Coordination Synergy between Iridium Photosensitizers and Metal Nanoclusters Leading to Enhanced CO2 Cycloaddition under Mild Conditions

The achievement of photocatalytic CO2 and epoxide cycloaddition under mild conditions such as room temperature and atmospheric pressure is important for green chemistry, which can be achieved by developing coordination synergies between catalysts and photosensitizers. In this context, we exploit the use of coordinate bonds to connect pyridine-appended iridium photosensitizers and catalysts for CO2 cycloaddition, which is systematically demonstrated by 1H nuclear magnetic resonance titration and X-ray photoelectron spectroscopic measurements. It is shown that the hybrid Ir­(Cltpy)2/Mn2Cd4 photocatalytic system with coordination synergy exhibits excellent catalytic performance (yield ≈ 98.2%), which is 3.75 times higher than that of the comparative Ir­(Cltpy-Ph)2/Mn2Cd4 system without coordination synergy (yield ≈ 26.2%), under mild conditions. The coordination between the Mn2Cd4 catalyst and the Ir­(Cltpy)2 photosensitizer enhances the light absorption and photoresponse properties of the Mn2Cd4 catalyst. This has been confirmed through transient photocurrent, electrochemical impedance, and electron paramagnetic tests. Consequently, the efficiency of cycloaddition was enhanced by utilizing mild conditions.