Synthesis, X-ray Crystal Structure, and Photochromism of a Sandwich-Type Mono-Aluminum Complex Composed of Two Tri-Lacunary α-Dawson-Type Polyoxotungstates
Synthesis, X-ray Crystal Structure, and Photochromism of a Sandwich-Type Mono-Aluminum Complex Composed of Two Tri-Lacunary α-Dawson-Type Polyoxotungstates
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DOI：
10.3390/ma12152383
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发表时间：
2019-08-01
期刊：
影响因子：
3.4
通讯作者：
Nagatani, Shunpei
中科院分区：
文献类型：
--
作者：
Kato, Chika Nozaki;Kato, Daichi;Nagatani, Shunpei
本文描述了由两个三缺位α-Dawson多金属氧酸盐[H14Al(B-α-P2W15O56)(2)](7-)(1)组成的二聚体单铝配合物的合成和分子结构。1，[(n-C4H9)(4)N](7)[H14Al(B-α-P2W15O56)(2)](TBA-1)的合成方法是将K-6[B-α-H3P2W15O59{Al(OH2)}(3)]·14H(2)O的水溶液通过离子交换树脂柱(H+型)，然后加入四丁基溴化铵。通过乙腈/甲醇在25℃下的蒸气扩散，得到了分析纯的无色TBA-1晶体。单晶X射线结构分析表明，六配位的铝离子被夹在两个三缺位的α-Dawson结构单元之间，导致了整体的C-2H对称性。通过元素分析、热重/差热分析、傅立叶变换红外光谱和P-31溶液核磁共振光谱对TBA-1进行了表征。研究了TBA-1在甲醇溶液中的光致变色性能。
The synthesis and molecular structure of a dimeric, mono-aluminum complex composed of two tri-lacunary alpha-Dawson polyoxometalates, [H14Al(B-alpha-P2W15O56)(2)](7-) (1), is described herein. The tetra-n-butylammonium salt of 1, [(n-C4H9)(4)N](7)[H14Al(B-alpha-P2W15O56)(2)] (TBA-1) was prepared by passing an aqueous solution of K-6[B-alpha-H3P2W15O59{Al(OH2)}(3)].14H(2)O through an ion-exchange resin column (H+-form), followed by addition of tetra-n-butylammonium bromide. Analytically pure and colorless crystals of TBA-1 were obtained via vapor diffusion from acetonitrile/methanol at 25 degrees C. Single-crystal X-ray structure analysis revealed that a six-coordinate aluminum ion was sandwiched between two tri-lacunary alpha-Dawson-type units, resulting in an overall C-2h symmetry. The characterization of TBA-1 was accomplished by elemental analyses, thermogravimetric/differential thermal analyses, Fourier-transform infrared spectroscopy, and solution P-31 nuclear magnetic resonance spectroscopy. The photochromic properties of TBA-1 were also characterized in methanol under light irradiation (lambda = 365 nm and >= 400 nm).