Search results for "PHOTOCHEMISTRY"
showing 10 items of 2034 documents
Aluminum Nanocrystals as a Plasmonic Photocatalyst for Hydrogen Dissociation
2016
Hydrogen dissociation is a critical step in many hydrogenation reactions central to industrial chemical production and pollutant removal. This step typically utilizes the favorable band structure of precious metal catalysts like platinum and palladium to achieve high efficiency under mild conditions. Here we demonstrate that aluminum nanocrystals (Al NCs), when illuminated, can be used as a photocatalyst for hydrogen dissociation at room temperature and atmospheric pressure, despite the high activation barrier toward hydrogen adsorption and dissociation. We show that hot electron transfer from Al NCs to the antibonding orbitals of hydrogen molecules facilitates their dissociation. Hot elect…
Rapid Surface Functionalization of Hydrogen-Terminated Silicon by Alkyl Silanols
2017
Surface functionalization of inorganic semiconductor substrates, particularly silicon, has focused attention toward many technologically important applications, involving photovoltaic energy, biosensing and catalysis. For such modification processes, oxide-free (H-terminated) silicon surfaces are highly required, and different chemical approaches have been described in the past decades. However, their reactivity is often poor, requiring long reaction times (2-18 h) or the use of UV light (10-30 min). Here, we report a simple and rapid surface functionalization for H-terminated Si(111) surfaces using alkyl silanols. This catalyst-free surface reaction is fast (15 min at room temperature) and…
Capturing Hydrophobic Trifluoroiodomethane in Water into an M 4 L 6 Cage
2016
Synthetically important trifluoroiodomethane (CF3I) was trapped in water by using a metal–organic supramolecular anionic cage. Under ambient conditions, nearly 1:1 encapsulation of the hydrophobic, gaseous CF3I substrate with the cage was observed, and its binding constant was calculated by relative comparison with benzene encapsulation.
Selectivity in the direction of photoisomerization reactions in liquid-crystalline guest-host systems
1995
E ⇄ Z photoisomerization reactions of stilbenes la-c were studied in liquid-crystalline (LC) phases and in the corresponding isotropic melts. Whereas viscosity has a moderate influence on the photostationary states, a strong effect caused by the regular incorporation of the stilbene molecules in the LC phases was observed. The direction of the isomerization can be reversed, up to the case of a one-way isomerization Z E for the tailored guest-host system 1b/BS. Such an LC-matrix effect is of typical highly ordered (smectic) phases with free volumina which are strictly limited by hydrophobic interactions; it could not be detected in a much more mobile nematic phase. Textures based on the bire…
A versatile methodology for the controlled synthesis of photoluminescent high-boron-content dendrimers.
2013
Fluorescent star-shaped mol- ecules and dendrimers with a 1,3,5-tri- phenylbenzene moiety as the core and 3 or 9 carborane derivatives at the pe- riphery, have been prepared in very good yields by following different ap- proaches. One procedure relies on the nucleophilic substitution of Br groups in 1,3,5-tris(4-(3-bromopropoxy)phe- nyl)benzene with the monolithium salts of methyl and phenyl-o-carborane. The second method is the hydrosilylation reactions on the peripheral allyl ether functions of 1,3,5-tris(4-allyloxy-phe- nyl)benzene and 1,3,5-tris(4-(3,4,5-tris- AAA with suitable carboranyl-silanes to produce different generations of dendrimers decorated with carboranyl fragments. This ap…
New Internal-Charge-Transfer Second-Order Nonlinear Optical Chromophores Based on the Donor Ferrocenylpyrazole Moiety
2016
A series of new N-arylated ferrocenepyrazole structures, carrying different donor or acceptor substituents in the para position of the aryl ring, has been synthesized by the Chan-Lam cross-coupling reaction. The nonplanar geometric molecular structure of some of these chromophores together with their crystal packing was determined by X-ray diffraction, and the HOMO and LUMO energy levels were evaluated by electrochemical and optical measurements and by density functional theoretical (DFT) calculations. By the investigation of solvent effects and time-dependent DFT (TD-DFT) calculations, the intense electronic absorption band around 270-310 nm was confirmed to be an internal-chargetransfer (…
The Pyridyl Functional Groups Guide the Formation of Pd Nanoparticles Inside A Porous Poly(4-Vinyl-Pyridine)
2015
The reactivity of palladium acetate inside a poly(4-vinylpyridine-co-divinylbenzene) polymer is strongly influenced by the establishment of interaction between the Pd precursor and the pyridyl functional group in the polymer. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and simultaneous X-ray absorption near edge structure (XANES) and small angle X-ray scattering (SAXS) techniques have been applied to monitor the reactivity of palladium acetate in the presence of H-2 and CO as a function of temperature. H-2 reduces palladium acetate to Pd nanoparticles and acetic acid. The pyridyl groups in the polymer play a vital role both in stabilizing the formed acetic acid, thu…
A photoactivated molecular gate.
2012
Light-controlled gate: A novel capped silica nanoscopic mesoporous hybrid material for photo-driven cargo release applications has been designed and prepared. The capped system, which shows a zero release, contains a photo-cleavable bulky o-methoxybenzylamine derivative. Upon irradiation at 254¿nm, photo-degradation of the o-methoxybenzylamine framework and the subsequent delivery of a fluorescent cargo were observed
Experimental and theoretical studies on polar Diels–Alder reactions of 1-nitronaphathalene developed in ionic liquids
2013
The reactions between 1-nitronaphthalene 1 and two nucleophilic dienes, Danishefsky´s diene 2 and 1-trimethylsilyloxy-1,3-butadiene 3, to yield phenanthrenols 7 and 8 developed in protic and aprotic ionic liquids (ILs) with an imidazolium cation base permit to conclude that the reactions occur in better experimental conditions than in molecular solvents. The yields obtained with protic ILs are better than those observed with aprotic ILs. In this sense, the higher yields obtained with aprotic ILs, (working at 60ºC, 48 h) are comparable with the lower yields observed in protic ILs (60 ºC, 24 h). DFT calculations for the reaction of 1-nitronaphthalene 1 with diene 3, in the absence and in the …
Off–on BODIPY-based chemosensors for selective detection of Al3+ and Cr3+versus Fe3+ in aqueous media
2014
[EN] Two new off-on BODIPY-based chemosensors that are highly sensitive for trivalent cations in aqueous solutions are described. Compound 2 exhibits selective sensing of Al3+ and Cr3+ versus Fe3+ through two different channels (UV-vis and fluorescence).