Molecular understanding on ultraviolet photolytic degradation of cyano liquid crystal monomers

Cyano liquid crystal monomers (LCMs) are proposed as emerging chemical pollutants with persistent, bioaccumulative, and toxic properties. Herein, five cyano LCMs, including 4-cyano-4'-ethylbiphenyl (2CB), 4-Butyl-4'-cyanobiphenyl (4CB), 4-cyano-4'-ethoxybiphenyl (2OCB), 4-(trans-4-Ethylcyclohexyl)benzonitrile (2CHB) and 4-(trans-4-Vinylcyclohexyl)benzonitrile (2eCHB), were selected to investigate the reaction kinetics and excited state characteristic variations with their molecular structures by ultraviolet (UV) photolysis. Theoretical calculations reveal that the benzene ring, ethoxy and double bond can deeply alter the electron distribution of cyano LCMs. This will affect the exciton separation ability, excitation properties and active sites to electrophilic attack, causing the distinction in photolysis efficiency. Due to the effective charge separation during local excitation (LE) process and the property of being most susceptible to electrophilic attack by ¹O₂ and O₂^•-, 2eCHB with double bond exhibits the largest degradation rate. Conversely, the weakest exciton separation of 2OCB with ethoxy during charge transfer (CT) process limits its subsequent sensitized photolysis process. The molecular orbital and fragment contributions to holes and electrons further deepen the understanding of the excited states charge transfer. This study confirmed that the intrinsic molecular structure, chemical nature and existing sites directly defined the excitation and decomposition activity in the UV photolysis of cyano LCMs.