Premium
A Series of Discrete Dichloride Dihydrates: Characterisation and Symmetry Effects
Author(s) -
Senthooran Rathiga,
Curnow Owen J.,
Brenner Thomas,
Weiss Robert,
Ferreras Manuel,
Crittenden Deborah L.
Publication year - 2020
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.202000563
Subject(s) - series (stratigraphy) , symmetry (geometry) , computational chemistry , chemistry , mathematics , statistical physics , physics , geometry , geology , paleontology
A series of three discrete dichloride dihydrates [Cl 2 (H 2 O) 2 ] 2− have been isolated with different triaminocyclopropenium (TAC) cations and with different crystallographic symmetries. The cluster exhibits D 2h symmetry with the tris(dimethylamino)cyclopropenium cation [C 3 (NMe 2 ) 3 ] + , C 2h symmetry with the fluorinated cation [C 3 (N(CH 2 CF 3 ) 2 )(NBu 2 ) 2 ] + (containing two 2,2,2‐trifluoroethyl substituents) and C 2v symmetry with the more fluorinated [C 3 (N(CH 2 CF 3 ) 2 ) 2 (NBu 2 )] + cation. The effect of symmetry on the infrared spectra of the dichloride ion‐pair clusters, as well as deuterated analogues, has been investigated. The D 2h ‐ and C 2h ‐symmetric clusters each exhibit two stretching bands in the infrared at 3427 and 3368 cm −1 for D 2h symmetry and 3444 and 3392 cm −1 for C 2h symmetry, whereas the C 2v ‐symmetric cluster exhibits three bands at 3475, 3426 and 3373 cm −1 . Computational studies were carried out on a [Cl 2 (H 2 O) 2 ] 2− cluster with C 2v symmetry to aid the infrared band assignments.