Surface functionalization of cadmium sulfide quantum confined nanoclusters - 6: Evidence of facile electronic communication between remote surface sites

摘要

The preparation and derivatization of a series of surface functionalized similar to 30 Angstrom cadmium sulfide nanoclusters possessing surfaces of varied electron demand, tethered covalently to an electroactive fluorescent ruthenium polypyridyl complex, are described. Electrochemical analyses of these nanoclusters bearing ruthenium moieties yield a monotonic relationship between the Ru(II/III) oxidation potential and the electron withdrawing nature of the cluster surface, indicating that the electron density at the electroactive ruthenium center is indeed influenced by remote electropositive and electronegative substituents attached to the nanocluster. Further evidence of cluster mediated electronic interactions between remote surface moieties presents itself in the form of a dependence of the integrated ruthenium based MLCT emission intensity on the mole per cent of attached thiolate capping agent possessing an electron withdrawing substituent in the position para to the point of cluster attachment. (C) 2000 Elsevier Science Ltd. All rights reserved. [References: 38]