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Molecular Encapsulation via Metal-to-Ligand Coordination in a Cu(I)-Folded Molecular Basket
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Abstract
A molecular basket, composed of a semirigid C3v symmetric tris-norbornadiene framework and three pyridine flaps at the rim, has been shown to coordinate to a Cu(I) cation and thereby fold in a multivalent fashion. The assembly was effective (Ka = 1.73 ± 0.08 × 105 M−1) and driven by enthalpy (ΔH° = −7.2 ± 0.1 kcal/mol, ΔS° = −0.25 eu). Variable temperature 1H NMR studies, assisted with 2D COSY and ROESY investigations, revealed the existence of Cu(I)-folded basket 10b with a molecule of acetonitrile occupying its interior and coordinated to the metal. Interestingly, 10b is in equilibrium with Cu(I)-folded 10a, whose inner space is solvated by acetone or chloroform. The incorporation of a molecule of acetonitrile inside 10a was found to be driven by enthalpy (ΔH° = −3.3 ± 0.1 kcal/mol), with an apparent loss in entropy (ΔS° = −9.4 ± 0.4 eu); this is congruent with a complete immobilization of acetonitrile and release of a “loosely” encapsulated solvent molecule during 10a/b interconversion. From an Eyring plot, the activation enthalpy for incorporating acetonitrile into 10a was found to be positive (ΔH = 6.5 ± 0.5 kcal/mol), while the activation entropy was negative (ΔS
= −20 ± 2 eu). The results are in agreement with an exchange mechanism whereby acetonitrile “slips” into an “empty” basket through its side aperture. In fact, DFT (BP86) calculations are in favor of such a mechanistic scenario; the calculations suggest that opening of the basket’s rim to exchange guests is energetically demanding and therefore less feasible.
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This article has been cited by 8 ACS Journal articles (5 most recent appear below).
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History
- Published In Issue July 04, 2008
- Article ASAPJune 04, 2008
- Received: April 5, 2008
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