Giant Negative Linear Compressibility, Isosymmetric Phase Transition, and Breathing Effect in a 3D Covalent Organic Framework

A set of remarkable piezo-mechanical properties, including isosymmetric phase transition, negative linear compressibility (NLC), and a breathing effect in a three-dimensional covalent organic framework (NPN-3), was uncovered using density functional theory. The pressure-induced first-order phase transition observed between 0.9 and 1 GPa is isosymmetric and irreversible. NPN-3 shows giant NLC along the c-axis (Kc = 42.04 TPa–1) prior to the phase transition. The high-density NPN-3-hd obtained as a result of the phase transition shows an exciting phase transition from a closed pore to an open pore under hydrostatic tensile pressure, similar to the breathing effect. These extraordinary piezo-mechanical attributes within NPN-3 can be attributed to the diamondoid (dia) topology, which is commonly found within flexible MOFs and COFs. Additionally, the remarkable adaptability of the tetraphenyl adamantane monomer to distinct conformations under pressure can be seen in these properties. These findings underscore the potential utility of COFs as materials for piezo-mechanical sensors and serve as a source of inspiration for further exploration into the intricate mechanical behaviors of COFs.