0000000001313186
AUTHOR
Hai-jun Xu
showing 18 related works from this author
Electrochemical and Spectroelectrochemical Properties of Free-Base Pyridyl- and N -Alkyl-4-Pyridylporphyrins in Nonaqueous Media
2015
International audience; Twelve structurally related pyridyl and meso-N-methylpyridylporphyrin derivatives are investigated electrochemically in different nonaqueous media. The UV/Vis spectrum of each newly investigated porphyrin was measured before and after electro-reduction and, based on this data, the site of electron transfer is proposed. An interaction occurs between the meso-pyridyl or meso-N-alkyl-4-pyridyl substituents and the porphyrin p-ring system, the magnitude of which depends upon the number of linked pyridyl or N-alkyl-4-pyridyl groups in the compound, the solvent, the supporting electrolyte, and/or other anions added to the solution.
Self-Assembled Molecular Rafts at Liquid|Liquid Interfaces for Four-Electron Oxygen Reduction
2011
The self-assembly of the oppositely charged water-soluble porphyrins, cobalt tetramethylpyridinium porphyrin (CoTMPyP(4+)) and cobalt tetrasulphonatophenyl porphyrin (CoTPPS(4-)), at the interface with an organic solvent to form molecular "rafts", provides an excellent catalyst to perform the interfacial four-electron reduction of oxygen by lipophilic electron donors such as tetrathiafulvalene (TTF). The catalytic activity and selectivity of the self-assembled catalyst toward the four-electron pathway was found to be as good as that of the Pacman type cofacial cobalt porphyrins. The assembly has been characterized by UV-visible spectroscopy, Surface Second Harmonic Generation, and Scanning …
Very fast singlet and triplet energy transfers in a tri-chromophoric porphyrin dyad aided by the truxene platform
2015
A trichromophoric dyad composed of an octa-β-alkyl-palladium(II)porphyrin (donor) and two tri-meso-aryl-zinc(II)porphyrins (acceptors) held by a truxene spacer exhibits very fast rates for triplet energy transfers at 77 (kET(T1) = 1.63 × 108 s-1) and 298 K (kET(T1) = 3.44 × 108 s-1), whereas the corresponding singlet energy transfer rates, kET(S1) = 3.9 × 1010 s-1 (77 K) and kET(S1) = 6.0 × 1010 s-1 (298 K), are also considered fast. The interpretation for these results is that the energy transfer processes proceed via a through bond Dexter mechanism (i.e. double electron exchange) supported by comparison with literature data and evidence for a moderate MO coupling between the donor and ac…
Shape-persistent poly-porphyrins assembled by a central truxene: synthesis, structure, and singlet energy transfer behaviors
2013
Four dyad systems composed of a central truxene and either one or three β-substituted zinc(II) porphyrins (ZnP: TruZnP (7) and TruTriZnP (9)) or free-bases (H2P: TruP (6) and TruTriP (8)) have been prepared. The presence of β-methyl groups minimizes π-conjugation through the quasi right angle made by the porphyrin and the truxene planes, and renders these dyads relatively rigid. The position of the absorption and emission 0–0 peaks confirms the role of the truxene and porphyrin as the energy donor and acceptor, respectively. Selective excitation of the truxene results in an efficient singlet energy transfer (S1 ET) from the truxene to the porphyrin unit. The rates for S1 ET (k ET ) are ext…
Harnessing nature's insights: synthetic small molecules with peroxidase-mimicking DNAzyme properties.
2011
International audience
Excited State N−H Tautomer Selectivity in the Singlet Energy Transfer of a Zinc(II)-Porphyrin-Truxene-Corrole Assembly
2017
International audience; An original corrole-containing polyad for S-1 energy transfer, in which one zinc(II)-porphyrin donor is linked to two free-base corrole acceptors by a truxene linker, is reported. This polyad exhibits a rapid zinc(II)-porphyrin*free-base corrole transfer (4.83x10(10)s(-1); 298K), even faster than the tautomerization in the excited state processes taking advantage of the good electronic communication provided by the truxene bridge. Importantly, the energy transfer process shows approximately 3-fold selectivity for one corrole N-H tautomer over the other even at low temperature (77K). This selectivity is due to the difference in the J-integral being effective in both t…
Design of guanidinium porphyrins as potential G-quadruplex ligands
2012
We report herein an easy and smooth synthesis of two novel tetra-meso-substituted porphyrins bearing terminal guanidinium functionalities. These two guanidine derivatives are the porphyrin-based analogs of ZnPC , a closely related phthalocyanine-based molecule with four guanidinium arms already reported as an efficient G-quadruplex ligand.
Room temperature ionic liquids based on cationic porphyrin derivatives and tetrakis(pentafluorophenyl)borate anion
2011
A series of 11 low melting ionic liquids based on meso-substituted A3B -porphyrins and A2B2-porphyrins containing one or two pyridyl substituents have been synthesized in high yields. Three of them are liquids at room temperature. All these porphyrinic salts were characterized by1H NMR,19F NMR, MALDI-TOF mass spectrometry, elemental analysis and UV-visible spectroscopy. The thermal properties and conductivity values of these salt derivatives have been also measured. A specific conductivity value of up to 4 mS.cm-1could be obtained for a compound having the counter-anion B(C6F5)4-.
