RESUMO
We have investigated the temperature-dependent behavior of thiolated azobenzene molecules on Au(111) using scanning tunneling microscopy. The addition of a thiol functional group to azobenzene molecules leads to increased surface anchoring of single azobenzene molecules to gold. Thiolated azobenzene shows diverse surface morphology and does not form well-ordered structures at low coverage. At elevated temperatures, anchored molecules are observed to spin in place via hindered rotation. By measuring the number of rotating molecules as a function of temperature and using a simple model, we are able to estimate the energy barrier and attempt frequency for thermally induced hindered rotation to be 102+/-3 meV and 110+/-2 GHz, respectively.
Assuntos
Compostos Azo/química , Ouro/química , Compostos de Sulfidrila/química , Termodinâmica , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
Photomechanical switching (photoisomerization) of molecules at a surface is found to strongly depend on molecule-molecule interactions and molecule-surface orientation. Scanning tunneling microscopy was used to image photoswitching behavior in the single-molecule limit of tetra-tert-butyl-azobenzene molecules adsorbed onto Au(111) at 30 K. Photoswitching behavior varied strongly with surface molecular island structure, and self-patterned stripes of switching and nonswitching regions were observed having approximately 10 nm pitch. These findings can be summarized into photoswitching selection rules that highlight the important role played by a molecule's nanoscale environment in determining its switching properties.
Assuntos
Nanotecnologia/instrumentação , Propriedades de Superfície , Adsorção , Algoritmos , Ouro/química , Luz , Microscopia de Tunelamento/métodos , Modelos Moleculares , Conformação Molecular , Estrutura Molecular , Nanoestruturas/química , Nanotecnologia/métodos , Temperatura , Raios UltravioletaRESUMO
We have observed reversible light-induced mechanical switching for individual organic molecules bound to a metal surface. Scanning tunneling microscopy (STM) was used to image the features of individual azobenzene molecules on Au(111) before and after reversibly cycling their mechanical structure between trans and cis states using light. Azobenzene molecules were engineered to increase their surface photomechanical activity by attaching varying numbers of tert-butyl (TB) ligands ("legs") to the azobenzene phenyl rings. STM images show that increasing the number of TB legs "lifts" the azobenzene molecules from the substrate, thereby increasing molecular photomechanical activity by decreasing molecule-surface coupling.
RESUMO
A set of 20 novel [2.2]paracyclophane ketimines with planar and central chirality has been synthesized from enantiomerically pure and racemic 5-acyl-4-hydroxy[2.2]paracyclophane and alpha-branched chiral amines. Their X-ray structures were determined to elucidate the three-dimensional structures and the absolute configuration. The ketimines were used as catalysts in the asymmetric 1,2-addition reactions of diethylzinc with substituted benzaldehydes to furnish chiral alcohols in up to 95 % ee.
RESUMO
A range of di- and tri-substituted triazenes have been synthesized from a polymer-supported diazonium salt and various primary and secondary amines. The triazenes obtained were treated with transition metal salts to form polymer-supported metal complexes in firstly a general screen and then in a specific manner.
Assuntos
Paládio/química , Polímeros/química , Rutênio/química , Triazenos/química , Aminas/química , Catálise , Química Orgânica/métodos , Técnicas de Química Combinatória , Compostos de Diazônio/química , Ligantes , Compostos Organometálicos/síntese química , Compostos Organometálicos/química , Triazenos/síntese químicaRESUMO
A range of polymer-supported triazenes and their metal-bound analogues were screened for use in catalysis. Fe, Cu and Zr complexes were, together with the polymer-supported triazene ligand alone, screened in the addition of Et(2)Zn to benzaldehyde. A supported Pd triazene complex was screened for activity in Suzuki and Sonogashira reactions and a supported Ru triazene complex screened for transfer hydrogenation.