Controlled Synthesis of Inorganic Polymers by the Use of Multibilayr Cast Films as Molecular Template.

采用H_2S气体与预组织于铸膜中的CdCl_2-cyclam配合物反应制备了量子级CdS粒子。颗粒大小受双膜组分的化学结构以及基体的物理状态的影响。中性CdS粒子似乎是通过物理吸附质子化cyclam头基团来稳定的，并且双层膜表面不作为可以定义客体结构的模板。另一方面，在双层铵- cdbr_3 ^-复合薄膜中，每4个Cd^<2+>离子中引入一个S，而配位结构没有发生实质性变化，表明形成了新的Cd- br -S簇。卤化铅簇是由铵态铸造膜的反离子与PbBr_4^<2->通过浸渍进行离子交换而形成的。保持规则层状结构的离子交换铸膜比2d交联钙钛矿结构（PbI_4^<2->簇）的波长更短。这表明，PbBr_4^<2->簇的尺寸较小（线状或点状）是由于分子面积与双层铵的不平衡而形成的。

Quantum-sized CdS particles are prepared by reaction of H_2S gas with CdCl_2-cyclam complexes preorganized in cast multibilayr films. The particle size is affected by the chemical structure of the bilayr component as well as by the physical state of the matrix. Neutral CdS particles are stabilized seemingly by physical adsorption of protonated cyclam head groups, and the bilayr surface does not act as a template that can define guest structures. On the other hand, in the case of an ammonium bilayr-CdBr_3^- composite film, one S is introduced per four Cd^<2+> ions without substantial changes in the coordination structure, suggesting the formation of a novel Cd-Br-S cluster.Lead halide clusters are formed by ion exchange of counterions of an ammonium cast film with PbBr_4^<2-> through dipping. The ion-exchanged cast film that maintains the regular layr structure displays electronic absorption at wavelength shorter than that of the 2D-cross-linked perovskite structure(PbI_4^<2-> cluster). This suggests that PbBr_4^<2-> clusters of lesser dimensions(linear of dot-shaped) are formed due to imbalance of the molecular area with that of the ammonium bilayr.