Degradation Kinetics of Organic–Inorganic Hybrid Materials from Micro‐Raman Spectroscopy and Density‐Functional Theory: The Case of β‐ZnTe(en)_0.5

Abstract Organic–inorganic hybrid materials often face a stability challenge. β‐ZnTe(en)_0.5, which uniquely has over 15‐year real‐time degradation data, is taken as a prototype structure to demonstrate an accelerated thermal aging method for assessing the intrinsic and ambient‐condition long‐term stability of hybrid materials. Micro‐Raman spectroscopy is used to investigate the thermal degradation of β‐ZnTe(en)_0.5 in a protected condition and in air by monitoring the temperature dependences of the intrinsic and degradation‐product Raman modes. First, to understand the intrinsic degradation mechanism, the transition state of the degradation is identified, then using a density functional theory, the intrinsic energy barrier between the transition state and ground state is calculated to be 1.70 eV, in excellent agreement with the measured thermal degradation barrier of 1.62 eV in N₂ environment. Second, for the ambient‐condition degradation, a reduced thermal activation barrier of 0.92 eV is obtained due to oxidation, corresponding to a projected ambient half‐life of 40 years at room temperature, in general agreement with the experimental observation of no apparent degradation over 15 years. Furthermore, the study reveals a mechanism, conformation distortion enhanced stability, which plays a pivotal role in forming the high kinetic barrier, contributing greatly to the impressive long‐term stability of β‐ZnTe(en)_0.5.