Photoconductive novel mesomorphic oxotitanium phthalocyanines

The synthesis and photoconductivity properties of the alkylthia and triethyleneoxysulfonyl substituted oxotitanium(IV) phthalocyanines (1a and 2a) are reported for the first time. The new compounds have been characterized by elemental analysis, IR, ¹H and ¹³C NMR spectroscopy, electronic spectroscopy and mass spectroscopy. The mesogenic properties of these new materials were studied by differential scanning calorimetry and optical microscopy. The electrical dark conductivities (σ_d) and photoconductivities (σ_ph) of deposited films of 1a and 2a were investigated in various media with different concentrations of oxygen. Molecular oxygen increases photoconductivities (σ_ph) significantly. The photoconductivity mechanism and formation of Pc⁺ which is positive charge carrier under the light irradiation of the phthalocyanine molecules are demonstrated using the theoretical calculations. The geometries of the oxotitanium(IV) phthalocyanines (TiOPc) are optimized with PM3 semi-empirical method, and their visible absorption maxima are calculated with ZINDO/S method. The results agree well with the observed values. It was found that for the calculation of visible absorption of neutral and positively charged substituted TiOPc molecules using ZINDO/S method could rapidly yield excellent results. Dipole moment, HOMO, LUMO energies and atomic charges are also calculated for clarification of the oxygen effect on the photoconductivity using PM3 and ZINDO/S methods.     

Synthesis and optical properties of perylene diimide derivatives with triphenylene-based dendrons linked at the bay positions through a conjugated ethynyl linkage

A number of groups including trimethylsilyl, phenyl, triphenylene, and triphenylene-based dendron have been linked to the bay positions of a perylene diimide (PDI) core through an ethynyl bridge. The photophysical properties of the resulting bay-substituted PDI derivatives have been carefully studied in different solvents and as thin films. Without any capping group, the two ethynyl bay-substituted PDI derivates PAT and PRT both aggregate strongly even in dilute solutions but in different perylene-perylene π–π stacking modes; PRT aggregates through slipped (or longitudinal) stacking while PAT self-assembles by rotational (or cross) stacking. With capping groups, the perylene core stacking is completely blocked for PATS in both solution and solid film. For PRTS, the slipped stacking is observed only for its film sample, while for PTB, association only occurs after excitation (excimer formation). When triphenylene or triphenylene-based G1 dendron is attached to the acetylene bridge, the resulting donor–acceptor systems (PTG0 and PTG1) exhibit strong electronic coupling between the dendritic donors and the PDI acceptor, leading to significantly red-shifted absorption bands. The conjugated linkage also facilitates photoinduced electron transfer from the triphenylene or triphenylene dendron to the PDI core, effectively quenching fluorescence emissions of both the donor and the acceptor. The significantly red-shifted absorption bands and the efficient photoinduced electron transfer observed on PTG0 and PTG1 indicate that these new PDI derivatives may find applications in solar cells.     

Cationic porphyrins with inverted pyridinium groups and their fluorescence properties

One of the applications of cationic porphyrins is their use in microbial photodynamic inactivation (PDI). For this purpose there is a constant quest for new cationic photoactive derivatives. In this work, we synthesized and fully characterized a new porphyrin 3a and the corresponding cationic derivative 3b. The results presented here show that meso-tetrakis(pentafluorophenyl)porphyrin (TPPF₂₀, 1) can be used as scaffold to prepare different soluble compounds with interesting photophysical properties.     

Diastereoselective synthesis of 4-substituted 5-(p-tolylsulfinyl)-5,6-dehydropiperidin-2-ones. A new approach to methyl l-(2S,4S)-4-methyl-6-oxopipecolate

The sulfoxide-mediated diastereoselective Michael reaction of homochiral α-sulfinylketimines 1a–d and β-substituted ene esters 2a–d (Hua's reaction) was explored. Straightforward cyclization of the open-chain adducts take place under the reaction conditions to provide the 4-substituted 5-(p-tolylsulfinyl)-5,6-dehydropiperidin-2-ones 3 and 7–12, whose stereochemistry is formed in the prior step. Furthermore, the role of the metal ion of the aza-enolate reagents and the steric demands of the O-alkyl ester group have been examined. It seems that the anti-diastereoselectivity depends on metal chelation by the oxygen of the ester as well as the oxygen of the sulfinyl group and the nitrogen in the aza-enolate ((Z)-configuration). In addition, the synthesis of methyl l-(2S,4S)-4-methyl-6-oxopipecolate has been achieved from the suitably functionalized 2-sulfinylketimine 1a (five steps; overall yield: 53–65%).     

