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Counterion Dynamics in an Interpenetrated Coordination Cage Capable of Dissolving AgCl
Author(s) -
Freye Sabrina,
Engelhard David M.,
John Michael,
Clever Guido H.
Publication year - 2013
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.201203086
Subject(s) - chemistry , ion , counterion , crystallography , ligand (biochemistry) , chloride , supramolecular chemistry , nuclear magnetic resonance spectroscopy , dissolution , stereochemistry , crystal structure , organic chemistry , biochemistry , receptor
In solution, the eight BF 4 − counterions of a positively charged D 4 ‐symmetric interpenetrated [Pd 4 ligand 8 ] 8+ double cage ( 1 ) are localized in distinct positions. At low temperatures, one BF 4 − ion is encapsulated inside the central pocket of the supramolecular structure, two BF 4 − ions are bound inside the equivalent outer pockets, and the remaining five BF 4 − ions are located outside the cage structure (expressed by the formula [3 BF 4 @ 1 ][BF 4 ] 5 ). On warming, the two BF 4 − ions in the outer pockets are found to exchange with the exterior ions in solution whereas the central BF 4 − ion stays locked inside the central cavity (here written as [BF 4 @ 1 ][BF 4 ] 7 ). The exchange kinetics were determined by exchange spectroscopy (EXSY) NMR experiments and line‐shape fitting in different solvents. The tremendously high affinity of this double cage for the binding of two chloride ions inside the outer pockets allows for complete exchange of two BF 4 − ions by the addition of solid AgCl to give [2 Cl+BF 4 @ 1 ][BF 4 ] 5 . The uptake of the two chloride ions is allosteric and is thus accompanied by a structural rearrangement (compression along the Pd 4 axis) of the double cage structure. An analysis by using 900 MHz NOESY NMR spectroscopy shows that this compression of about 3.3 % is associated with a helical twist of 8°, which together resemble a screw motion. As a consequence of squeezing each of the outer two pockets by 53 %, the volume of the central pocket is increased by 43 %, which results in an increase of 36 % in the 19 F spin‐lattice relaxation time ( T 1 ) of the central BF 4 − ion. The packing coefficients ( PC ) for the ions in the outer pockets (103 % for BF 4 − and 96 % for Cl − ) were calculated.