RESUMO
Humidity-responsive ON/OFF switching of CO2 inclusion, associated with cooperative structural changes of heterogeneous cavities in crystalline peptide NiII macrocycles, 1â NO3 , is demonstrated. The structural transformation between an "open form" and a "closed form" was caused by reversible water uptake into one of the cavities. The adsorption behavior of CO2 was studied with and without water vapor, combined with gas-composition analysis by using gas chromatography. The studies revealed that the open form of 1â NO3 adsorbs CO2 gas up to 34â g mol-1 , whereas the closed form adsorbs only a negligible amount of CO2 gas. Also, structural studies (X-ray and IR spectroscopies) and investigation of water-content dependence of CO2 adsorption revealed that the switching of gas inclusion occurred abruptly over a narrow range of water-vapor pressure and was caused by the cooperative opening of vacant space to give the open form due to the structural transformation by water uptake.
RESUMO
Crystalline peptide Ni(ii)-macrocycles (BF4(-) salt) exhibited moderate CO2 gas adsorption (ca. 6-7 CO2 molecules per macrocycle) into very narrow cavities (narrowest part <2 Å), accompanied by the expansion of the cavities. The BF4(-) salt demonstrated selective uptake of CO2 gas in preference to CH4 and N2 gases.