Preparation of polysilsesquioxanes with hierarchical structures and their functionalization

在本研究中，我们制备了以手性基团和氯化铵为侧链的梯形聚倍半硅氧烷(PSQs)，形成了手性构象和六方堆积结构。这是由手性有机三乙氧基硅烷和3-氨丙基三乙氧基硅烷在盐酸和甲醇的混合溶剂中通过溶胶-凝胶共缩聚实现的。通过1H核磁共振、红外光谱、~(29)Si核磁共振、静态光散射、X射线衍射、振动圆二色谱等手段对产物结构进行了表征。此外，我们还研究了四苯基卟啉、四磺酸等阴离子卟啉的手性聚集体的形成。电子圆二色谱(ECD)和紫外可见光谱(UV-Vis)表明，作为PSQs侧链的TPPS形成了手性H-聚集体。

In this study, we prepared ladder-like polysilsesquioxanes (PSQs) containing chiral and ammonium chloride groups as side-chains, forming chiral conformations and hexagonal stacking structures. This was achieved by sol-gel copolycondensation of chiral organotriethoxysilane and 3-aminopropyltriethoxysilane in a mixed solvent of aqueous hydrochloric acid and methanol. The structures of the resulting products were characterized by 1H NMR, IR, ^29Si NMR, static light scattering (SLS), X-ray diffraction (XRD), vibrational circular dichroism (VCD) measurements. In addition, we investigated the formation of chiral aggregates of anionic porphyrin such as tetraphenylporphine tetrasulfonic acid (TPPS) using the resulting PSQs. The electronic circular dichroism (ECD) and UV-Vis spectra of aqueous mixtures of TPPS/PSQs indicated the formation of chiral H-aggregates of TPPS along the ammonium groups as side-chains of the PSQs.