Functional transformation of four-bladed rylene propellers utilizing non-metal and d8 metal core shifting strategy: significant impact on photovoltaic performance and electrocatalytic hydrogen evolution activity†
Two kinds of four-bladed perylene diimide (PDI) propellers with d8 metal and non-metal cores are efficiently synthesized. The Ni-PDI, Pd-PDI, and Pt-PDI propellers, equipped with d8 metal cores, have two absorption bands at 350–650 nm and 780–1200 nm with deep LUMO levels of −4.40 eV to −4.51 eV. The TTF-PDI, QU-PDI, and PH-PDI propellers with non-metal cores have only one absorption band at 350–650 nm with upshifted LUMO levels. Interestingly, the organic photovoltaic (OPV) results show that reducing the intramolecular charge traps between the blade and core subunits of the PDI propellers can effectively improve the power conversion efficiency (PCE). The device based on the QU-PDI acceptor exhibits a PCE that is up to more than 300 times higher (9.33%) than that of the d8 metal core PDI propellers (Pd-PDI, PCE = 0.03%), which is one of the best photovoltaic performances with an excellent fill factor (FF = 71.8%) exhibited by PDI-derivative acceptors. Conversely, the electro-catalytic H2 evolution activity of Pt-PDI (current destiny = 10.00 mA cm−2 at −0.377 V), which exhibited a record performance for PDI-based catalysts to date, is up to 1000 times greater than that of the non-metal core PDI propellers (QU-PDI, 0.01 mA cm−2 at −0.377 V). Our results indicate that both highly efficient OPV and electrochemical H2 evolution catalysts can be achieved via the rational functionalization of PDI propellers with non-metal and d8 metal cores.