Design and Synthesis of Photofunctional Organic and Inorganic Composite Crystals

蒙脱土黏土矿物通过静电相互作用在其夹层中容纳各种有机阳离子客体。本课题通过将SPO染料与锌离子交换蒙脱土中的酚氧络合形成Zn阳离子，将SPO染料插入到蒙脱土中，研究SPO染料的光致变色性能。用SPO （50mol%）和氯化锌（500mol%）的混合物处理疏水蒙脱土插层六基三甲基铵离子，室温搅拌40h。用300-400nm的紫外光照射复合材料。结果与讨论。观察到嵌入复合材料以彩色开放结构的形式被吸收，在黑暗条件下稳定数天。然而，这种开放形式在450nm光的照射下逐渐转变为相应的封闭形式。在插层过程中，虽然有紫外光照射，但照射时间对SPO的吸附程度影响不大。此外，SPO的锌配合物在粘土中被紧紧地保持，因此锌与粘土中间层的相互作用很强。综上所述，SPO染料是通过络合层有效嵌入蒙脱土中的，其光致变色性质受络合层的控制。

Montmorrilonite clay minerals accommodate various organic cation guests in their interlayers by means of electrostatic interactions. In this project we attempted an intercalation of spirooxadine dyes (SPO) into zinc (II) ion exchanged montmorrilonite clay by complex formation of the Zn cation with phenolic oxygen of SPO dyes to study their photochromic properties.Experiments. Hydrophobic montmorrilonite intercalated hexytrimethylammonium ions was treated with a mixture of SPO (50mol%) and zinc chloride (500mol%) with stirring for 40hrs at room temperature. The resulting composite materials were irradiated with UV light between 300-400nm.The results and Discussion. The intercalated composite was observed to be absorbed in a form of colored open structure, which is stable under dark condition for several days. However, irradiation of this open form with 450nm light gradually changes into the corresponding closed form. Though SPO is irradiated by UV light during the intercalation procedures, adsorption degree was little affected by the length of irradiation periods. In addition, the zinc complex of SPO is holded tight in clay, and so the interaction of zinc and clay interlayers is quite strong.In conclusion, SPO dyes is efficiently intercalated in montmorrilonite clay by complex formation and its photochromic nature was controlled by the complex formation.