Hierarchical Self-Assembly of Superlattice Hybrids Consisting of Periodic and Alternating Cores of Porphyrin Molecules Separated by Nanoscale Silica Walls

Molecularly engineered superlattice hybrids consisting of periodic and alternating cores of porphyrin molecules separated by nanoscale silica walls were synthesized through a one-step organic inorganic hierarchical self-assembly approach. The self-assembly process not only could lock both porphyrin and inorganic building blocks into ordered 3D nanostructure but also could allow for the molecular-level controllable organization of porphyrin molecules in the central regions of the silica pore channels, which leads to the formation of porphyrin core-silica wall superlattice hybrids with molecular-scale and mesoscale ordering. It was demonstrated that both the mesostructure and morphology of the hybrids can be finely tailored by turning the cooperative self-assembly process. It is significant that the hybrids show self-assembled optical properties consistent with the orientational arrangement of the porphyrins within periodic nanoscale silica channels. The methodology introduced herein demonstrates high versatility with respect to the self-assembly of optical active macrocycles into highly ordered superlattice hybrid architectures.