The coating of conducting copolymer on coordination polymer nanorod: A visible light active p-n heterojunction photocatalyst for H2 production

A visible light active p-n heterojunction photocatalyst was synthesized successfully through in-situ chemical oxidation copolymerization of aniline (ANI) and diphenylamine-4-sulfonate (DPAS) with the existence of coordination polymer nanorod (CPNR) under initiation of ammonium persulfate (APS). Compared with neat coordination polymer nanorod, the resulted p-n heterojunction photocatalyst exhibits higher H₂ generationrate under visible light irradiation. In this heterojunction photocatalyst, as a p-type semiconductor possessing suitable energy levels with coordination polymer nanorod, poly-(aniline-co-N-(4-sulfophenyl)-aniline) (PAPSA) forms p-n heterojunction with n-type coordination polymer nanorod, the inner electric field of p-n heterojunction accelerates the separation of electrons and holes, which enhances H₂ production performance. Furthermore, the influence of concentration ratio between DPAS and ANI on photocatalytic property of the p-n heterojunction photocatalyst was discussed and a reasonable condition to fabricate photocatalyst with high H₂ generationrate had been obtained. During photocatalytic water splitting H₂ generation, the p-n heterojunction photocatalyst exhibited outstanding stability.     

Donor-acceptor interaction-mediated arrangement of hydrogen bonded dimers

The donor-acceptor interaction-driven supramolecular arrangement of a new series of quadruply hydrogen-bonded homo- and heterodimers have been investigated in chloroform with ¹H NMR and UV-Vis spectroscopy. Two kinds of structurally complementary monomers have been prepared. Monomers 3 and 4 are incorporated with one ureidopyrimidone unit and one electron deficient pyromellitic diimide (PDI) or naphthalene diimide (NDI) unit, respectively, monomers 5 and 6 are incorporated with two ureidopyrimidone units and one PDI or NDI unit, respectively, whereas monomers 7 and 8 consist of one electron rich bis-p-phenylene[34]crown-10 unit and one or two 2,7-diamido-1,6-naphthyridine units, respectively. Compounds 3 and 4 exist exclusively as homodimers, respectively. Adding 1 equiv. of 7 to the solution of 3·3 and 4·4 induced them to partially or fully dissociate to produce heterodimers 3·7 and 4·7 due to intermolecular donor-acceptor interaction and the formation of a new binding mode between the ureidopyrimidone of 3 or 4 and the 2,7-diamido-1,6-naphthyridine unit of 7. Both 5 and 6 exist as cyclic monomer and dimer in chloroform. Adding 1 equiv. of 8 to the solution of 5 or 6 in chloroform caused all the cyclic dimer and most of the cyclic monomer to de-cyclize to form new heterodimers 5·8 and 6·8, respectively. ¹H NMR and UV-vis study revealed that heterodimer 5·8 has a structure in which the PDI of 5 is not threaded through the cavity of the bis-p-phenylene[34]crown-10 unit of 8. In contrast, in addition to the heterodimer similar to 5·8, about 40% of heterodimer 6·8 is generated, in which the PDI of 6 is threaded through the cavity of the bis-p-phenylene[3]crown-10 unit of 8 due to the increased donor-acceptor interaction between NDI and bis-p-phenylene[34]crown-10. Steric hindrance and mismatching of the hydrogen bonding moiety play important roles in the arrangement of the new homo- and heterodimers.     

Atom transfer radical polymerisation of styrene controlled by phosphine-containing coordination compounds of Mo(III)/Mo(IV)

A controlled polymerisation of styrene has been achieved under ATRP conditions by using a phosphine-containing Mo^III/Mo^IV system. Linearity of the M_n vs conversion plot and low PDI’s are observed in bulk, in a 30% (v/v) PhCl solution, and in a chain extension experiment when using MoCl₃(PMe₃)₃/BIB. Controlled polymerisation is also observed for a reverse ATRP experiment starting from MoCl₄(PMe₃)₃/AIBN. The absence of chain transfer and termination is confirmed by NMR and MALDI–TOF analyses of polymers obtained by employing BEB and BIB as initiators. To cite this article: F. Stoffelbach et al., C. R. Chimie 5 (2002) 37–42     

