[2.2]Paracyclophane(pCp)scaffolds,unlike manyπ-conjugated building blocks,have been rarely explored in supramolecular self-assembly.Herein we report the synthesis and characterization of two ligands,pCpd3py and pCpd4...[2.2]Paracyclophane(pCp)scaffolds,unlike manyπ-conjugated building blocks,have been rarely explored in supramolecular self-assembly.Herein we report the synthesis and characterization of two ligands,pCpd3py and pCpd4py,composed of a pCp core functionalized at its 7-and 15-positions respectively with 3-pyridyl and 4-pyridyl units.The self-assembly of pCpd4py with Pd^(2+)metal ions afforded a[Pd_(3)(pCpd4py)_(6)]^(6+)cage structure,pCpd4py-Pd,where the six pCpd4py ligands doubly bridge each edge of the Pd_(3)triangular core.The ligand pCpd4py and the palladium cage pCpd4py-Pd have been characterized by NMR spectroscopy,ESI-MS spectrometry and X-ray diffraction analyses and their photophysical properties investigated by steady-state and time-resolved emission spectroscopy as well as time-dependent density functional theory calculations.展开更多
基金the University of St Andrews and EPSRC(EP/M02105X/1)for financial support.
文摘[2.2]Paracyclophane(pCp)scaffolds,unlike manyπ-conjugated building blocks,have been rarely explored in supramolecular self-assembly.Herein we report the synthesis and characterization of two ligands,pCpd3py and pCpd4py,composed of a pCp core functionalized at its 7-and 15-positions respectively with 3-pyridyl and 4-pyridyl units.The self-assembly of pCpd4py with Pd^(2+)metal ions afforded a[Pd_(3)(pCpd4py)_(6)]^(6+)cage structure,pCpd4py-Pd,where the six pCpd4py ligands doubly bridge each edge of the Pd_(3)triangular core.The ligand pCpd4py and the palladium cage pCpd4py-Pd have been characterized by NMR spectroscopy,ESI-MS spectrometry and X-ray diffraction analyses and their photophysical properties investigated by steady-state and time-resolved emission spectroscopy as well as time-dependent density functional theory calculations.
