Nonspherical anion sequestration by C-H hydrogen bonding

被引:17
作者
Mirzaei, Saber [1 ]
Espinoza Castro, Victor M. [1 ]
Hernandez Sanchez, Raul [1 ]
机构
[1] Univ Pittsburgh, Dept Chem, 219 Parkman Ave, Pittsburgh, PA 15260 USA
基金
美国安德鲁·梅隆基金会;
关键词
HOST-GUEST; BINDING; RECOGNITION; MACROCYCLES; RECEPTORS; FLUORIDE; ENCAPSULATION; COMPLEXATION; CAVITANDS; CHEMISTRY;
D O I
10.1039/d1sc07041j
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Macrocyclic arenes laid the foundations of supramolecular chemistry and their study established the fundamentals of noncovalent interactions. Advancing their frontier, here we designed rigidified resorcin[4]arenes that serve as hosts for large nonspherical anions. In one synthetic step, we vary the host's anion affinity properties by more than seven orders of magnitude. This is possible by engineering electropositive aromatic C-H bond donors in an idealized square planar geometry embedded within the host's inner cavity. The hydrogen atom's electropositivity is tuned by introducing fluorine atoms as electron withdrawing groups. These novel macrocycles, termed fluorocages, are engineered to sequester large anions. Indeed, experimental data shows an increase in the anion association constant (K-a) as the number of F atoms increase. The observed trend is rationalized by DFT calculations of Hirshfeld Charges (HCs). Most importantly, fluorocages in solution showed weak-to-medium binding affinity for large anions like [PF6](-) (10(2)< K-a <10(4) M-1), and high affinity for [MeSO3](-) (K-a >10(6)).
引用
收藏
页码:2026 / 2032
页数:7
相关论文
共 63 条
[1]   Versatile Launch Pad for Facile Functionalization of Cavitands [J].
Aakeroey, Christer B. ;
Chopade, Prashant D. ;
Schultheiss, Nate ;
Desper, John .
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2011, 2011 (33) :6789-6793
[2]   ELECTRONEGATIVITY VALUES FROM THERMOCHEMICAL DATA [J].
ALLRED, AL .
JOURNAL OF INORGANIC & NUCLEAR CHEMISTRY, 1961, 17 (3-4) :215-221
[3]   Population-Wide Exposure to Per- and Polyfluoroalkyl Substances from Drinking Water in the United States [J].
Andrews, David Q. ;
Naidenko, Olga, V .
ENVIRONMENTAL SCIENCE & TECHNOLOGY LETTERS, 2020, 7 (12) :931-936
[4]   A Versatile Tripodal Amide Receptor for the Encapsulation of Anions or Hydrated Anions via Formation of Dimeric Capsules [J].
Arunachalam, M. ;
Ghosh, Pradyut .
INORGANIC CHEMISTRY, 2010, 49 (03) :943-951
[5]   New "cholapod" anionophores; high-affinity halide receptors derived from cholic acid [J].
Ayling, AJ ;
Pérez-Payán, MN ;
Davis, AP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (50) :12716-12717
[6]  
Balan Simona A., 2021, ENVIRON HEALTH PERSP, V129
[7]   Solution phase measurement of both weak σ and C-H•••X- hydrogen bonding interactions in synthetic anion receptors [J].
Berryman, Orion B. ;
Sather, Aaron C. ;
Hay, Benjamin P. ;
Meisner, Jeffrey S. ;
Johnson, Darren W. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (33) :10895-10897
[8]   VAN DER WAALS VOLUMES + RADII [J].
BONDI, A .
JOURNAL OF PHYSICAL CHEMISTRY, 1964, 68 (03) :441-+
[9]   Alfred Werner revisited: The coordination chemistry of anions [J].
Bowman-James, K .
ACCOUNTS OF CHEMICAL RESEARCH, 2005, 38 (08) :671-678
[10]   HOST GUEST COMPLEXATION .55. GUEST CAPTURE DURING SHELL CLOSURE [J].
BRYANT, JA ;
BLANDA, MT ;
VINCENTI, M ;
CRAM, DJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (06) :2167-2172