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Enhanced Macroanion Recognition of Superchaotropic Keggin Clusters Achieved by Synergy of Anion–π and Anion–Cation Interactions
Author(s) -
Qi Bo,
An Sai,
Luo Jiancheng,
Liu Tianbo,
Song YuFei
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202003083
Subject(s) - polyoxometalate , isostructural , ion , chemistry , pyridine , molybdenum , electrochemistry , molecule , crystallization , crystallography , molecular recognition , template , tungsten , combinatorial chemistry , inorganic chemistry , crystal structure , materials science , nanotechnology , organic chemistry , electrode , catalysis
Keggin clusters are the most widely used polyoxometalate building blocks for the construction advanced materials, but effective methods for precisely recognizing the isostructural analogues of Keggins are still limited. In this study we employed the zwitterionic molecule 4,4′‐dipyridyl N , N′ ‐dioxide as a recognition receptor to specifically bind to the three Keggin analogues PW 12 O 40 3− , PMo 12 O 40 3− , and SiW 12 O 40 4− , which separately co‐assembled into three different types of spherical charged colloids of different sizes. The recognition phenomena were confirmed by electrochemical methods and their crystallization behavior. Compared with solely anion–cation interaction‐driven systems, the synergism with the anion–π interactions between the superchaotropic Keggins and the electron‐deficient pyridine rings is believed to enhance the recognition. This observation is intriguing as the long‐range solution assembly of Keggins is mainly driven by short‐range anion–π interactions. Our results show that the little‐noticed hydration shell of Keggins is significantly influenced by the superchaotropic effect, leading to differentiated binding affinity to the receptors and more obvious recognition phenomena between tungsten/molybdenum Keggin analogues.