Design and Synthesis of Photofunctional Organic and Inorganic Composite Crystals

蒙脱石粘土矿物通过静电作用在其层间容纳各种有机阳离子客体。在本项目中，我们尝试通过锌离子与酚氧形成络合物，将螺恶烷染料(SPO)插层到锌离子交换蒙脱石粘土中，以研究其光致变色性能。将疏水蒙脱土插层到己三甲铵离子上，用50mol%的SPO和500mol%的氯化锌的混合物在室温下搅拌40h。用300-400 nm的紫外光照射得到的复合材料。结果和讨论。观察到插层复合材料以有色开放结构的形式被吸收，该结构在黑暗条件下稳定数天。然而，用450 nm光照射这种开放形式逐渐转变为相应的封闭形式。虽然在插层过程中SPO受到紫外光的照射，但光照时间的长短对SPO的吸附程度影响不大。此外，由于SPO的锌络合物在粘土中结合紧密，因此锌与粘土之间的相互作用很强。因此，SPO染料以络合物的形式有效地插层到蒙脱石粘土中，其光致变色性质受络合物的形成控制。

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.