A Versatile Tripodal Amide Receptor for the Encapsulation of Anions or Hydrated Anions via Formation of Dimeric Capsules

被引:71
作者
Arunachalam, M. [1 ]
Ghosh, Pradyut [1 ]
机构
[1] Indian Assoc Cultivat Sci, Dept Inorgan Chem, Kolkata 700032, India
关键词
SELF-ASSEMBLING CAPSULES; HYDROGEN-BONDS; REVERSIBLE ENCAPSULATION; SUPRAMOLECULAR CHEMISTRY; CONFORMATIONAL CONTROL; MOLECULAR RECOGNITION; BICYCLIC CYCLOPHANE; TEMPLATED SYNTHESIS; OCTAAMINO CRYPTAND; METALLO-CAPSULE;
D O I
10.1021/ic901644h
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A bowl-shaped tripodal receptor with an appropriately positioned amide functionality on the benzene platform and electron-withdrawing p-nitrophenyl terminals (L) has been designed, synthesized, and studied for the anion binding properties. The single-crystal X-ray crystallographic analysis on crystals of L-1 with tetrabutylammonium salts of nitrate (1), acetate (2), fluoride (3), and chloride (4) obtained in moist dioxane medium showed encapsulation of two NO3-, [(AcO)(2)(H2O)(4)](2-), [F-2(H2O)(6)](2-), and [Cl-2(H2O)(4)](2-) respectively as the anionic guests inside the staggered dimeric capsular assembly of L-1, The p-nitro substitution in the aryl terminals assisted the formation of dimeric capsular assembly of L-1 exclusively upon binding/encapsulating above different guests, Though L-1 demonstrates capsule formation upon anion or hydrated anion complexation for all of the anions studied here, its positional isomer with the o-nitro-substituted tripodal triamide receptor L-2 selectively formed the dimeric capsular assembly upon encapsulation of [F-2(H2O)(6)](2-) and noncapsular aggregates in the cases of other anions such as Cl-, NO3-, and AcO-. Interestingly, structural investigations upon anion exchange of the complexes revealed that both isomers have selectivity toward the formation of a [F-2(H2O)(6)](2-) encapsulated dimeric capsule. In contrast, solution-state H-1 NMR titration studies of L-1 and L-2 in DMSO.d(6) with AcO- indicated 1:3 (host:guest) binding.
引用
收藏
页码:943 / 951
页数:9
相关论文
共 104 条
[1]   Longer guests drive the reversible assembly of hyperextended capsules [J].
Ajami, Dariush ;
Rebek, Julius, Jr. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (48) :9283-9286
[2]   Pulsed gradient spin echo (PGSE) diffusion measurements as a tool for the elucidation of a new type of hydrogen-bonded bicapsular aggregate [J].
Alajarín, M ;
Pastor, A ;
Orenes, RA ;
Martínez-Viviente, E ;
Pregosin, PS .
CHEMISTRY-A EUROPEAN JOURNAL, 2006, 12 (03) :877-886
[3]   Self-assembly of tris(2-ureidobenzyl)amines:: A new type of capped, capsule-like dimeric aggregates derived from a highly flexible skeleton [J].
Alajarín, M ;
Pastor, A ;
Orenes, RA ;
Steed, JW ;
Arakawa, R .
CHEMISTRY-A EUROPEAN JOURNAL, 2004, 10 (06) :1383-1397
[4]   Dimeric self-assembling capsules derived from the highly flexible tribenzylamine skeleton [J].
Alajarín, M ;
Pastor, A ;
Orenes, RA ;
Steed, JW .
JOURNAL OF ORGANIC CHEMISTRY, 2002, 67 (20) :7091-7095
[5]   Highly diastereoselective self-assembly of chiral tris(m-ureidobenzyl) amino capsules [J].
Alajarin, Mateo ;
Pastor, Aurelia ;
Orenes, Raul-Angel ;
Goeta, Andres E. ;
Steed, Jonathan W. .
CHEMICAL COMMUNICATIONS, 2008, (34) :3992-3994
[6]   Structure, stability and guest affinity of tris(3-ureidobenzyl)amine capsules in solution [J].
Alajarin, Mateo ;
Pastor, Aurelia ;
Orenes, Raul-Angel ;
Martinez-Viviente, Eloisa ;
Rueegger, Heinz ;
Pregosin, Paul S. .
CHEMISTRY-A EUROPEAN JOURNAL, 2007, 13 (05) :1559-1569
[7]   A metal-based trisimidazolium cage that provides six C-H hydrogen-bond-donor fragments and includes anions [J].
Amendola, Valeria ;
Boiocchi, Massimo ;
Colasson, Benoit ;
Fabbrizzi, Luigi ;
Douton, Maria-Jesus Rodriguez ;
Ugozzoli, Franco .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (41) :6920-6924
[8]  
[Anonymous], 1995, SAINT XPREP VERS 5 1
[9]  
[Anonymous], 2003, COORD CHEM REV
[10]  
[Anonymous], 2003, MERC 1 3 SUPPL CAMBR