Transformations of S-substituted 5,7-dimethyl-4а,5а-diphenyl-3-thioxoperhydroimidazo[4,5-e]-1,2,4-triazin-2-ones under treatment of 1,2-benzoquinones and photochemical properties of reaction products

For the first time 5,7-di-tert-butyl-1,3-dimethyl-3a,9a-diphenyl-3,3a-dihydro-1H-benzo[5,6][1,4]dioxino[2,3-d]imidazol-2(9aH)-one 13 and complex 9 of 4,6-di-tert-butyl-3-nitrobenzene-1,2-diol with 1,3-dimethyl-4,5-diphenyl-1H-imidazol-2(3H)-one 10a were prepared by the reactions of 3-alkylthio-5,7-dimethyl-4a,7a-diphenyl-4a,5,7,7a-tetrahydro-1H-imidazo[4,5-e]-1,2,4-triazin-6(4H)-ones with 3,5-di-tert-butyl-1,2-benzoquinone 1 and 4,6-di-tert-butyl-3-nitro-1,2-benzoquinone 2, respectively. Photochemical transformations of compounds 9 and 10a as well as products of its photooxygenation involving singlet oxygen under UV irradiation: urea 16, isomeric 1,3-dimethyl-4,5-diphenylimidazolidin-2-ones 17 and 17′, and compound 18 were studied by the spectral-kinetic method. Data on the absorption and fluorescence properties of synthesized compounds and their photoproducts were obtained.     

Bis(N-benzyl-N-furfuryldithiocarbamato-S,S′)mercury(II) as a precursor for the preparation of mercury sulfide nanoparticles

Bis(N-benzyl-N-furfuryldithiocarbamato-S,S′)mercury(II), [Hg(bzfdtc)₂] (1) and bis(N,N-difurfuryldithiocarbamato-S,S′)mercury(II), [Hg(dfdtc)₂] (2) were synthesized and characterized by IR, NMR and single-crystal X-ray crystallography. Single-crystal X-ray structures of 1 and 2 indicate that both complexes are dimeric, with each mercury in a distorted [HgS₅] square pyramidal geometry. The thioureide (N¹³CS₂) carbon signals were observed at 206.8 and 206.7 ppm for 1 and 2, respectively, with very weak intensity, characteristic of the quaternary carbon signal. Complex 1 has been used as a precursor for the preparation of HgS nanoparticles. The as-prepared HgS nanoparticles have been characterized by powder XRD, FESEM, EDAX, UV–visible and IR spectroscopies. FESEM images of HgS nanoparticles show that the particles are spherical in shape. The blue shift in the absorption maxima in the UV–visible spectra of HgS1 and HgS2 is a consequence of the quantum confinement effect.     

Stereochemistry of retro-diel-salder fragmentation in gas-phase ions formed by chemical ionization

Retro Diels Alder fragmentation is highly stereospecific in the diones 1 under chemical ionization conditions, both with methane and isobutane as the reagent gases. Only the cis-isomers yield abundant protonated diene and quinone ions. The isotope effect indicates preferential protonation on a CO oxygen, and a subsequent H-migration prior to the formation of the protonated diene cations in the cis isomers.     

A valuable synthetic route to spiro-cyclopropane derivatives containing multiple stereogenic centers

The unusual, functionalized spiro-cyclopropane derivatives containing four stereogenic centers 8a–8f were obtained in good yields with d.e. ≥98% via tandem double Michael addition/internal nucleophilic substitution of the novel chiral synthon, 5-l-menthyloxy-3-bromo-2(5H)-furanone 5a, with various oxygen nucleophiles under mild conditions. (S)-(−)-Ethyl lactate also reacted under the same conditions to afford the corresponding spiro-cyclopropane derivative 8g. Interestingly, reaction of 5a with ethyl bromo- and chloroacetate, in the usual manner, gave the spiro-cyclopropane 8h rather than the expected C-linked derivative. The absolute configuration of the interesting spiro-cyclopropanes 8 was established by X-ray crystallography. These results provide a valuable synthetic route to some complex molecules containing the spiro-cyclopropane skeleton with multiple stereogenic centers.     

