Optimal control of gas adsorption properties in metal–organic frameworks (MOFs) or porous coordination polymers (PCPs) remains a great challenge in the field of materials science. An efficient strategy to capture electron-acceptor-type gas molecules such as nitrogen monooxide (NO) is to use host–guest interactions by utilizing electron-donor-type MOFs/PCPs as host frameworks. Herein, we focus on a highly electron-donating chain compound by using the paddlewheel-type [Ru 2 II,II ] complex [Ru 2 (2,4,5-Me 3 PhCO 2 ) 4 ] (2,4,5-Me 3 PhCO 2 − =2,4,5-trimethylbenzoate) with the phenazine (phz) linker: [Ru 2 (2,4,5-Me 3 PhCO 2 ) 4 (phz)] (1). Compound 1 exhibited a specific gated adsorption for NO under gas pressures greater than 60 kPa at 121 K, which finally resulted in approximately seven molar equivalents being taken up at 100 kPa followed by four molar equivalents remaining under vacuum at 121 K; its Rh isomorph (2) with weaker donation ability was inactive for NO. When the sample of 1⊃4 NO was heated to room temperature, the compound underwent a crystal-to-crystal phase transition to give [Ru 2 (2,4,5-Me 3 PhCO 2 ) 4 (NO) 2 ](phz) (1-NO), involving a post-synthetic nitrosylation on the [Ru 2 ] unit, accompanied by an eventful site-exchange with phz. This drastic event, which is dependent on the NO pressure, temperature, and time, was coherently monitored by using several different in situ techniques, revealing that the stabilization of NO molecules in nanosized pores dynamically and stepwisely occurred with the support of strong electronic/magnetic host–guest interactions.
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