Quantification of Photocyclization Kinetics and Its Temperature Dependence in a Cofacial Metal–Organic Framework

As complex materials are widely used in emerging technologies for environmental and energy applications, it is important to be able to quantify their stimuli-response behaviors. Light is a useful stimulus to modulate multifunctional electrochemical, magnetic, optical, and structural properties in metal–organic frameworks (MOFs); however, the underlying mechanisms and kinetics of light-induced structural changes are not well understood. Herein, a double [2 + 2] photocyclization in photoactive [Cd2(stil)2(Py2TTF)2] (stil2– = 4,4′-stilbenedicarboxylic acid, Py2TTF = 2,6-bis(4′-pyridyl)-tetrathiafulvalene) offers a powerful platform to quantitatively probe solid-state photocyclization kinetics. Variable-temperature Raman spectroscopy revealed a nonlinear temperature dependence of these parameters, which could be analyzed using the Johnson–Mehl–Avrami–Kolmogorov (JMAK) kinetic model to yield a maximum rate observed between 0 °C and 20 °C of approximately 0.172 s–1. These results offer the first example of the quantification of the photocyclization kinetics in a MOF. Density functional theory (DFT) calculations support a singlet reaction mechanism for the double [2 + 2] photocyclization, which is facilitated by the cofacial alignment of Py2TTF ligands. Establishing mechanistic and kinetic models that can be applied to multistimuli-responsive materials provides a powerful platform for their future design for applications in sensing, switching, and molecular separations.