Trans Influence across a Metal–Metal Bond of a Paddle-Wheel Unit on Interaction with Gases in a Metal–Organic Framework

Metal–organic frameworks (MOFs) are known as promising adsorbent materials that can recognize gases specifically. In the frameworks, gases favor interacting with specific binding sites such as open metal sites (OMSs), which can consist of various metals and show characteristic adsorption properties. A recently reported framework possessing OMSs of rhodium paddle-wheel (Rh-PW) showed distinct adsorption properties between NO and CO. We investigated theoretically the reasons for stronger NO binding to the Rh-PW and different adsorption amounts between NO and CO using Rh-PW cluster models, as well as the frequently reported Cu-PW for comparison. We also analyzed the cases of CO2 and N2, which are often used to probe functions of MOFs. We observed an increase in binding energy of NO at the second adduction of NO. On the basis of energy decomposition analysis, we found that Rh–NO bond formation inducing a trans influence is important for the stronger binding than with CO. Furthermore, we proposed a reason for twice the adsorption amount of NO than CO. The results are consistent with experimental observations, giving us insight into design functions of MOFs by selecting metal species.