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- Title
In Situ Tracking of Dynamic NO Capture through a Crystal‐to‐Crystal Transformation from a Gate‐Open‐Type Chain Porous Coordination Polymer to a NO‐Adducted Discrete Isomer.
- Authors
Zhang, Jun; Kosaka, Wataru; Kitagawa, Susumu; Takata, Masaki; Miyasaka, Hitoshi
- Abstract
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 [Ru2II,II] complex [Ru2(2,4,5‐Me3PhCO2)4] (2,4,5‐Me3PhCO2−=2,4,5‐trimethylbenzoate) with the phenazine (phz) linker: [Ru2(2,4,5‐Me3PhCO2)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 [Ru2(2,4,5‐Me3PhCO2)4(NO)2](phz) (1‐NO), involving a post‐synthetic nitrosylation on the [Ru2] 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. In situ techniques: Selective NO capture in a Ru dimer chain porous compound through strong host–guest magnetic/electronic interactions was evaluated multilaterally by using in situ techniques of powder magnetic and permittivity measurements, IR spectroscopy, and X‐ray diffraction. A dynamic change with respect to the NO trapping in pores can be followed, which undergoes a crystal‐to‐crystal transformation from a gate‐opened NO adsorbed form to an NO‐adducted form.
- Subjects
METAL-organic frameworks; SORBENTS; POROUS polymers; NITROGEN oxides emission control; NITROGEN oxides &; the environment; ORGANORUTHENIUM compounds
- Publication
Chemistry - A European Journal, 2019, Vol 25, Issue 12, p3020
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201805833