Dynamic Characterization of Crystalline Supramolecular Rotors Assembled through Halogen Bonding

被引：83

作者：

Catalano, Luca ^{[1
,2
]}

Perez-Estrada, Salvador ^{[2
]}

Terraneo, Giancarlo ^{[1
]}

Pilati, Tullio ^{[1
]}

Resnati, Giuseppe ^{[1
]}

Metrangolo, Pierangelo ^{[1
,3
]}

Garcia-Garibay, Miguel A. ^{[2
]}

机构：

[1] Politecn Milan, Dept Chem Mat & Chem Engn Giulio Natta, Lab Nanostruct Fluorinated Mat NFMLab, I-20131 Milan, Italy

[2] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

[3] VTT Tech Res Ctr Finland, FI-02044 Espoo, Finland

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2015年 / 137卷 / 49期

基金：

美国国家科学基金会;

关键词：

MOLECULAR ROTORS; ROTATIONAL-DYNAMICS; TEREPHTHALATE PHENYLENES; FLUORINATION; DIFFRACTION; INCLUSION; SYMMETRY; MOTIONS;

D O I：

10.1021/jacs.5b10776

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A modular molecular kit for the preparation of crystalline molecular rotors was devised from a set of stators and rotators to gain simple access to a large number of structures with different dynamic performance and physical properties. In this work, we have accomplished this with crystalline molecular rotors self-assembled by halogen bonding of diazabicyclo[2.2.2]octane, acting as a rotator, and a set of five fluorine-substituted iodobenzenes that take the role of the stator. Using variable-temperature H-1 T-1 spin-lattice relaxation measurements, we have shown that all structures display ultrafast Brownian rotation with activation energies of 2.4-4.9 kcal/mol and pre-exponential factors of the order of (1-9) x 10(12) s(-1). Line shape analysis of quadrupolar echo H-2 NMR measurements in selected examples indicated rotational trajectories consistent with the 3-fold or 6-fold symmetric potential of the rotator.

引用

页码：15386 / 15389

页数：4

共 41 条

[1] Molecular rotor of Cs2([18]crown-6)3 in the solid state coupled with the magnetism of [Ni(dmit)2] [J].