Structural diversity of nanoscale zirconium porphyrin MOFs and their photoactivities and biological performances.

Photoactive MOF-based delivery systems are highly attractive for photodynamic therapy (PDT), but the fundamental interplay among structural parameters and photoactivity and biological properties of these MOFs remains unclear. Herein, porphyrinic MOF isomers (TCPP-MOFs), constructing using the same building blocks into distinct topologies, have been selected as ideal models to understand this problem. Both the intramolecular distances and molecular polarization within TCPP-MOFs isomers collectively contribute to the photoactivity of generating reactive oxygen species. Remarkably, the morphology-determined endocytic pathways and cytotoxicity, as well as good biocompatibility have been confirmed for TCPP-MOF isomers without any chemical modification for the first time. Besides the topology-dependent photoactive regulation, this work also provides in-depth insights into the biological effect from the MOF nanoparticles with controllable structural factors, benefiting further in vivo applications and clinical transformation.