期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 10, 期 10, 页码 2555-2564出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200305725
关键词
molecular shuttles; nanotechnology; NMR spectroscopy; rotaxanes; self-assembly; template synthesis
Six different degenerate [2]rotaxanes were synthesized and characterized. ne rotaxanes contained either two tetrathiafulvalene (TTF) units or two 1,5-dioxynaphthalene (DNP) ring systems, both of which serve as recognition sites for a cyclobis(paraquat-p-phenylene) (CBPQT(4+)) ring. Three different spacer units were incorporated into the dumbbell components of the [2]rotaxanes between the recognition sites. They include a polyether chain, a terphenyl unit, and a diphenyl ether linker, all of which were investigated in order to probe the effect of the spacers on the rate of the shuttling process. Data from dynamic H-1 NMR spectroscopy revealed a relatively small difference in the DeltaG(double dagger) values for the shuttling process in the [2]rotaxanes containing the three different spacers, in contrast to a large difference between the TTF-containing rotaxanes (18 kcal mol(-1)) and the DNP-containing rotaxanes (15 kcal mol(-1)). This 3 kcal mol(-1) difference is predominantly a result of a ground-state effect, reflecting the much stronger binding of TTF units to the CBPQT(4+) ring in comparison with DNP ring systems. An examination of the enthalpic (DeltaH(double dagger)) and entropic (DeltaS(double dagger)) components for the shuttling process in the DNP-containing rotaxanes revealed significant differences between the three spacers, a property which could be important in designing new molecules for incorporation into molecular electronic and nanoelectromechanical (NEMs) devices.
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