Metal鈥揙rganic Nanotube with Helical and Propeller-Chiral Motifs Composed of a C10-Symmetric Double-Decker Nanoring

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• 作者：Hiroshi Yamagishi ; Takahiro Fukino ; Daisuke Hashizume ; Tadashi Mori ; Yoshihisa Inoue ; Takaaki Hikima ; Masaki Takata ; Takuzo Aida
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：June 24, 2015
• 年：2015
• 卷：137
• 期：24
• 页码：7628-7631
• 全文大小：396K
• ISSN：1520-5126

文摘

Coassembly of an achiral ferrocene-cored tetratopic pyridyl ligand (FcL) with AgBF₄ in CH₂Cl₂/MeCN (7:3 v/v) containing chiral Bu₄N⁺ (+)- or (鈭?-menthylsulfate (MS*^{鈥?/sup>) results in the formation of an 鈥渙ptically active鈥?metal鈥搊rganic nanotube (FcNT) composed of a C₁₀-symmetric double-decker nanoring featuring 10 FcL units and 20 Ag+ ions. The circular dichroism spectrum of FcNT along with its 2D X-ray diffraction (2D XRD) pattern indicates that the constituent metal鈥搊rganic nanorings in FcNT stack one-handed helically on top of each other. A crystal structure of the dimeric double-decker model complex (Ag₂(FcL鈥?₂) from a ditopic ferrocene ligand (FcL鈥? and AgBF₄ allowed for confirming the binding of MS*鈥?/sup> onto the Ag+ center of the complex. The results of detailed spectroscopic studies indicate that in its double-decker aromatic arrays, FcNT possibly possesses propeller-chiral twists in addition to the helically chiral structure, where the former is considerably more dynamic than the latter. Notably, both chiral structural motifs responded nonlinearly to an enantiomeric excess of MS*鈥?/sup> (majority rule) though with no stereochemical influence on one another.}