5 research outputs found

    Selective Alternate Derivatization of the Hexaphenylbenzene Framework through a Thermodynamically Controlled Halogen Dance

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    We report a practical synthetic protocol and mechanistic details for the selective alternate derivatization of the hexaphenylbenzene (HPB) framework through a thermodynamically controlled halogen dance. The stability of the alternately trilithiated species of HPB is interpreted by the through-space interaction at the <i>ipso</i>-carbons of the phenyl groups of the HPB framework. By using this approach, <i>C</i><sub>3</sub>-symmetric and lower-symmetric HPB derivatives possessing two or three kinds of substituents on the periphery have become easily and practically available

    Multiple Pathways in the Self-Assembly Process of a Pd<sub>4</sub>L<sub>8</sub> Coordination Tetrahedron

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    The self-assembly of a Pd<sub>4</sub><b>1</b><sub>8</sub> coordination tetrahedron (<b>Tet</b>) from a ditopic ligand, <b>1</b>, and palladium­(II) ions, [PdPy*<sub>4</sub>]<sup>2+</sup> (Py* = 3-chloropyridine), was investigated by a <sup>1</sup>H NMR-based quantitative approach (quantitative analysis of self-assembly process, QASAP), which allows one to monitor the average composition of the intermediates not observed by NMR spectroscopy. The self-assembly of <b>Tet</b> takes place mainly through three pathways and about half of the <b>Tet</b> structures were produced through the reaction of a kinetically produced Pd<sub>3</sub>L<sub>6</sub> double-walled triangle (<b>DWT</b>) and 200-nm-sized large intermediates (<b>Int</b><sup><b>L</b></sup>). In two of the three pathways, the leaving ligand (Py*), which is not a component of <b>Tet</b>, catalytically assisted the self-assembly. Such a multiplicity of the self-assembly process of <b>Tet</b> suggests that molecular self-assembly takes place on an energy landscape like a protein-folding funnel