Premium
Effect of Directional Hydrogen Bonding on the Self‐Assembly of Anisotropically‐Shaped Macroions
Author(s) -
Haso Fadi,
Luo Jiancheng,
Bassil Bassem S.,
Artetxe Beñat,
Zhou Jing,
Yin Panchao,
Reinoso Santiago,
GutiérrezZorrilla Juan M.,
Kortz Ulrich,
Liu Tianbo
Publication year - 2016
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201601154
Subject(s) - counterion , hydrogen bond , polarity (international relations) , solvent , acetone , attraction , chemistry , chemical physics , self assembly , crystallography , chemical engineering , nanotechnology , materials science , ion , molecule , organic chemistry , biochemistry , linguistics , philosophy , engineering , cell
The two polyoxometalate salts K 9 LiNa[Fe 16 O 2 (OH) 23 (H 2 O) 9 (P 8 W 49 O 189 )Gd 4 (H 2 O) 20 ] and Na 22 [(2,3‐pyzdc) 2 {NaNi 2 (H 2 O) 4 Sb 2 W 20 O 70 } 2 ] (2,3‐pyzdc: 2,3‐pyrazinedicarboxylate) demonstrate macroionic self‐assembly phenomenon in dilute solution, but with the trends of assembly size vs. solvent polarity opposite to what has been reported to date. This reveals the influence of additional, directional attractive forces beyond conventional counterion‐mediated attraction. The fact that the size of the assemblies decreases with increasing acetone content in acetone/water mixed solvents is shown to be due to hydrogen bonding. The role of hydrogen bonding is further demonstrated by changes of the assembly size with temperature. In the presence of a hydrogen bond‐cutting solvent such as hexafluoroisopropanol, the counterion‐mediated attraction becomes the dominant driving force and the trend of the assembly size vs. solvent polarity reverts back to the usual charge‐regulated process.