Host-guest molecular crystals of diamino-4,4-bithiazole and dynamic molecular motions via guest sorption
Host-guest molecular crystals of diamino-4,4-bithiazole and dynamic molecular motions via guest sorption
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二氨基-4,4-联噻唑的主客体分子晶体和客体吸附的动态分子运动
DOI：
10.1021/acs.cgd.7b01236
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发表时间：
2018
影响因子：
3.8
通讯作者：
Tomoyuki Akutagawa
中科院分区：
文献类型：
--
作者：
Hiroshi Nishiyama;Takashi Takeda;Norihisa Hoshino;Kiyonori Takahashi;Shin-ichiro Noro;Takayoshi Nakamura;Tomoyuki Akutagawa
二氨基-4，4-联噻唑（1）与吡啶（Py）、苯甲腈（PhCN）、哌啶（Pipe）、DMF、THF、1，4-二氧六环（Diox）、CH 3OH、苯胺（Ani）、香豆素（Coum）、硝基苯（PhNO 2）、六亚甲基四胺（HMTA）和喹啉（Quino）等各种有机客体分子形成主-客体二元分子晶体。100 K下的单晶X射线结构分析表明，形成了1·（客体）或1·（客体）2晶体。可逆的分子吸附-脱附反应，观察到与Py，PhCN，Pipe，DMF，和Diox在室温左右的结晶粉末在脱附过程中被加热，并在再吸附过程中暴露于客体蒸气。在298 K下，晶体粉末1与Diox的吸附-脱附等温线表明，晶体粉末1与Diox的吸附-脱附过程为可逆的开门吸附-脱附过程。虽然在100 K下通过X射线晶体结构分析证实了主-客体分子晶体1·（THF）2和1·（CH 3OH）2，但THF和CH 3OH客体在室温下已经被消除。在含有Ani、Coum、PhNO 2、HMTA和Quino的主-客体分子晶体中，晶体粉末加热后没有观察到1·（客体）x的客体脱附过程。客体分子的偶极矩和蒸气压的平衡对引发可逆客体吸附起着至关重要的作用。晶体结构的形成是由于− NH 2基团和1的环氮原子之间的双N-H···N氢键一维（1D）链，它们通过π堆积和/或S···S相互作用形成二维（2D）片状结构。1和客体分子的N-H···N氢键人字形堆积交替层导致了其他类型晶格的形成。1的氢键分子组装体表现出晶格的灵活性，通过改变分子排列中的构型，根据客体分子的沸点。
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 of1·(guest) or1·(guest)2crystals. 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 powders1with Diox at 298 K indicated a reversible gate-opening adsorption–desorption process. Although the host–guest molecular crystals1·(THF)2and1·(CH3OH)2were 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 powders1·(guest)xwere 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 −NH2group and the ring nitrogen atom of1, 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 of1and the guest molecules led to the formation of other types of crystal lattices. The hydrogen-bonding molecular assemblies of1demonstrated lattice flexibly via the configuration change in the molecular arrangements according to the boiling point of the guest molecules.