ABSTRACT
The self-assembly of three nanoscopic prisms of approximate size 1 x 4 nm is reported. Tetrahedral carbon, silicon, and phosphorus were used as structure-defining elements in these coordination-based cages. A carbon-based assembly completes a pair of nanoscopic complementary 3-D structures. The formation of the structures is supported by multinuclear NMR, ESI FT-ICR mass spectrometry, and elemental analysis data.
Subject(s)
Anthracenes/chemistry , Benzene Derivatives/chemistry , Cross-Linking Reagents/chemistry , Organophosphorus Compounds/chemistry , Organosilicon Compounds/chemistry , Anthracenes/chemical synthesis , Benzene Derivatives/chemical synthesis , Cross-Linking Reagents/chemical synthesis , Crystallography, X-Ray , Fourier Analysis , Magnetic Resonance Spectroscopy , Models, Molecular , Molecular Structure , Organophosphorus Compounds/chemical synthesis , Organosilicon Compounds/chemical synthesis , Spectrometry, Mass, Electrospray IonizationABSTRACT
The design and self-assembly of three supramolecular triangles is described. A novel 60 degrees corner unit directs the exclusive formation of triangular assemblies that are not in detectable equilibrium with other macrocycles. The resulting triangles have sides ranging from 2.7 to 3.5 nm in length and molecular masses as high as 5396 amu. The crystal structure of one of the assemblies shows an approximately 1.4 nm cavity; the crystal packing forms open, triangular channels. The characterization of the supramolecular triangles by multinuclear NMR, elemental analysis, and electrospray mass spectrometry is also reported.
Subject(s)
Organoplatinum Compounds/chemistry , Phenanthrenes/chemistry , Cross-Linking Reagents/chemistry , Crystallography, X-Ray , Ethylenes/chemistry , Magnetic Resonance Spectroscopy , Mass Spectrometry , Models, Molecular , Molecular Conformation , Phenanthrenes/chemical synthesis , Pyridines/chemistryABSTRACT
We provide a summary of our results in three-dimensional, coordination-driven self-assembly based on the directional-bonding methodology, in which the stoichiometric mixing of complementary building blocks, with appropriate, predefined geometries, leads to targeted, nanoscopic cages. Using this motif, we have synthesized high-symmetry ensembles resembling the Platonic solids, such as dodecahedra, and the Archimedean solids, such as truncated tetrahedra and cuboctahedra, as well as other cages, like trigonal bipyramids, adamantanoids, and trigonal prisms. The synthesis and characterization of these compounds is discussed, as is some host-guest chemistry.
Subject(s)
Models, Chemical , Models, Molecular , Macromolecular Substances , Molecular StructureABSTRACT
We report that an equilibrium mixture of triangular and square supramolecular species results when the flexible, ditopic donor unit, trans-bis(4-pyridyl)ethylene, is reacted with the ditopic acceptor unit, cis-(Me(3)P)(2)Pt(OTf)(2), in a one-to-one ratio. Both products are characterized in solution, by way of multinuclear NMR, and in the solid state, via X-ray crystallography. The effects of water and anions, cobalticarborane versus triflate, on the equilibrium are probed. The selective crystallization of either of the two species can be accomplished via the appropriate choice of solvents and ratio of anions present in the system. The dominant species in solution is not always consistent with the most prevalent species in the solid state.
Subject(s)
Anions/chemistry , Organoplatinum Compounds/chemistry , Pyridines/chemistry , Catalysis , Crystallization , Crystallography, X-Ray , Macromolecular Substances , Magnetic Resonance Spectroscopy , Molecular Conformation , Molecular Structure , TimeABSTRACT
[reaction: see text] Under the appropriate conditions, the combination of two tritopic pyridyl ligands with three metal-containing molecular "clips" spontaneously generates supramolecular coordination cages with trigonal prismatic frameworks.
Subject(s)
Organometallic Compounds/chemistry , Magnetic Resonance Spectroscopy , Spectrometry, Mass, Electrospray IonizationABSTRACT
A family of nanoscale-sized supramolecular cage compounds with a trigonal prismatic framework was prepared by means of spontaneous self-assembly from the combination of a predesigned molecular "clip" with tritopic pyridyl subunits. As confirmed by x-ray crystallography, the smallest structure of the reported series is approximately 1 x 2 nm and possesses a nitrate anion incarcerated inside its molecular cavity. The largest structure has dimensions of approximately 1 x 4 nm.
Subject(s)
Models, Chemical , Nitrates/chemistry , Anions , Crystallography, X-Ray , Macromolecular Substances , Magnetic Resonance Spectroscopy , Models, Molecular , NanotechnologyABSTRACT
Coordination-driven assembly based on manganese(II) centers and flexible 1,3-bis(4-pyridyl)propane leads to the solid-state formation of electronically neutral, self-templated homochiral helices, closed ring structures, and racemic mixtures of helices depending upon the presence or absence of guests such as benzene and 1,2-diphenylethane.
