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ABSTRACT: The coordination-driven self-assembly of four different trigonal prisms from 3 equiv of one of four different tetrapyridyl star connectors and 6 equiv of a platinum linker dication in nitromethane is presented. This face-directed approach affords high yields without template assistance. The prisms have been characterized by multinuclear and DOSY NMR and dual ESI-FT-ICR mass spectrometry. The use of a conformationally chiral star connector leads to a conformationally chiral prism when connector arm ends attached to a vertex have a strongly correlated twist sense and chirality is communicated across polyhedral faces, edges, and vertices. Molecular mechanics results suggest that in the smallest prism 3d collective effects dominate and the all-P and all-M conformers are strongly favored. NMR data prove that the two edges of the pyridine rings in the triflate salts of 3a-3d are distinct. An Eyring plot of rates obtained from line-shape analysis and 1-D EXCHSY NMR yields an activation enthalpy DeltaH(double dagger) of approximately 12 kcal/mol and activation entropy DeltaS(double dagger) of approximately -15 cal/mol x K for the edge interconversion process, compatible with pyridine rotation around the Pt-N bond. For 3c, this behavior is observed only up to approximately 318 K. At higher temperatures, the Eyring plot is again linear but follows a very different straight line, with a DeltaH(double dagger) of approximately 35 kcal/mol and DeltaS(double dagger) of approximately 60 cal/mol x K. This highly unusual result is further investigated and discussed in the following companion paper.
Journal of the American Chemical Society 07/2008; 130(24):7620-8. · 9.91 Impact Factor
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Chemical Reviews 05/2005; 105(4):1281-376. · 40.20 Impact Factor
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ABSTRACT: We have measured the dielectric response of monolayer films of surface mounted chloromethyl-and dichloromethylsilyl dipolar rotors on fused silica at frequencies in the 1 kHz range and temperatures from 4 to 300 K. The torsional potentials, calculated from molecular mechanics, show an asymmetrical three-fold barrier to rotation with a barrier height sufficient to hinder motion of the rotor at experimental temperatures. A broad distribution of barrier heights is observed experimentally, consistent with calculated results showing that the intrinsic barrier of the rotor is modified by interactions with the underlying substrate. For a series of samples with differing concentrations of the rotor, the observed signal strength varies in proportion to the rotor coverage measured by Auger spectroscopy; however, the absolute strength of the signal is about three times larger than expected.
Nanotechnology 07/2002; 13(4):533. · 3.98 Impact Factor
