Hybrid
metal-organic frameworks (MOFs) with core/shell-like hierarchical structure comprised of
zirconium metal and
porphyrin (e.g., TPP) and its isomer, N-confused
porphyrin (NCP), were synthesized through a seed-mediated reaction. The hierarchical structures of hybrid MOFs were characterized by the microscopic image analyses (e.g., scanning electron microscope (SEM), energy dispersive X-ray (EDX) spectrometry, and confocal
laser scanning microscope (CLSM)). Taking advantage of the intrinsic light-harvesting properties of the
porphyrin dye and the N-confused isomer, changing the core/shell layer structures of hybrid MOFs allows for tuning of the visible-to-near-infrared (NIR) absorption/emission characters, excited-state energy migrations, and
photosensitization capabilities. The Förster energy transfer event occurring in the bulk MOF samples by photoexcitation enabled us to control the photoinduced
singlet oxygen generation through the comprehensive light-harvesting ability of these hybrid porphyrinic MOFs. Therefore, implementation of a precisely designed
porphyrin "substitute" into the MOF-based materials indeed provides a new mimic of the photosynthetic pigment system and should be potentially applicable for solar-light-driven devices.