Halogenide anions as halogen and hydrogen bond acceptors in iodopyridinium halogenides

Abstract

Structures of iodopyridinium halogenides have demonstrated why iodide, the weakest halogen bond acceptor among the halogenides, preferentially forms halogen bonds.

Crystal engineering strategies towards halogen-bonded metal–organic multi-component solids: salts, cocrystals and salt cocrystals

“…Although the strength of the halogen bond with 'free' halogenide ions generally decreases with the size of the acceptor halogenide, the halogen bonds with lighter halogenides occur less frequently than those with heavier ones. 89 A similar trend seems to hold for coordinated halogenides. Mosquera and coworkers studied the reaction of tetrakis(tert-butylisocyanido)dichlororuthenium(II) with iodine and obtained three cocrystals (some of them as intermediates): a cocrystal of the starting compound (Fig.…”

Halogen Bonding in N-Alkyl-3-halogenopyridinium Salts

“…To date, various Lewis bases (neutral molecules or charged species) have been employed as halogen bond acceptors in constructing halogenbonded supramolecular assemblies. These have most commonly been organic [13,14] and metal-organic [15] molecules containing electron-rich nitrogen [16][17][18][19][20][21][22][23][24][25][26] and oxygen atoms [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41], as well as inorganic anions such as halogenides [42][43][44][45][46][47][48][49][50][51][52][53][54]. The most commonly used halogen bond donors have traditionally been neutral organic molecules where a halogen atom is bonded to electron-withdrawing molecular residues.…”

“…There is an alternative approach to making a reliable halogen bond donor by placing a halogen atom on a positively charged species. To date, a number of halogenoimidazolium and halogenopyridinum cations employed as halogen bond donors in salts with organic [78,79] and inorganic [13,25,[44][45][46][47][48][49][50][51][52][53][54][80][81][82][83][84][85][86][87][88][89][90][91] counterions have been published. Halogenopyridinium cations have been studied as anion receptors [92][93][94][95][96], catalysts in halogenide abstraction [97], colour tuning [98,99] and as counterions for tuning conductivity and magnetic properties in supramolecular conductors [100][101][102][103].…”

The Amine Group as Halogen Bond Acceptor in Cocrystals of Aromatic Diamines and Perfluorinated Iodobenzenes

“…From the beginning of the intensive research into halogen bonding at the turn of the millennium [1][2][3][4][5], one of the main areas of interest (apart from the fundamental studies of the nature and properties of the halogen bond) has been to utilize the halogen bond as a reliable non-covalent molecular interaction in supramolecular chemistry in general [6][7][8][9], and particularly in crystal engineering [10][11][12][13][14], as a means of the deliberate design of multi-component organic [15,16] and metal-organic [17][18][19][20] materials, both comprising ionic species (salts) [21][22][23][24][25][26] and neutral molecules (cocrystals) [27][28][29][30][31][32][33][34][35][36].…”