title: Construction of endo-functionalized two dimensional metallacycles via coordination-driven self-assembly.
abstract: The synthesis of three endofunctionalized two-dimensional supramolecular metallacycles including two [2 + 2] rhomboids (5 and 6) and a [3 + 3] hexagon (7) is reported. The resulting self-assembled supramolecular structures, containing several nitrobenzyl moieties at their interior surface, have been fully characterized by multinuclear NMR ((31)P and (1)H) and electrospray ionization mass spectrometry. A significant C-H...O hydrogen bonding between the nitrobenzyl acceptor and the edge molecules of the supramolecular architecture is observed in the small rhomboid 5 and this interaction gradually decreases upon the enlargement of the resulting polygonal structures from a small rhomboid 5 through a large rhomboid 6 to a hexagon 7. Molecular modeling with the MMFF force field gives a possible conformation of each self-assembly in different solvents and shows that the hydrophilic nitrobenzyl moiety prefers to be buried in the cavity of the resulting polygonal structures in nonpolar solvents, thus forming hydrogen bonds with the peripheral component building units.
authors.affiliation: Department of Chemistry, University of Utah, 315 South 1400 East, Room 2020, Salt Lake City, Utah 84112, USA.
authors.forename: Liang
authors.initials: L
authors.lastname: Zhao
authors.forename: Koushik
authors.initials: K
authors.lastname: Ghosh
authors.forename: Yao-Rong
authors.initials: YR
authors.lastname: Zheng
authors.forename: Peter J
authors.initials: PJ
authors.lastname: Stang
mesh_terms: D003500:Cyclization; D008024:Ligands; D046911:Macromolecular Substances / Q000138:chemical synthesis / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D008024:Ligands; D046911:Macromolecular Substances; D009942:Organometallic Compounds