TY - JOUR
T1 - Host-Guest Molecular Crystals of Diamino-4,4-bithiazole and Dynamic Molecular Motions via Guest Sorption
AU - Nishiyama, Hiroshi
AU - Takeda, Takashi
AU - Hoshino, Norihisa
AU - Takahashi, Kiyonori
AU - Noro, Shin Ichiro
AU - Nakamura, Takayoshi
AU - Akutagawa, Tomoyuki
N1 - Funding Information:
This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas “π-Figuration” (JP26102007), KAKENHI Kibankenkyu (B) (JP15H03791), and “Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials” from MEXT.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2018/1/3
Y1 - 2018/1/3
N2 - Diamino-4,4-bithiazole (1) formed host-guest binary molecular crystals with various types of organic guest molecules including pyridine (Py), benzonitrile (PhCN), piperidine (Pipe), DMF, THF, 1,4-dioxane (Diox), CH3OH, aniline (Ani), coumarin (Coum), nitrobenzene (PhNO2), hexamethylenetetramine (HMTA), and quinoline (Quino). Single crystal X-ray structural analyses at 100 K revealed the formation of 1·(guest) or 1·(guest)2 crystals. Reversible molecular adsorption-desorption responses were observed with Py, PhCN, Pipe, DMF, and Diox around room temperature as the crystalline powders were heated during the desorption process and exposed to guest vapor during the readsorption process. The adsorption-desorption isotherms of crystalline powders 1 with Diox at 298 K indicated a reversible gate-opening adsorption-desorption process. Although the host-guest molecular crystals 1·(THF)2 and 1·(CH3OH)2 were confirmed by X-ray crystal structural analyses at 100 K, the THF and CH3OH guests were already eliminated at room temperature. Guest desorption processes of crystalline powders 1·(guest)x were not observed in the host-guest molecular crystals with Ani, Coum, PhNO2, HMTA, and Quino after the crystalline powders were heated. A balance of both the dipole moment and vapor pressure of the guest molecules played an essential role to elicit reversible guest sorption. The crystal structures formed on account of double N-H⋯N hydrogen-bonded one-dimensional (1D) chains between the -NH2 group and the ring nitrogen atom of 1, which interacted to form two-dimensional (2D) sheet structures through π-stacking and/or S⋯S interactions. Alternating layers of N-H⋯N hydrogen-bonded herringbone packing of 1 and the guest molecules led to the formation of other types of crystal lattices. The hydrogen-bonding molecular assemblies of 1 demonstrated lattice flexibly via the configuration change in the molecular arrangements according to the boiling point of the guest molecules.
AB - Diamino-4,4-bithiazole (1) formed host-guest binary molecular crystals with various types of organic guest molecules including pyridine (Py), benzonitrile (PhCN), piperidine (Pipe), DMF, THF, 1,4-dioxane (Diox), CH3OH, aniline (Ani), coumarin (Coum), nitrobenzene (PhNO2), hexamethylenetetramine (HMTA), and quinoline (Quino). Single crystal X-ray structural analyses at 100 K revealed the formation of 1·(guest) or 1·(guest)2 crystals. Reversible molecular adsorption-desorption responses were observed with Py, PhCN, Pipe, DMF, and Diox around room temperature as the crystalline powders were heated during the desorption process and exposed to guest vapor during the readsorption process. The adsorption-desorption isotherms of crystalline powders 1 with Diox at 298 K indicated a reversible gate-opening adsorption-desorption process. Although the host-guest molecular crystals 1·(THF)2 and 1·(CH3OH)2 were confirmed by X-ray crystal structural analyses at 100 K, the THF and CH3OH guests were already eliminated at room temperature. Guest desorption processes of crystalline powders 1·(guest)x were not observed in the host-guest molecular crystals with Ani, Coum, PhNO2, HMTA, and Quino after the crystalline powders were heated. A balance of both the dipole moment and vapor pressure of the guest molecules played an essential role to elicit reversible guest sorption. The crystal structures formed on account of double N-H⋯N hydrogen-bonded one-dimensional (1D) chains between the -NH2 group and the ring nitrogen atom of 1, which interacted to form two-dimensional (2D) sheet structures through π-stacking and/or S⋯S interactions. Alternating layers of N-H⋯N hydrogen-bonded herringbone packing of 1 and the guest molecules led to the formation of other types of crystal lattices. The hydrogen-bonding molecular assemblies of 1 demonstrated lattice flexibly via the configuration change in the molecular arrangements according to the boiling point of the guest molecules.
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U2 - 10.1021/acs.cgd.7b01236
DO - 10.1021/acs.cgd.7b01236
M3 - Article
AN - SCOPUS:85040189791
SN - 1528-7483
VL - 18
SP - 286
EP - 296
JO - Crystal Growth and Design
JF - Crystal Growth and Design
IS - 1
ER -