Self-Assembled Metallocycles with Two Interactive Binding Domains
Five metallocycles 1 a–e have been self‐assembled from S‐shaped bispyridyl ligands 2 a–e and a palladium complex, [Pd(dppp)(OTf)2] (dppp=1,3‐bis(diphenylphosphanyl)propane), and have been characterized by elemental analysis and various spectroscopic methods including 1H NMR spectroscopy and electros...
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Veröffentlicht in: | Chemistry : a European journal 2004-09, Vol.10 (17), p.4358-4366 |
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Zusammenfassung: | Five metallocycles 1 a–e have been self‐assembled from S‐shaped bispyridyl ligands 2 a–e and a palladium complex, [Pd(dppp)(OTf)2] (dppp=1,3‐bis(diphenylphosphanyl)propane), and have been characterized by elemental analysis and various spectroscopic methods including 1H NMR spectroscopy and electrospray ionization (ESI) mass spectrometry. These metallocycles all are monocyclic compounds, but can fold to generate two binding domains bearing hydrogen‐bonding sites based on pyridine‐2,6‐dicarboxamide units. The binding properties of the metallocycles with N,N,N′,N′‐tetramethylterephthalamide (G) have been probed by means of ESI mass spectrometry and 1H NMR spectroscopy. The results both in the gas phase and in solution are consistent with the fact that the metallocycles accommodate two molecules of the guest G. Thus, the ESI mass spectra clearly show fragments corresponding to the 1:2 complexes in all cases. 1H NMR studies on 1 a and G support the formation of a 1:2 complex in solution; the titration curves are nicely fitted to a 1:2 binding isotherm, but not to a 1:1 binding isotherm. In addition, a Job plot also suggests a 1:2 binding mode between 1 a and G, showing maximum complexation at ∼0.33 mol fraction of the metallocycle 1 a in CDCl3. The binding constants K1 and K2 are calculated to be 1600 and 1400 M−1 (±10 %), respectively, at 25 °C in CDCl3, indicative of positively cooperative binding. This positive cooperativity was confirmed by the Hill equation, affording a Hill coefficient of n = 1.6. Owing to insufficient solubility in CDCl3, for comparison purposes the binding properties of the metallocycles 1 b–e were investigated in a more polar medium, 3 % CD3CN/CDCl3. 1H NMR titrations revealed that the metallocycles all bind two molecules of the guest G with Hill coefficients ranging from 1.4 to 1.8. This positive cooperativity may be attributed to a structural reorganization of the second binding cavity when the first guest binds to either one of the subcavities present in the metallocycles.
Positive homotropic allosterism has been demonstrated by five metallocycles that were self‐assembled from S‐shaped bispyridyl ligands and a palladium complex, [Pd(dppp)(OTf)2]. Because the metallocycles fold to generate two binding domains bearing hydrogen‐bonding sites (see picture), two molecules of a diamide guest, one to each domain, bind in a positively cooperative manner with Hill coefficients ranging from 1.4 to 1.8. (dppp=1,3‐bis(diphenylphosphanyl)propan |
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ISSN: | 0947-6539 1521-3765 |
DOI: | 10.1002/chem.200400227 |