Direct Experimental Evidence for Halogen-Aryl π Interactions in Solution from Molecular Torsion Balances

被引：32

作者：

Sun, Han ^{[1
]}

Horatscheck, Andre ^{[1
,2
]}

Martos, Vera ^{[1
]}

Bartetzko, Max ^{[1
,3
]}

Uhrig, Ulrike ^{[4
]}

Lentz, Dieter ^{[5
]}

Schmieder, Peter ^{[1
]}

Nazare, Marc ^{[1
]}

机构：

[1] Leibniz Inst Mol Pharmakol FMP, Dept Chem Biol & Struct Biol, Campus Berlin Buch,Robert Roessle Str 10, D-13125 Berlin, Germany

[2] Univ Cape Town, Dept Chem, Drug Discovery & Dev Ctr H3D, ZA-7701 Rondebosch, South Africa

[3] Max Planck Inst Colloids & Interfaces, Muhlenberg 1, D-14476 Potsdam, Germany

[4] EMBL, Chem Biol Core Facil, Meyerhofstr 1, D-69117 Heidelberg, Germany

[5] Free Univ Berlin, Inst Chem & Biochem Anorgan Chem, Fabeckstr 34-36, D-14195 Berlin, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2017年 / 56卷 / 23期

关键词：

halogen bonding; halogen-aryl pi interactions; molecular balances; molecular recognition; residual dipolar coupling; ORTHOGONAL DIPOLAR INTERACTIONS; FACE AROMATIC INTERACTIONS; FUNCTIONAL-GROUP ARRAYS; PROTEIN-LIGAND BINDING; STACKING INTERACTIONS; SYNTHETIC RECEPTORS; ARENE INTERACTIONS; ORGANIC FLUORINE; SIGMA-HOLE; SUBSTITUTION;

D O I：

10.1002/anie.201700520

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We dissected halogen-aryl pi interactions experimentally using a bicyclic N-arylimide based molecular torsion balances system, which is based on the influence of the non-bonded interaction on the equilibria between folded and unfolded states. Through comparison of balances modulated by higher halogens with fluorine balances, we determined the magnitude of the halogen-aryl pi interactions in our uni-molecular systems to be larger than -5.0 kJ mol(-1), which is comparable with the magnitude estimated in the biomolecular systems. Our study provides direct experimental evidence of halogen-aryl pi interactions in solution, which until now have only been revealed in the solid state and evaluated theoretically by quantum-mechanical calculations.

引用

页码：6454 / 6458

页数：5

共 58 条

[1]

Aliev A. E., 2015, ANGEW CHEM, V127, P561, DOI DOI 10.1039/B822665M

[2] Surfing π Clouds for Noncovalent Interactions: Arenes versus Alkenes [J].