TY - JOUR
T1 - 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
AU - Zhang, Jun
AU - Kosaka, Wataru
AU - Kitagawa, Susumu
AU - Takata, Masaki
AU - Miyasaka, Hitoshi
N1 - Funding Information:
The authors thank Prof. Ryotaro Matsuda (Nagoya University) for his advice on synchrotron X-ray crystallography and in situ IR spectroscopy. This work was supported by a Grant-in-Aid for Scientific Research (Grant Nos. 16H02269, 18K19050, 18K05055) and a Grant-in-Aid for Scientific Research on Innovative Areas (‘p-System Figuration“ Area 2601, No. 17H05137) from the Ministry of Education, Culture, Sports, Science and Technology, Japan, and the E-IMR project. J.Z. is thankful for the JSPS Research Fellowship for Young Scientists (No. 17J02497).
Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/2/26
Y1 - 2019/2/26
N2 - 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.
AB - 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.
KW - electron donors
KW - gate-opening behavior
KW - in situ techniques
KW - porous coordination polymers
KW - selective NO sorption
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U2 - 10.1002/chem.201805833
DO - 10.1002/chem.201805833
M3 - Article
C2 - 30614084
AN - SCOPUS:85061496740
SN - 0947-6539
VL - 25
SP - 3020
EP - 3031
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 12
ER -