Search results for "PHOTOCHEMISTRY"
showing 10 items of 2034 documents
Factors affecting the UV-Transparency of Molecular Sieves
1994
The optical properties in the UV-region of several types of molecular sieves were studied. The initial onset of absorption around 280 nm which was observed for basically all samles synthesized without special precautions is not due to an early onset of band gap absorption, but might be correlated to the crystal size as well as structural defects within the crystals, e.g. E'-center or peroxy-radical. Using template free synthesis procedures which lead to small crystals containing few defect sites, we were able to synthesize molevular sieves which were almost completely transparent down to 200 nm. Such crystals can become very important in the development of technical luminophores.
Decoupling the artificial special pair to slow down the rate of singlet energy transfer
2012
Trimer 2, composed of a cofacial heterobismacrocycle, octamethyl-porphyrin zinc(II) and bisarylporphyrin zinc(II) held by an anthracenyl spacer, and a flanking acceptor, bisarylporphyrin free-base ( Ar = -3,5-(t Bu )2 C 6 H 3), has been studied by means of absorption spectroscopy, "steady state and time-resolved fluorescence" and fs transient absorption spectroscopy, and density functional theory (DFT) in order to assess the effect of decoupling the chromophores' low energy MOs on the rate of the singlet, S1, energy transfer, k ET , compared to a recently reported work on a heavily coupled trimeric system, Trimer 1, [biphenylenebis(n-nonyl)porphyrin zinc(II)]-bisarylporphyrin free-base ( A…
Supramolecular order of stilbenoid dendrons: importance of weak interactions
2006
Stilbenoid dendrons with various donor and acceptor groups on the focal unit were synthesised by a Wittig–Horner reaction, starting from an aldehyde functionalised dendron and various substituted phosphonic acid esters. The target molecules are composed of meta-branched arms, two of them with extended conjugation (distyrylbenzene) and three flexible dodecyloxy chains; the focal group consists of a donor or acceptor substituted styryl unit. The cross-conjugation of the arms prevents the strong electronic influence of substituents on the two extended oligophenylenevinylene chromophores. However, intermolecular interactions mediated by the focal unit allow control of the supramolecular stackin…
Anomalous binding sequence of CO ligands to an anionic triplatinum carbonyl complex
2005
Abstract A systematic density functional theory study on the structures and binding energies of triplatinum carbonyls Pt 3 ( CO ) x q , with x = 1–6 and q = 0, −1, reveals an anomalous trend in binding energies of the CO ligands to the triangular platinum core, with the first three ligands strongly bound at terminal Pt sites, followed by weaker bound ligands at Pt–Pt bridge sites for x = 4–6. This work provides a novel explanation to the anomalous CO binding trend reported in mid-1990s from collision-induced dissociation and photodissociation experiments.
Synthesis of Areno-Condensed [24]Annulenes
2001
[24]Annulenes condensed with three phenanthrene units (11a−d) or with three chrysene ring systems (22) were prepared by multi-step syntheses. The cyclic condensation reaction in the final step led to highly symmetrical compounds. Long flexible alkoxy groups attached to the periphery enhance the solubility and give rise to a strong aggregation of the molecules which was observed in solution by NMR and fluorescence excitation spectroscopy, and in the pure state by the detection of liquid crystalline phases in differential scanning calorimetry and polarization microscopy.
The influence of sigma and pi acceptors on two-photon absorption and solvatochromism of dipolar and quadrupolar unsaturated organic compounds.
2003
Two-photon absorption cross sections delta and solvatochromic properties were determined for a series of quadrupolar and dipolar compounds by using femtosecond excitation in the spectral range between 710 and 960 nm. The compounds investigated were distyrylbenzenes and polyenes bearing appropriate pi or sigma acceptors. The delta values for the centrosymmetric compounds trans, trans- 1,4-bis[2-(2',5'-dihexyloxy)phenylethenyl]-2,3,5,6-tetrafluorobenzene (6), trans, trans-1,4-bis[2-(4'-dibutylamino)phenylethenyl]- 2,3,5,6-tetrafluorobenzene (2), trans, trans-1,4-bis[2-(4'dimethylamino)phenylbutadienyl]- 2,3,5,6-tetrafluorobenzene (7), trans,-trans-1,4-bis[2-(4'-dimethylamino)phenylethenyl]2,5…
Syntheses, crystal structures and magnetic properties of di- and trinuclear croconato-bridged copper(ii) complexes
2002
The new croconato-bridged copper(II) compounds [Cu2(terpy)2(H2O)2(C5O5)](NO3)2·H2O (1) and [Cu3(phen)5(C5O5)2](CF3SO3)2 (2) (C5O52− = croconate, dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione; terpy = 2,2′:6′,2″-terpyridine; phen = 1,10-phenanthroline) have been prepared, and their crystal structures and variable temperature magnetic susceptibilities determined. The structure of complex 1 consists of croconato-bridged dinuclear [Cu2(terpy)2(H2O)2(C5O5)]2+ complex ions, nitrate counter ions and water of hydration. The croconato ligand exhibits an asymmetrical bis-bidentate coordination mode through four of its five oxygen atoms. The two crystallographically independent copper atoms hav…
Evidence for an Intermediate in the Methylation of CB11H12−with Methyl Triflate: Comparison of Electrophilic Substitution in Cage Boranes and in Aren…
2013
The trideuteriomethylation of BH vertices in CB11H12− and its derivatives with CD3OTf (OTf=triflate, trifluoromethanesulfonate) yields a mixture of BCD3 and BCHD2 substitution products, thus demonstrating the intermediacy of a species with a long enough lifetime for hydrogen scrambling between the boron vertex and the methyl substituent. No such scrambling is observed if CD3OTf is used to methylate toluene. According to density functional theory calculations, the intermediate in BH vertex methylation is a three-center bonded σ adduct of a methyl cation to the BH bond and the proton scrambling occurs via a transition structure containing a distorted square-pyramidal methane attached axially …
Structure-reactivity relationship for aromatics transalkylation and isomerization process with TNU-9, MCM-22 and ZSM-5 zeolites, and their industrial…
2011
[EN] TNU-9 is a medium pore zeolite with a complex tridimensional channel system. Its catalytic properties have been studied in some reactions that involve the BTX fraction, such as benzene and toluene alkylation with methanol, ethanol or isopropanol. These reactions use in practice medium pore zeolites such as ZSM-5 (MFI) or MCM-22 (MWW), and the selectivities obtained with TNU-9 are compared and analyzed from the point of view of the zeolite structure and pore topology, as well as from its possible industrial application. For benzene alkylation to give ethylbenzene (EB), TNU-9 is an active and selective catalyst with selectivities to EB much higher than ZSM-5 and close to those of the ind…
Epoxidation of stilbene using supported gold nanoparticles: cumyl peroxyl radical activation at the gold nanoparticle surface.
2014
The catalytic epoxidation of cis-stilbene using cumene as a solvent in the presence of supported gold nanoparticles (AuNP) yields a mixture of cis and trans-stilbene oxides. EPR and product distribution studies support a new mechanistic proposal where oxygen centred radicals activate the AuNP surface and form active surface oxygen species responsible for the epoxidation products.