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Electronic Spectroscopy (electronic + spectroscopy)
Selected AbstractsSynthesis, Structures, and Electronic Spectroscopy of Luminescent Acetylene- and (Buta-1,3-diyne)platinum ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 3 2007Ke Zhang Abstract The electronic absorption and emission spectroscopy of a series of diphenylaceylene- and (buta-1,3-diyne)-Pt0 complexes (L)Pt[(1,2-,2)-R,(C,C)n,R] and [(dppp)Pt]2[,-(1,2-,2):(3,4-,2)-R,(C,C)2,R] {R = Ph or CH3, L = dppp or(PPh3)2, n = 1 or 2} was investigated. The structures of(dppp)Pt[(1,2-,2)-Ph,C,C,Ph], (dppp)Pt[(1,2-,2)-PhC4Ph] and [(dppp)Pt]2[,-(1,2-,2):(3,4-,2)-Ph,(C,C)2,Ph] were characterized by X-ray diffraction. The complexes all display intense absorptions that were attributed to Pt,P(d,*) and Pt,acetylene(,x*) transitions. Except for the CH3C4CH3 complexes, the complexes all exhibit two emissions at 380,550 nm and 500,800 nm. The higher energy emission could arise from the 3[P(d,*),Pt] transition, and the lower energy emission, which has a longer lifetime than the higher energy one, was attributed to the 3[acetylene(,x*),Pt] transition. The energy of the MLCT absorption and emission was affected by the electronic properties of the acetylenes and the ancillary phosphanes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Structural Diversity in the Self-Assembly of Pseudopeptidic MacrocyclesCHEMISTRY - A EUROPEAN JOURNAL, Issue 4 2010Ignacio Alfonso Dr. Abstract The self-assembling abilities of several pseudopeptidic macrocycles have been thoroughly studied both in the solid (SEM, TEM, FTIR) and in solution (NMR, UV, CD, FTIR) states. Detailed microscopy revealed large differences in the morphology of the self-assembling micro/nanostructures depending on the macrocyclic chemical structures. Self-assembly was triggered by the presence of additional methylene groups or by changing from para to meta geometry of the aromatic phenylene backbone moiety. More interestingly, the nature of the side chain also plays a fundamental role in some of the obtained nanostructures, thus producing structures from long fibers to hollow spheres. These nanostructures were obtained in different solvents and on different surfaces, thus implying that the chemical information for the self-assembly is contained in the molecular structure. Dilution NMR studies (chemical shift and self-diffusion rates) suggest the formation of incipient aggregates in solution by a combination of hydrogen-bonding and ,,, interactions, thus implicating amide and aryl groups, respectively. Electronic spectroscopy further supports the ,,, interactions because the compounds that lead to fibers show large hypochromic shifts in the UV spectra. Moreover, the fiber-forming macrocycles also showed a more intense CD signature. The hydrogen-bonding interactions within the nanostructures were also characterized by attenuated total-reflectance FTIR spectroscopy, which allowed us to monitor the complete transition from the solution to the dried nanostructure. Overall, we concluded that the self-assembly of this family of pseudopeptidic macrocycles is dictated by a synergic action of hydrogen-bonding and ,,, interactions. The feasibility and geometrical disposition of these interactions finally render a hierarchical organization, which has been rationalized with a proposal of a model. The understanding of the process at the molecular level has allowed us to prepare hybrid soft materials. [source] Photophysical and Photochemical Properties of Fluorinated and Nonfluorinated n -Propanol-Substituted Zinc PhthalocyaninesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2010lke Gürol Abstract The synthesis of symmetrical fluorinated and nonfluorinated zinc(II) phthalocyanine derivatives obtained from 4,5-dichlorophthalonitrile, 4-nitrophthalonitrile and 3-nitrophthalonitrile substituted with 2,2,3,3-tetrafluoro-1-propanol and n -propanol are described. The comparison of the photophysicochemical properties of fluorinated and nonfluorinated substituted zinc(II) phthalocyanines is reported for the first time. The new compounds have been characterized by elemental analysis, IR, 1H NMR and 19F NMR spectroscopy, electronic spectroscopy and mass spectra. The photophysical and photochemical properties of the compounds were studied in dimethyl sulfoxide (DMSO). The complexes were quenched with benzoquinone (BQ), and their fluorescence-quenching properties were investigated in the same solvent. The effects of the number of the substitution and the position on the photophysical and photochemical parameters of the zinc(II) phthalocyanines 1a,7a are also reported. Photophysical and photochemical properties of phthalocyanine complexes are very useful for photodynamic therapy (PDT) of cancer applications. In particular, high singlet-oxygen quantum yields are very important for Type