 9(4) nm~3, Z - 4, D_c = 1.417 Mg/m~3, μ = 0.232 mm~(- 1), F(000) = 672, R = 0.033 4, wR = 0.089 6。结构分析表明：其光致变色现 象是由于它在溶剂与光的共同作用下发生了从醇式到酮式的异构化。同时该化合物 经分子间氢键形成二聚体，又通过甲醇与本体分子之间的氢键使化合物形成具有三 维网络结构的超分子化合物。

Synthesis, Crystal Structure and Photochromism Properties of 1- Phenyl-3-methyl-4-(6-hydro-4-amino-5-sulfo-2,3-pyrazine)-pyrazole-5-one

A novel photochromic compound (PMCP-TSC) containing NNS hexa-atomic heterocycle was obtained by the reaction of 1-phenyl-3-methyl-4- chloroacetyl-pyrazolone-5 with thiosemicarbazine. The compound has been characterized by elemental analysis, MS, ~1H NMR spectra, IR spectrum and X-ray single crystal diffraction. The photochromic properties and photochemical kinetics of PMCP-TSC have been studied by UV spectra under irradiation of 365 nm light. The crystal belongs to monoclinic system with space group P2_1/c. The unit cell parameters are a = 0.105 10 (2) nm, b = 0.150 61(3) nm, c = 0.993 70(10) nm, β = 107.890(10)°, V = 1.496 9(4) nm~3, Z = 4, D_c = 1.417 Mg/m~3, μ = 0.232 mm~(-1), F (000) = 672, R = 0.033 4, wR = 0.089 6. The crystal structure analysis of photocolored product showed that the photochromic phenomenon was due to photoisomerization from enol form to keto form. Three types of hydrogen bonds [N(1)…O(1), N(1)…O(2), O(1)…O(2)] lead to the formation of supramolecular compound with three-dimensional network structure.