Exploration of Charge-Transfer Solids Utilizing Nucleobases: Nanoarchitectures by Hydrogen-Bonds in the Ionic Assemblies of Guanine and TCNQ Derivatives

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• 作者：Tsuyoshi Murata ; Gunzi Saito ; Kenji Nakamura ; Mitsuhiko Maesato ; Takaaki Hiramatsu ; Yukihiro Yoshida
• 刊名：Crystal Growth & Design
• 出版年：2013
• 出版时间：July 3, 2013
• 年：2013
• 卷：13
• 期：7
• 页码：2778-2792
• 全文大小：1343K
• 年卷期：v.13,no.7(July 3, 2013)
• ISSN：1528-7505

文摘

We studied formation and structural characteristics of charge-transfer solids of 9-n-butylguanine (BuG) with fluorinated tetracyanoquinodimethane derivatives (F_nTCNQ, n = 4, 2, and 1). Complex formation in a methanol (MeOH)-containing solvent generated two types of salts composed of either a methoxy-substituted anion or a fully ionic anion radical of F_nTCNQ. In all anion radical salts, BuG existed as a protonated or a hemiprotonated species, BuGH⁺ or (BuG)(BuGH⁺), respectively, and formed hydrogen-bonded (H-bonded) assemblies. In these BuGH⁺ assemblies, F_nTCNQ^{鈥⑩€?/sup> molecules were fixed and aligned periodically, providing H-bonded polycationic templates. In (BuGH+)(F₄TCNQ鈥⑩€?/sup>), BuGH+ dimers by complementary H-bonds formed a two-dimensional (2D) polycationic sheet. The F₄TCNQ鈥⑩€?/sup> face-to-face dimers formed a one-dimensional (1D) segregated column aided by formation of H-bonds with BuGH+. In (BuGH+)(F₂TCNQ鈥⑩€?/sup>)(MeOH), BuGH+ dimers by complementary double H-bonds formed a 1D polycationic ribbon supported by MeOH-mediated H-bonds. A 1D mixed stack column of (BuGH+)₂ and (F₂TCNQ鈥⑩€?/sup>)₂ dimers was formed owing to their complementary geometry and size. In (BuG)(BuGH+)(F₁TCNQ鈥⑩€?/sup>), a new type of BuG鈥?b>BuGH+ pair formed a 1D ribbon supported by complementary H-bonds, and F₁TCNQ鈥⑩€?/sup> dimers were aligned by H-bonds with the BuG鈥?b>BuGH+ ribbon.}