Interfacial Self-Assembly of Water-Soluble Cationic Porphyrins for the Reduction of Oxygen to Water
2012
Meet at the border: Assembly of the water-soluble cobalt tetrakis(N-methylpyridinium-4-yl)porphyrin [CoTMPyP]4+ at soft interfaces is enhanced and stabilized by its interfacial interaction with the lipophilic anion (C6F5)4B−. The supramolecular structure thus formed (see picture) provides excellent catalytic activity in the four-electron reduction of oxygen.
Antenna effects in truxene-bridged BODIPY triarylzinc(ii)porphyrin dyads: evidence for a dual Dexter–Förster mechanism
2014
The antenna process from an energy donor (BODIPY; 4′,4′-difluoro-1′,3′,5′,7′-tetramethyl-4′-bora-3a′,4a′-diaza-s-indacene) in its singlet state to two acceptors (two zinc(II) 5,15-p-tolyl-10-phenylporphyrin) bridged by a central truxene residue (5′,5′′,10′,10′′,15′,15′′-hexabutyltruxene), 5, has been analysed by means of comparison of the energy transfer rates with those of a structurally similar β-substituted BODIPY-(zinc(II) 5,10,15-p-tolyl-porphyrin), 6, where no conjugation is present between the donor and the two acceptors using the Forster resonance energy transfer (FRET) approximation. It is estimated that the energy transfer in 5 operates mostly via a Dexter mechanism (>99%), and th…
Porphyrin-templated synthetic G-quartet (PorphySQ): a second prototype of G-quartet-based G-quadruplex ligand.
2012
Template-assembled synthetic G-quartet (TASQ) has been reported recently as a G-quadruplex ligand interacting with DNA according to an unprecedented, nature-inspired ‘like likes like’ approach, based on the association between two G-quartets, one being native (quadruplex) and the other one artificial (ligand). Herein, a novel TASQ-based ligand is designed, synthesized and its quadruplex-recognition properties are evaluated in vitro: PorphySQ (for porphyrin-templated synthetic G-quartet) displays enhanced quadruplex recognition properties as compared to the very first reported prototype (DOTASQ, for DOTA-templated synthetic G-quartet), since the porphyrin template insures a more stable intra…
Origin of the temperature dependence of the rate of singlet energy transfer in a three-component truxene-bridged dyads
2014
We report a truxene-based dyad built upon one donor (tri-meso-phenylzinc(II)porphyrin) and two acceptors (octa-β-alkylporphyrin free base) in which the donor exhibits free rotation around a Ctruxene-Cmeso single bond at 298 K in fluid solution but not at 77 K in a glass matrix, whereas the acceptors have very limited motion as they are blocked by β-methyl groups. This case is interesting because all the structural and spectroscopic parameters affecting the rate for singlet energy transfer according to a Förster Resonance Energy Transfer are only weakly temperature dependent, leaving only the Dexter mechanism explaining the larger variation in rate of energy transfers with the temperature h…
Biomimetic oxygen reduction by cofacial porphyrins at a liquid-liquid interface.
2012
Oxygen reduction catalyzed by cofacial metalloporphyrins at the 1,2-dichlorobenzene−water interface was studied with two lipophilic electron donors of similar driving force, 1,1'-dimethylferrocene (DMFc) and tetrathiafulvalene (TTF). The reaction produces mainly water and some hydrogen peroxide, but the mediator has a significant effect on the selectivity, as DMFc and the porphyrins themselves catalyze the decomposition and the further reduction of hydrogen peroxide. Density functional theory calculations indicate that the biscobaltporphyr- in, 4,5-bis(5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl))-9,9-dimethylxanthene, Co2(DPX), actually catalyzes oxygen reduction to hydrogen p…
CCDC 1830060: Experimental Crystal Structure Determination
2019
Related Article: Jian Yang, Yoann Rousselin, Léo Bucher, Nicolas Desbois, Frédéric Bolze, Hai-Jun Xu, Claude P. Gros|2018|ChemPlusChem|83|838|doi:10.1002/cplu.201800361
CCDC 852358: Experimental Crystal Structure Determination
2013
Related Article: Hai-Jun Xu, P.Richard, J.-M.Barbe, C.P.Gros|2012|J.Porphyrins Phthalocyanines|16|1073|doi:10.1142/S108842461250109X
CCDC 1830057: Experimental Crystal Structure Determination
2019
Related Article: Jian Yang, Yoann Rousselin, Léo Bucher, Nicolas Desbois, Frédéric Bolze, Hai-Jun Xu, Claude P. Gros|2018|ChemPlusChem|83|838|doi:10.1002/cplu.201800361
CCDC 1830059: Experimental Crystal Structure Determination
2019
Related Article: Jian Yang, Yoann Rousselin, Léo Bucher, Nicolas Desbois, Frédéric Bolze, Hai-Jun Xu, Claude P. Gros|2018|ChemPlusChem|83|838|doi:10.1002/cplu.201800361
CCDC 1830058: Experimental Crystal Structure Determination
2019
Related Article: Jian Yang, Yoann Rousselin, Léo Bucher, Nicolas Desbois, Frédéric Bolze, Hai-Jun Xu, Claude P. Gros|2018|ChemPlusChem|83|838|doi:10.1002/cplu.201800361