Wavelength-Dependent Energy and Charge Transfer in MOF: A Step toward Artificial Porous Light-Harvesting System.

Chromophore assemblies within well-defined porous coordination polymers, such as metal-organic frameworks (MOFs), can emulate the functionality of the antenna rings of chlorophylls in light-harvesting complexes (LHCs). The chemical, electronic, and structural diversities define MOFs as a promising platform where photogenerated excitons can be displaced to redox catalysts similar to the reaction center of the LHC. The precise positioning of the pigments and complementary redox units enables us to understand the charge/energy-transfer process within these crystalline solid compositions. In this study, we postsynthetically anchored tetraphenylporphyrinato zinc(II) (TPPZn)-derived complementary pigment within the 1D pores of 1,3,6,8-tetrakis(p-benzoicacid)pyrene (H4TBAPy)-derived NU-1000 MOF to form a high-density donor-acceptor system. The ground- and excited-state redox potentials of the donor and acceptor were chosen to facilitate an energy transfer (EnT) from the excited MOF (i.e., NU-1000*) to TPPZn and a charge transfer (CT) from excited porphyrin (i.e., TPPZn*). Thus, the processes depend on the excitation wavelength. The energy transfer process was spectroscopically probed by excitation-emission mapping: MOF emission was completely quenched at 460 nm, where the pyrene-centered emission was expected. Instead, the excited MOF efficiently transfers the energy to manifest a TPPZn-centered emission at 670 nm (kEnT ≈ 4.7 × 1011 s-1). The excited TPPZn pigment, with a neighboring TBAPy linker, forms an artificial "special-pair"-like system driving the charge-separation process (kCT = 1.2 × 1010 s-1). The findings demonstrate a synthetic MOF-based artificial LHC system where their well-defined structure will open up new possibilities as the separated charge can hop along the 1D pore channel for further mechanistic understanding and future developments.