Synthesis and photochemistry of novel bromo substituted stilbene derivatives as triplet state sensitizers for the generation of singlet oxygen

We have presented the synthesis and characterization of three new bromo substituted stilbene derivatives,p-3,4,5-trimethoxy-p'- 2,3,4,5,6-pentabromostilbene(C1),p-N,N-dimethylamino-p'-2,3,4,5,6-pentabromostilbene(C2) and p-N,N-diphenylamino-p'- 2,3,4,5,6-pentabromostilbene(C3) in this letter.The UV/vis absorption and photoluminescence were investigated in various solvents.The maximal absorption wavelength of C1 exhibited blue-shift to those of C2 and C3 in different solvents.No florescence emission could...     

Stepwise synthesis of two inorganic–organic hybrids based on the manganese monosubstituted Keggin polyanion chains

Two new hybrid compounds based on the manganese monosubstituted Keggin polyanion chains, [H₂bpy][Ag(bpy)]₂[HPMnMo₁₁O₃₉] (1) and [H₂bpy]₂[Hbpy][PMnMo₁₁O₃₉]·H₂O (2), (bpy = 4,4′-bipyridine) have been stepwise synthesized under hydrothermal condition and characterized by elemental analyses, IR spectra, thermogravimetry, and single-crystal X-ray diffraction technique. Structural characterization reveals that although both 1 and 2 contain manganese monosubstituted Keggin polyanion chains, the polyanion chains are not in the full consistent way. In 1, the neighboring manganese monosubstituted Keggin clusters are connected via sharing the para position oxygen atoms of the clusters to form a linear polyanion chain in which the monosubstituted Keggin clusters are further grafted by silver coordination polymer chains forming a 2D network. Whereas the polyanion chain in 2 exhibits a zigzag structure, which is formed by sharing the metaposition terminal oxygen atoms of the clusters, rather than para position terminal oxygen atoms as that in 1. Each zigzag chain contacts with four adjacent chains along four directions through short interspecies contacts, forming a 3D supramolecular framework. The protonated Hbipy⁺ and H₂bipy²⁺ molecules as the counter cations exist in voids of the supramolecular framework in 2. Furthermore, photocatalytic experiments indicate that 1 has good activities for photocatalytic degradation of RhB under UV irradiation.     

2-acyl-4-alk(en)yltetronic acid,a new oxidation product of hop α-acids

Singlet oxygen transforms(?)(R)-humulone 2b and (?)(R)-tetrahydrohumulone 2a into ketene radical intermediates via a radical reaction, which are intramolecularly trapped to give the 2-acyl-4-alkyl- or akenyl-tetronic acids. These are isolated as a 50:50 mixture of the two enol forms 5 and 6.     

Unexpected formation of new photochromic compounds derived from 3,3-diphenyl-3H-naphtho[2,1-b]pyran-1-one

Two new unexpected photochromic compounds were obtained from naphtho[2,1-b]pyran-1-one 1. The reaction of this ketone with the silyl enol ether methyl trimethylsilyl dimethylketene acetal, catalyzed by TiCl₄, afforded the photochromic dihydronaphtho[2,1-b]pyranone 2. The Reformatsky reaction of ketone 1 with ethyl bromoacetate led to the formation of the expected alcohol that under acid treatment gave, unexpectedly, the novel photochromic benzocoumarin 6. UV irradiation compounds 2 and 6 in solution provided thermally stable photoproducts that returned to the initial uncoloured forms under visible irradiation. The photochromic behaviour of these compounds and the structures of the photoproducts formed in these reactions were characterized by 1D and 2D NMR.     

Versatile transamination in quinonediimine chemistry: Towards a novel class of water soluble UV/violet chromophores

The transamination reaction of 2,5-diaminobenzoquinonediimine (QDI) with ethylenediamine gave fluorescent 1,2,3,4-tetrahydropyrazino[2,3-g]quinoxaline (1). When the same reaction was carried out with N,N’-bis(aminoethyl)-1,3-propanediamine, a novel cationic quinoxalinium species (2) was isolated, which can be further condensed with p-cyanobenzaldehyde to afford a benzimidazolo-fused quinoxaline dye (3) that is a water-soluble fluorophore in the UV–visible range.     

