Charge-Transfer-Driven Inclusion of Neutral TCNQ Molecules in the Galleries of a Layered Double Hydroxide: An Experimental and Computational Study

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• 作者：Dipak Dutta ; Anil Kumar Tummanapelli ; Sukumaran Vasudevan
• 刊名：The Journal of Physical Chemistry C
• 出版年：2013
• 出版时间：February 28, 2013
• 年：2013
• 卷：117
• 期：8
• 页码：3930-3939
• 全文大小：559K
• 年卷期：v.117,no.8(February 28, 2013)
• ISSN：1932-7455

文摘

The layered double hydroxides (LDH) or anionic clays are an important class of ion-exchange materials. They consist of positively charged brucite-like inorganic sheets with charge-compensating exchangeable anions in the interlamellar space. Here we show how neutral TCNQ (7,7,8,8-tetracyanoquinodimethane) molecules can be included within the galleries of an LDH. To do so, we exploit the fact that TCNQ is a good electron acceptor that forms donor鈥揳cceptor complexes with a variety of donors. The electron donor aniline was intercalated into a Mg鈥揂l LDH as p-aminobenzoate (AB) ions by a conventional ion-exchange reaction. We show here that neutral TCNQ molecules may be driven into the galleries of the layered solid by charge-transfer complex formation with the intercalated p-aminobenzoate anions. We use diffraction and spectroscopic measurements in combination with molecular dynamics simulations and quantum chemical calculations to establish the nature of interactions and arrangement of the charge-transfer complex within the galleries of the layered double hydroxide. Electrostatic interactions between the TCNQ molecules and the anchored AB ions, subsequent to charge transfer, are the driving force for the inclusion of TCNQ molecules in the galleries of the LDH.