Unsymmetrical Imidazopyrimidine-Based Ligand and Bimetallic Complexes.

With bimetallic catalysts becoming increasingly important, the development of electronically and structurally diverse binucleating ligands is desired. This work describes the synthesis of unsymmetric ligand 2,7-di(pyridin-2-yl)imidazo[1,2-a]pyrimidine (dpip) that is achieved in four steps on a multigram scale in an overall 54% yield. The ability of dpip to act as a scaffold for the formation of bimetallic complexes is demonstrated with the one-step syntheses of the dicopper complex [Cu2(dpip)(µ-OH)(CF3COO)3] (4), the dipalladium complex [Pd2(dpip)(µ-OH)(CF3COO)2](CF3COO)·CF3COOH (5), and the dimeric dinickel complex [Ni4(dpip)2(µ-Cl)4Cl2MeOH6][2Cl] (6) in good yields (79-92%). All bimetallic complexes were characterized by spectroscopic methods and X-ray crystallography, which revealed metal-metal distances between 3.4821(9) and 4.106(2) Å. Additionally, quantum chemical calculations were conducted on complex 4 and an analogous 1,8-naphthyridine-based dicopper complex to investigate the differences between the imidazopyrimidine motif reported here and the widely used 1,8-naphthyridine motif. Natural bonding orbital (NBO) and Mayer bond order (MBO) analyses validated the ability of dpip to coordinate metals more strongly. Finally, NBO calculations quantified the differences in the binding energy between the two pockets of the unsymmetrical dpip ligand.

N-Oxide S-O chalcogen bonding in conjugated materials.

Non-covalent bonding interactions, such as chalcogen bonding, can have a substantial effect on the electronic and physical properties of conjugated polymers and is largely dependent on the strength of interaction. Functional groups that are traditionally used to instill chalcogen bonding such as alkoxy or fluorine substituents can demand challenging synthetic effort, as well as have drastic effects on the electronics of a π-system. The incorporation of a N-oxide functionality into bithiazole-containing materials, a synthetically simple transformation, has been entirely overlooked until now. A systematic analysis of the effects of N-oxidation on the electronic and physical properties of bithiazole-containing materials has been undertaken. N-Oxidation has been found to affect the electronic band gap through increase of the HOMO and lowering of the LUMO. Furthermore, exceptionally strong intramolecular S-O chalcogen bonding interactions in the bithiazole core contribute to rigidification of the conjugated system. Computational analysis of this system has shown this N-oxide chalcogen bonding interaction to be significantly stronger than other chalcogen bonding interactions commonly exploited in conjugated materials.

π-Concave Hosts for Curved Carbon Nanomaterials.

Carbon nanomaterials have been at the forefront of nanotechnology since its inception. At the heart of this research are the curved carbon nanomaterial families: fullerenes and carbon nanotubes. While both have incredible properties that have been capitalized upon in a wide variety of applications, there is an aspect that is not commonly exploited by nanoscientists and organic chemists alike: the interaction of curved carbon nanomaterials with curved organic small molecules. By taking advantage of these interactions, new avenues are opened for the use of fullerenes and carbon nanotubes.

Orientation Control of Molecularly Functionalized Surfaces Applied to the Simultaneous Alignment and Sorting of Carbon Nanotubes.

Self-assembly has been relied upon for molecular alignment in many advanced technological applications. However, although effective, it is inherently limited in its capability for optimization. Despite the potential benefits, the seemingly fundamental strategy of external orientation control has yet to be realized. Herein we demonstrate an approach that allows control of the orientation of small molecules covalently bound to a surface. The method exploits an alignment relay technique, passing alignment information through a liquid-crystal medium to small molecules to control surface functionalization events. The method is technically simple and can be carried out on a bench top without the need for specialized equipment. Moreover, we demonstrate the utility of the resulting surfaces to address two long-standing problems in nanoscience: the sorting and alignment of single-walled carbon nanotubes. This new method enabled significant alignment of the nanotubes as well as length and diameter sorting.

Copper-Mediated Nucleophilic Addition/Cascade Cyclization of Aryl Diynes.

Treatment of diyne substrates with sulfinate salts under the action of copper(II) triflate results in a cascade cyclization reaction. The reaction involves nucleophilic addition of the sulfinate and formation of two new C-C bonds with concomitant cleavage of an aryl C-H bond. The reaction proceeds in good yields with a range of diyne precursors and sulfinate salts. Preliminary mechanistic analysis reveals a rare example of an operative ionic mechanism in contrast to other related cyclizations.

Dithiolodithiole as a building block for conjugated materials.

The development of new conjugated organic materials for dyes, sensors, imaging, and flexible light emitting diodes, field-effect transistors, and photovoltaics has largely relied upon assembling π-conjugated molecules and polymers from a limited number of building blocks. The use of the dithiolodithiole heterocycle as a conjugated building block for organic materials is described. The resulting materials exhibit complimentary properties to widely used thiophene analogues, such as stronger donor characteristics, high crystallinity, and a decreased HOMO-LUMO gap. The dithiolodithiole (C4S4) motif is readily synthetically accessible using catalytic processes, and both the molecular and bulk properties of materials based on this building block can be tuned by judicious choice of substituents.

Polycyclic aromatic triptycenes: oxygen substitution cyclization strategies.

The cyclization and planarization of polycyclic aromatic hydrocarbons with concomitant oxygen substitution was achieved through acid catalyzed transetherification and oxygen-radical reactions. The triptycene scaffold enforces proximity of the alcohol and arene reacting partners and confers significant rigidity to the resulting π-system, expanding the tool set of iptycenes for materials applications.

A catalytic tethering strategy: simple aldehydes catalyze intermolecular alkene hydroaminations.

Herein we describe a catalytic tethering strategy in which simple aldehyde precatalysts enable, through temporary intramolecularity, room-temperature intermolecular hydroamination reactivity and the synthesis of vicinal diamines. The catalyst allows the formation of a mixed aminal from an allylic amine and a hydroxylamine, resulting in a facile intramolecular hydroamination event. The promising enantioselectivities obtained with a chiral aldehyde also highlight the potential of this catalytic tethering approach in asymmetric catalysis and demonstrate that efficient enantioinduction relying only on temporary intramolecularity is possible.

Rhodium(III)-catalyzed intermolecular hydroarylation of alkynes.

The rhodium(III)-catalyzed hydroarylation of internal alkynes is described. Good yields are obtained for a variety of alkynes, and excellent regioselectivity is observed for unsymmetrically substituted alkynes. The reaction also gives good yields for a range of arenes. Preliminary mechanistic investigations suggest that this reaction proceeds through arene metalation with the cationic rhodium catalyst, which enables challenging intermolecular reactivity.