Tripodal halogen bonding iodo-azolium receptors for anion recognition

The synthesis, characterization and anion binding properties of 1,3,5-tri-substituted benzene platform-based tripodal receptors containing halogen bonding (XB) iodo-imidazolium and iodo-triazolium motifs, and hydrogen bonding (HB) analogues are described. Proton NMR anion binding investigations reveal the XB receptors are superior halide complexants compared to hydrogen bonding (HB) receptor analogues, with the iodo-imidazolium tripodal receptor exhibiting notably higher association constant values in comparison to the iodo-triazolium host system. In contrast, the HB tripod receptors, display higher affinities for dihydrogen phosphate than the XB receptors. Computational DFT and molecular dynamics were used to corroborate the experimental observations, and to give a clearer insight into the intimate nature of halide binding. The studies reveal a fundamental different binding behavior for the imidazolium-based and the iodo-imidazolium-based receptors.

[1]  Pall Thordarson,et al.  The death of the Job plot, transparency, open science and online tools, uncertainty estimation methods and other developments in supramolecular chemistry data analysis. , 2016, Chemical communications.

[2]  P. Beer,et al.  Halogen bonding anion recognition. , 2016, Chemical communications.

[3]  Weizhou Wang,et al.  σ-Hole Bond vs π-Hole Bond: A Comparison Based on Halogen Bond. , 2016, Chemical reviews.

[4]  Pierangelo Metrangolo,et al.  The Halogen Bond , 2016, Chemical reviews.

[5]  P. Beer,et al.  Anion Recognition in Water: Recent Advances from a Supramolecular and Macromolecular Perspective , 2015, Angewandte Chemie.

[6]  S. Chakraborty,et al.  Halogen bonding assisted selective removal of bromide. , 2015, Chemical communications.

[7]  Philip A. Gale,et al.  Anion sensing by small molecules and molecular ensembles. , 2015, Chemical Society reviews.

[8]  Claudia Caltagirone,et al.  Applications of Supramolecular Anion Recognition. , 2015, Chemical reviews.

[9]  Pierre Kennepohl,et al.  Evidence for Halogen Bond Covalency in Acyclic and Interlocked Halogen-Bonding Receptor Anion Recognition , 2014, Journal of the American Chemical Society.

[10]  P. Beer,et al.  Halogen Bonding in Supramolecular Chemistry. , 2008, Chemical reviews.

[11]  J. Sessler,et al.  Neutral CH and cationic CH donor groups as anion receptors. , 2014, Chemical Society reviews.

[12]  R. Noto,et al.  Di‐ and Tricationic Organic Salts: An Overview of Their Properties and Applications , 2014 .

[13]  Ulrich S Schubert,et al.  Beyond click chemistry - supramolecular interactions of 1,2,3-triazoles. , 2014, Chemical Society reviews.

[14]  Cally J E Haynes,et al.  Anion receptor chemistry: highlights from 2011 and 2012. , 2014, Chemical Society reviews.

[15]  M. Mayor,et al.  Dumbbells, trikes and quads: organic-inorganic hybrid nanoarchitectures based on "clicked" gold nanoparticles. , 2014, Small.

[16]  H. Gunaratne,et al.  Solution and thermal behaviour of novel dicationic imidazolium ionic liquids. , 2013, Organic & biomolecular chemistry.

[17]  Pierangelo Metrangolo,et al.  The Halogen Bond in the Design of Functional Supramolecular Materials: Recent Advances , 2013, Accounts of chemical research.

[18]  Paulo J. Costa,et al.  A Catenane Assembled through a Single Charge-Assisted Halogen Bond , 2013, Angewandte Chemie.

[19]  M. Chudziński,et al.  Halogen bonding in solution: thermodynamics and applications. , 2013, Chemical Society reviews.

[20]  A. Lowe,et al.  Determining binding constants from 1H NMR titration data using global and local methods: a case study using [n]polynorbornane-based anion hosts , 2012 .

[21]  P. Thordarson.  Determining association constants from titration experiments in supramolecular chemistry. , 2011, Chemical Society reviews.

[22]  Juyoung Yoon,et al.  Revisit to imidazolium receptors for the recognition of anions: highlighted research during 2006-2009. , 2010, Chemical Society reviews.

[23]  M. Boiocchi,et al.  A metal-based trisimidazolium cage that provides six C-H hydrogen-bond-donor fragments and includes anions. , 2006, Angewandte Chemie.

[24]  J. Schatz,et al.  Influence of the Number and Geometry of Binding Sites on Host–Guest Affinity: Imidazolium-Substituted Receptor Molecules for Small Inorganic Anions , 2006 .

[25]  Kwang S. Kim,et al.  Tripodal nitro-imidazolium receptor for anion binding driven by (C-H)+- - -X- hydrogen bonds. , 2002, Organic letters.

[26]  Keiji Hirose.  A Practical Guide for the Determination of Binding Constants , 2001 .

[27]  Kiyoshi Sato,et al.  A new tripodal anion receptor with CH···X− hydrogen bonding , 1999 .

[28]  C. Alvarez-Rúa,et al.  Hydrogen bonded driven anion binding by dicationic [14]imidazoliophanes , 1999 .