Reversible Accommodation and Desorption of Aromatics on a Charge Transfer Cocrystal Involving an Anthracene Derivative and TCNQ

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• 作者：Xiaojuan Wu ; Mingliang Wang ; Man Du ; Jiao Lu ; Jinxi Chen ; Arshad Khan ; Rabia Usman ; Xiang Wei ; Qi Feng ; Chunxiang Xu
• 刊名：Crystal Growth & Design
• 出版年：2015
• 出版时间：January 7, 2015
• 年：2015
• 卷：15
• 期：1
• 页码：434-441
• 全文大小：406K
• ISSN：1528-7505

文摘

A charge transfer organic cocrystal 1 was constructed from an anthracene derivative, 1-(5-(anthracen-9-yl)-3-(4-methoxyphen-yl)-4,5-dihydropyrazol-1-yl)ethanone (AMPE) and TCNQ. Eight cocrystal solvates which can be placed into types I and II were obtained from solution. Type I solvates include 1路toluene, 1路chlorobenzene, 1路o-chlorotoluene, 1路p-chlorotoluene, 1路o-xylene, 1路m-xylene, and 1路p-xylene-1, while 1路p-xylene-2 belongs to type II solvate. Crystal structure analysis revealed that cocrystal 1 was an isomorphic desolvate of type I solvates. Slitlike channels were created in 1 through charge transfer, hydrogen bond, and 蟺鈥撓€ interactions, which are expanded in corresponding type I solvates, while the type II solvate shows a different structure from that of type I solvates. The neighboring racemic chains were connected by one kind of p-xylene molecules through C鈥揌路路路蟺 interactions and formed square-grid channels. Cocrystal 1 selectively accommodates aromatic solvents over other polar and nonpolar nonaromatic solvents such as acetone, CH₂Cl₂, and cyclohexane to form type I solvates. These solvates converted to 1 again upon desolvation, and the transformation occurs in a crystal-to-crystal manner. Type II solvate (1路p-xylene-2) can also be converted to 1 upon desolvation, but 1 cannot accommodate p-xylene to form the type II solvate again. This result can be used to certify the conversion from 1 to type I solvates by the absorption mechanism.