Synthesis,characterization and evaluation of biological properties of selenium nanoparticles from Solanum lycopersicum

Synthesis of nanoparticles by green synthesis has a large number of biomedical applications worldwide. In this study, Selenium Nanoparticles (SeNPs) were synthesized by using sodium salt of selenium and Solanum lycopersicum (tomato) fruit juice and seeds extract. The plant extracts were used as a reducing agent in ratio 1:4 i.e. sodium selenite salt (Na₂SeO₃). SeNPs were characterized by UV–visible spectrophotometry, FTIR and Zeta Sizer analysis. The UV-graphs indicated the highest peak of absorbance at 350 nm. Whereas, FTIR analysis of SeNPs indicated absorbance bands at 3262.35–1633.72 cm^?1. Zeta sizer analysis showed the average size of SeNPs for Fruit juice extract as 1020 d.nm. with PDI 0.432. In case of seeds extract, average size was 1155 d.nm. with PDI 0.761; and the PDI value for both extracts showed polyderse nature of these NPs. SeNPs possessed significant antimicrobial activity against selected strains of E. coli, S. aureus, M. luteus, S. enterica, B. subtilis, K. pneumoniae and P. aureginosa. The α-amylase inhibitory assay of these SeNPs indicated that they had antidiabetic role with IC₅₀ value 24.4642 µg/mL. The DPPH assay showed that SeNPs of Solanum lycopersicum have antioxidant activity with IC₅₀ value of 20.7398 µg/mL.     

A structural examination of the impact of oxygenated side chains in Ephedra compounds in the catalytic asymmetric addition of diethylzinc to aldehydes

An investigation of the impact of oxygenated side chains in Ephedra compounds on the catalytic asymmetric addition of diethylzinc to aldehydes has been conducted. (1R,2S)-Ephedrine and (1S,2S)-pseudoephedrine were alkylated with either alkyl halides or β-alkoxyalkyl halides to afford a series of ligands 9a–h and 10a–h. These compounds were employed in the enantioselective addition of diethylzinc to a variety of aldehydes. It was determined that the presence of oxygen could have a negative effect in terms of obtaining high levels of enantiomeric discrimination, but the effect is diminished with higher levels of substitution near the oxygen.     

The visible light-triggered nonvolatile memory performances in melamine-decorated <110>-oriented lead halide perovskites: A photo-responsive structural evolution insight

The exploration of novel photo/thermal-responsive nonvolatile memorizers will be beneficial for energy-saving memories. Herein, new <110>-oriented perovskites using single template melamine, i.e., [(MLAI-H₂)(PbX₄)]_n (X = Br (α-1), Cl (α-2), MLAI = melamine) have been prepared and their structures upon irradiation of visible light have been investigated. They have been fabricated as nonvolatile memory devices with structures of ITO/[(MLAI-H₂)(PbX₄)]_n/PMMA/Ag (device-1: X = Br, device-2: X = Cl), which can exhibit unique visible light-triggered binary nonvolatile memory performances. Interestingly, the silent or working status can be monitored by visible chromisms. Furthermore, the light-triggered binary resistive switching mechanisms of these ITO/[(MLAI-H₂)(PbX₄)]_n/PMMA/Ag memory devices have been clarified in terms of EPR, fluorescence, and single-crystal structural analysis. The presence of light-activated traps in <110>-oriented [(MLAI-H₂)(PbX₄)]_n perovskites are dominated in the appearance of light-triggered resistive switching behaviors, based on which the inverted internal electrical fields can be established. According to the structural analysis, the more distorted PbX₆ octahedra, higher corrugated <110>-oriented perovskite sheets, and more condensed organic-inorganic packing in Br-containing perovskite are beneficial for the stabilization of light-activated traps, which lead to the better resistive switching behavior of device-1. This work can pave a new avenue for the establishment of novel energy-saving nonvolatile memorizers used in aerospace or military industries.     

Synthesis and photochromic properties of quinoxalino[e]-annelated dimethyldihydropyrene with planar chirality

9,10-Diacetyl-2,7-di-tert-butyl-trans-10b,10c-dimethyl-10b,10c-dihydropyrene annelated with a quinoxaline unit (q-DM-DHP, 3) was prepared from 5,13-di-tert-butyl-8,16-dimethyl[2.2]metacyclophane-1,2,9,10-tetraoxide (2) and o-phenylenediamine in two steps. The photochromic isomers of q-DM-DHP 3, closed form 3a and open form 3b, were separated by reverse-phase HPLC, and their isolated UV–visible spectra were estimated. The chiral HPLC analyses of q-DM-DHP 3 indicated their planar chirality, and their CD spectra were measured. The photochromic properties and thermodynamic properties of 3 were also discussed based on their UV–visible, ¹H NMR, CD, and fluorescence spectra.