Diiodo-BODIPY Sensitizing of the [Mo<sub>3</sub>S<sub>13</sub>]<sup>2–</sup> Cluster for Noble-Metal-Free Visible-Light-Driven Hydrogen Evolution within a Polyampholytic Matrix
Daniel Costabel, Afshin Nabiyan, Avinash Chettri, Franz Jacobi, Magdalena Heiland, Julien Guthmuller, Stephan Kupfer, Maria Wächtler, Benjamin Dietzek‐Ivanšić, Carsten Streb, Felix H. Schacher, Kalina Peneva
Abstract
We report on a photocatalytic setup that utilizes the organic photosensitizer (PS) diiodo-BODIPY and the non-precious-metal-based hydrogen evolution reaction (HER) catalyst (NH 4 ) 2 [Mo 3 S 13 ] together with a polyampholytic unimolecular matrix poly(dehydroalanine)- graft -poly(ethylene glycol) (PDha- g -PEG) in aqueous media. The system shows exceptionally high performance with turnover numbers (TON > 7300) and turnover frequencies (TOF > 450 h –1 ) that are typical for noble-metal-containing systems. Excited-state absorption spectra reveal the formation of a long-lived triplet state of the PS in both aqueous and organic media. The system is a blueprint for developing noble-metal-free HER in water. Component optimization, e.g., by modification of the meso substituent of the PS and the composition of the HER catalyst, is further possible.