Search results for "Charge-transfer complex"
showing 9 items of 9 documents
Intermolecular oxidative dehydrogenative 3,3′-coupling of benzo[b]furans and benzo[b]thiophenes promoted by DDQ/H+: total synthesis of shandougenine B
2016
With an excess of a strong acid, 2,3-dichloro-5,6-dicyano-1,4-quinone (DDQ) is shown to promote metal-free intermolecular oxidative dehydrogenative (ODH) 3,3'-coupling of 2-aryl-benzo[b]furans and 2-aryl-benzo[b]thiophenes up to 92% yield as demonstrated with 9 substrates. Based on the analysis of oxidation potentials and molecular orbitals combined with EPR, NMR and UV-Vis observations, the studied reaction is initiated by a DDQ-substrate charge transfer complex and presumably proceeds via oxidation of the substrate into an electrophilic radical cation that further reacts with another molecule of a neutral substrate. The coupling reactivity can easily be predicted from the oxidation potent…
Theoretical study of new acceptor and donor molecules based on polycyclic aromatic hydrocarbons
2011
Functionalized polcyclic aromatic hydrocarbons (PAHs) are an interesting class of molecules in which the electronic state of the graphene-like hydrocarbon part is tuned by the functional group. Searching for new types of donor and acceptor molecules, a set of new PAHs has recently been investigated experimentally using ultraviolet photoelectron spectroscopy (UPS). In this work, the electronic structure of the PAHs is studied numerically with the help of B3LYP hybrid density functionals. Using the DELTA-SCF method, electron binding energies have been determined which affirm, specify and complement the UPS data. Symmetry properties of molecular orbitals are analyzed for a categorization and a…
The natural compound chrysosplenol-D is a novel, ultrasensitive optical sensor for detection of Cu(II)
2020
Abstract Herein, we introduce a novel, ultrasensitive optical sensor for determination of Cu(II) ions over the concentration range of 0 to 1 μM Cu(II). The optical sensor is based on the natural molecule chrysosplenol-D (Chp-D) extracted from the flowering plant Chiliadenus montanus (Vahl.) Brullo. Free Chp-D emits fluorescence at 566 nm when excited at 292 nm. Chp-D chelates Cu(II) ions to form a 1:1 (metal:ligand) complex, which quenches the fluorescence emission peak of the free probe at 566 nm. “Turn-off” luminescence could be easily determined and provided distinct proof of the chelation of Cu(II) ions by Chp-D. This novel optical sensor offers a considerable fluorescence mechanism (ch…
A Ubiquinol-Based Charge-Transfer Complex Obtained from a Solvent-Free Approach
2009
Unexpected photochemistry and charge-transfer complexes of [CB(11)H(12)](-) carborane.
2008
Although the [CB(11)H(12)](-) carborane does not exhibit an absorption band in UV, its triplet excited state can be generated upon 308 nm laser excitation; also unexpectedly carborane acts as electron donor forming a charge transfer complex with methylviologen that upon illumination gives rise to viologen radical cation.
Experimental and theoretical studies into the structural perturbations between neutral, oxidised and reduced forms of 1,4-dithiinoquinoxaline derivat…
2000
The syntheses and electrochemistry of thieno[3',4'r5,6][1,4]dithiino[2,3-b]quinoxaline (9), 2,3-bis(methylsulfanyl)[1,4]dithiino[2,3-b]quinoxaline (16) and 2,3-ethylenedisulfanyl[1,4]dithiino[2,3-b]quinoxaline (17) are reported, together with the X-ray crystal structures of 9, 16 and the charge-transfer complex 9.TCNQ. In the thieno derivative 9, the molecular structure undergoes a significant change from a boat conformer to a planar system, upon oxidation with TCNQ. Theoretical calculations show that oxidation leads to planarisation of the molecular structure due to the aromatisation of the dithiine moiety. The study of the oxidised/reduced species helps to rationalise the electrochemical …
Visible-light-induced oxidation of trans-ferulic acid by TiO2 photocatalysis
2012
Abstract The oxidation of trans-ferulic acid (C10H10O4) in aqueous TiO2 dispersion occurs via the formation of a charge-transfer complex on the TiO2 surface that is able to absorb visible light (λ ⩾ 400 nm). The main product is CO2, whereas secondary oxidation products are organic species such as vanillin, caffeic acid, homovanillic acid, and vanillylmandelic acid. Oxidation through the formation of a charge-transfer complex occurs only in the presence of specific TiO2 samples. Experiments in the absence of oxygen, in the presence of bromate ions and by using a phosphate-modified TiO2, have been carried out for investigating the reaction mechanism. In order to study the interaction between …
Synthèse de chalcones à base de tétrathiafulvalène: RC(O)CHC(CH3)TTF, TTFC(O)CHC(CH3)R (R TTF: C6H3S4; Bct: C6H5Cr(CO)3; Fc: C5H4FeC5H5). Propr…
1992
Abstract Novel chalcones that contain tetrathiafulvalene (TTF) and/or metallocene (ferrocenyl or benchrotrenyl) moieties: RC(O)CHC(CH 3 )R′ (R and/or R′ TTF: C 6 H 3 S 4 ; Fc: C 5 H 4 FeC 5 H 5 ; Bct: C 6 H 5 Cr(CO) 3 ) were prepared using TiCl 3 /Et 3 N as the condensation reagent. The 1-1 charge transfer complex with TCNQ (tetracyanoquinodimethane was obtained for the ditetrathiafulvalenic derivative (R R′ TTF). This complex exhibits the semiconducting behaviour.
2H NMR studies of phase behaviour and molecular motions of doped discotic liquid-crystalline systems
1990
Abstract A discotic triphenylene monomer as well as a dimer and a main chain polymer, all substituted with heptyloxy side groups, were doped with an electron acceptor (2,4,7-trinitrofluorenone (TNF)) to give charge transfer complexes. These doped systems were aligned in a magnetic field, thus proving their liquid crystallinity. 2H NMR measurements show that the electron acceptor molecules are incorporated into the columns built of triphenylene cores. In the charge transfer complex with the triphenylene monomer almost all the electron acceptor molecules stack in the columns even close to the clearing temperature T 1, while for the dimer and especially for the polymer a significant fraction o…