II mechanisms. These complexes have good singlet-oxygen quantum yields and show potential as Type-II photosensitizers. [source] The effect of temperature on the stability of compounds used as UV-MALDI-MS matrix: 2,5-dihydroxybenzoic acid, 2,4,6-trihydroxyacetophenone, ,-cyano-4-hydroxycinnamic acid, 3,5-dimethoxy-4-hydroxycinnamic acid, nor-harmane and harmaneJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 2 2009Olga I. Tarzi Abstract The thermal stability of several commonly used crystalline matrix-assisted ultraviolet laser desorption/ionization mass spectrometry (UV-MALDI-MS) matrices, 2,5-dihydroxybenzoic acid (gentisic acid; GA), 2,4,6-trihydroxyacetophenone (THA), ,-cyano-4-hydroxycinnamic acid (CHC), 3,5-dimethoxy-4-hydroxycinnamic acid (sinapinic acid; SA), 9H-pirido[3,4-b]indole (nor-harmane; nor-Ho), 1-methyl-9H-pirido[3,4-b]indole (harmane; Ho), perchlorate of nor-harmanonium ([nor-Ho + H]+) and perchlorate of harmanonium ([Ho + H]+) was studied by heating them at their melting point and characterizing the remaining material by using different MS techniques [electron ionization mass spectrometry (EI-MS), ultraviolet laserdesorption/ionization-time-of-flight-mass spectrometry (UV-LDI-TOF-MS) and electrospray ionization-time-of-flight-mass spectrometry (ESI-TOF-MS)] as well as by thin layer chromatography analysis (TLC), electronic spectroscopy (UV-absorption, fluorescence emission and excitation spectrosco y) and 1H nuclear magnetic resonance spectroscopy (1H-NMR). In general, all compounds, except for CHC and SA, remained unchanged after fusion. CHC showed loss of CO2, yielding the trans-/cis -4-hydroxyphenylacrilonitrile mixture. This mixture was unambiguously characterized by MS and 1H-NMR spectroscopy, and its sublimation capability was demonstrated. These results explain the well-known cluster formation, fading (vanishing) and further recovering of CHC when used as a matrix in UV-MALDI-MS. Commercial SA (SA 98%; trans -SA/cis -SA 5 : 1) showed mainly cis- to- trans thermal isomerization and, with very poor yield, loss of CO2, yielding (3,,5,-dimethoxy-4,-hydroxyphenyl)-1-ethene as the decarboxilated product. These thermal conversions would not drastically affect its behavior as a UV-MALDI matrix as happens in the case of CHC. Complementary studies of the photochemical stability of these matrices in solid state were also conducted. Copyright © 2008 John Wiley & Sons, Ltd. [source] Synthesis of phase-pure SnS particles employing dithiocarbamate organotin(IV) complexes as single source precursors in thermal decomposition experimentsAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 9 2010D. C. Menezes Abstract Preparation of tin(II) sulfide, semiconductor material, has been accomplished by thermal decomposition of easily prepared organotin dithiocarbamate complexes: [Sn{S2CNEt2}2Ph2] (1), [Sn{S2CNEt2}Ph3] (2), [Sn{S2CNEt2}3Ph] (3) and [Sn{S2CN(C4H8)}2Bu2] (4). Phase-pure tin(II) sulfide has been obtained by pyrolysis of these precursors at 350 °C in N2. Thermogravimetric analysis, X-ray powder diffraction, scanning electron microscopy, X-ray electron probe microanalysis and 119Sn Mössbauer spectroscopy revealed that the complexes decompose in a single and sharp step (1 and 2), or in pseudo-single stage (3 and 4), to produce SnS. We have also measured the bandgap energies of the residues using electronic spectroscopy in the solid state and the result relates well to that in the literature for SnS, 1.3 eV. A decomposition mechanism was also proposed for each complex based on electrospray ionization tandem mass spectrometric results. The synthetic method used in this work might be useful for the preparation of pure SnS on a large scale. Copyright © 2010 John Wiley & Sons, Ltd. [source] Supramolecular Complexes Self-assembled by Copper(II) Carboxylate and Monohelical Pyridylamino LigandCHINESE JOURNAL OF CHEMISTRY, Issue 3 2006Li-Jun Zhou Abstract Two novel supramolecular complexes [Cu(bpapa)(dhbd)]·CH3OH (1) and [Cu(bpapa)(ma)]·ma (2) (bpapa=bis[6-(2-pyridylamino)pyrid-2-yl]amine, dhbd=2,3-dihydroxybutanedioate dianion, ma=, -methacrylate) were rationally designed, synthesized and characterized by single crystal X-ray diffraction, IR, electronic spectroscopy and thermogravimetric analyses. Complex 1 was the first oligo- , -pyridylamino complex based on hydroxypolycarboxylate and self-assembled into a 3D honeycomb configuration network with open channels and tubes containing 1D ladder-shaped double chains formed by hydrogen bonds and aromatic ,-, stacking interactions. Complex 2 constructed a 2D supramolecular network extended by 1D chains from dimeric supramolecular synthon through noncovalent supramolecular interactions. In the two complexes, the chelating monohelical ligand adopted all- anti configuration. Density functional theory calculations were applied to 1 and 2. [source] | ||||||||||