Molecular architecture of inorganic complex multilayers based on surface coordination chemistry

表面介观分子结构的设计和制造是未来材料科学的一个重要和有吸引力的领域。为了构建二维介观分子结构，我们采用了两种方法在表面进行分子制备；一种是金的自组装单层（SAM）方法，另一种是Langmuir-Blodgett （LB）技术，这两种技术都使用配位键作为分子模块之间的化学“粘合剂”。合成了基于三齿2,6-二（苯并咪唑-2-基）吡啶（L18）及其Ru配合物[Ru(L18)(X)]^<n+>（X =三齿或tin单齿配体）的新型锚定或两亲性配体，并将其作为分子结构单元。在空气-水界面，含有2,2′：6′，2′-三吡啶-4-膦酸盐（X= tpy-PO_3H）的Ru配合物的表面压力-面积（pi-A）等温线与亚相条件(pH或金属离子（Zn^<2+>, Cd^<2+>和Mn^<2+>）有很强的依赖性。原子力显微镜（AFM）图像显示，在云母衬底上转移LB膜的表面形貌呈现相对规则的条形结构。在X = 2,3,5,6-四akis(2'-pyridyl)pyrazine的情况下，观察到圆形结构域结构。此外，在原位紫外光谱测量中，通过500 nm左右的MLCT波段强度证实了Ru配合物分子在空气-水界面的分子取向。我们发现，500 nm左右的MLCT波段的强度随着pH的变化或亚相的金属配位而改变。

The design and fabrication of meso molecular structures on the surface is one of the important and attractive areas in the future material science. In order to construct the meso molecular structures in two dimensions, we employed two methodologies for molecular fabrication on the surface ; one is the self-assembled monolayer (SAM) method on gold, and the other is Langmuir-Blodgett (LB) technique, in both of which coordination bond is used for a chemical "glue" between the molecular module. New anchoring or amphiphilic ligands based on tridentate 2,6-bis(benzimidazol-2-yl)pyridine(L18) and their Ru complexes, [Ru(L18)(X)]^<n+>(X = tridentate or tins monodentate ligand) were synthesized and used as a molecular building block. At the air-water interface, surface pressure-area (pi-A) isotherms showed strong dependence on the subphase condition such as pH or metal ion (Zn^<2+>, Cd^<2+> and Mn^<2+>) for Ru complex containing 2,2' : 6", 2'-terpyridine-4-phosphonate(X= tpy-PO_3H). The surface morphology of the transferred LB films on mica substrates, which was obtained from an AFM image, revealed a relatively regular stripe structure. The surface morphology was also dependent on the auxiliary ligand X.In the case of X = 2,3,5,6-tetrakis(2'-pyridyl)pyrazine, a circular domain structure was observed.Furthermore, the molecular orientation of the Ru complex molecules at the air-water interface was proved by the intensity of MLCT band around 500 nm in in-situ UV spectral measurements. We found that the intensity of MLCT band around 500 nm was changed by pH change or metal coordination from the subphase.