Structural and magnetic study of N2, NO, NO2, and SO2 adsorbed within a flexible single-crystal adsorbent of [Rh2(bza)4(pyz)]n.
The crystalline one-dimensional compound, [Rh(II)2(bza)4(pyz)]n (1) (bza = benzoate, pyz = pyrazine) demonstrates gas adsorbency for N2, NO, NO2, and SO2. These gas-inclusion crystal structures were characterized by single-crystal X-ray crystallography as 1 x 1.5 N2 (298 K), 1 x 2.5 N2 (90 K), and 1 x 1.95 NO (90 K) under forcible adsorption conditions and 1 x 2 NO2 (90 K) and 1 x 3 SO2 (90 K) under ambient pressure. Crystal-phase transition to the P1 space group that correlates with gas adsorption was observed under N2, NO, and SO2 conditions. The C2/c space group was observed under NO2 conditions without phase transition. All adsorbed gases were stabilized by the host lattice. In the N2, NO, and SO2 inclusion crystals at 90 K, short interatomic distances within van der Waals contacts were found among the neighboring guest molecules along the channel. The adsorbed NO molecules generated the trans-NO...NO associated dimer with short intermolecular contacts but without the conventional chemical bond. The magnetic susceptibility of the NO inclusion crystal indicated antiferromagnetic interaction between the NO molecules and paramagnetism arising from the NO monomer. The NO2 inclusion crystal structure revealed that the gas molecules were adsorbed in the crystal in dimeric form, N2O4.
Kachi-Terajima
Chihiro
C
International Graduate School of Arts and Sciences, Yokohama City University, 22-2 Seto, Kanazawa-ku, Yokohama 236-0027, Japan.
Akatsuka
Takamasa
T
Kohbara
Masa-aki
MA
Takamizawa
Satoshi
S