Unexpected Photodriven Linker-to-Node Hole Transfer in a Zirconium-Based Metal-Organic Framework.

Zr(μ-O)(μ-OH) node cores are indispensable building blocks for almost all zirconium-based metal-organic frameworks. Consistent with the insulating nature of zirconia, they are generally considered electronically inert. Contrasting this viewpoint, we present spectral measurements and calculations indicating that emission from photoexcited NU-601, a six-connected Zr-based MOF, comes from both linker-centric locally excited and linker-to-node charge-transfer (CT) states. The CT state originates from a hole transfer process enabled by favorable energy alignment of the HOMOs of the node and linker. This alignment can be manipulated by changing the pH of the medium, which alters the protonation state of multiple oxy groups on the Zr-node. Thus, the acid-base chemistry of the node has a direct effect on the photophysics of the MOF following linker-localized electronic excitation. These new findings open opportunities to understand and exploit, for energy conversion, unconventional mechanisms of exciton formation and transport in MOFs.