Boosting Photoelectric Conductivity in Porphyrin-Based MOFs Incorporating C₆₀

Electronic structure calculations show that guest C₆₀ in the porphyrin-containing metal organic frameworks Zn₂(TCPB)(DA-ZnP) (DA-MOF; H₄TCPB = 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, DA-ZnP = [5,15-bis[(4-pyridyl)ethynyl]-10,20-diphenylporphinato]zinc(II)) and Zn₂(TCPB)(F-ZnP) (F-MOF; F-ZnP = [5,15-di(4-pyridyl)-10,20-bis(pentafluorophenyl)porphinato]zinc(II)) engenders high photoelectrical conductivity due to efficient donor-acceptor charge-transfer (CT) interactions. Structural modifications at the meso position of the porphyrin influence the preferred positions of C₆₀ within the frameworks, giving rise to host-guest interactions with different anisotropic structural, electronic, and optoelectronic properties. A preferred slipped-parallel Ï-stacked interaction of C₆₀ that is predicted for NH₂-substituted DA-MOF and F-MOF fosters strong CT transitions and lowers band gaps by 1.0 eV compared to the pristine DA-MOF and F-MOF. Hopping rates computed using Marcus theory are found to be anisotropic and accelerated by multiple orders of magnitude across Ï-stacked interfaces created by C₆₀ incorporation, a consequence of strong electronic coupling between initial and final diabatic states. Calculations indicate that photoinduced electron transfer, as well as direct CT from porphyrin to C₆₀ upon irradiation, triggers a charge separation process that leads to the formation of what should be long-lived electron-trapped states at the heterojunctions. Design principles revealed here for the control of photophysical and electron-transfer processes will be useful for constructing new MOF-derived visible- A nd infrared-based optoelectronics.