UV-vis Electronic Absorption Research Articles

Photophysical and photochemical properties of novel peripherally triethyleneoxysulfanyl substituted monomeric and Si–Si bonded dimeric silicon phthalocyanines

Monomeric and Si–Si bonded dimeric silicon(IV) phthalocyanines bearing 4[Formula: see text],7[Formula: see text],10[Formula: see text]-trioxaundecylsulfanyl groups were synthesized. These novel phthalocyanine derivatives were characterized by general analysis methods such as FT-IR, MALDI-TOF or HRMS, 1H NMR and UV-vis electronic absorption. Their aggregation behaviors were described in dimethyl sulfoxide (DMSO). In addition, the photophysical and photochemical properties of these phthalocyanines were also investigated in DMSO to determine potential of these phthalocyanines to acts as photosensitizer for photodynamic therapy (PDT) of cancer. Their high singlet oxygen generation demonstrated their suitability for PDT applications. These peripherally 4[Formula: see text],7[Formula: see text],10[Formula: see text]-trioxaundecylsulfanyl substituted silicon(IV) phthalocyanines are promising Type II photosensitizers owing to their favorable singlet oxygen generation capability. In addition, their fluorescence quenching behavior by 1,4-benzoquinone were also studied in DMSO.

TTF based donor-pi-acceptor dyads synthesized for NLO applications

Two new TTF-pi-acceptor dyads that contain p-nitrophenyl group as acceptor and bis-(styryl)benzene system as an efficient π−conjugated bridge have been synthesized by multistep synthetic procedure and their electrochemical behavior has been studied by cyclic voltammetry (CV). The occurrence of an intramolecular charge transfer (ICT) in these molecules has been evidenced by UV–Visible electronic absorption spectroscopy and these studies were completed by DFT calculations in both gas phase and in solution. The nonlinear optical parameters obtained via SHG and THG measurements are described and indicate that these materials are valuable candidates for the construction of optoelectronic and photonic devices. The Optical Kerr Effect measurements indicate that these materials exhibit a great potential in the field of optical switchers construction, where the material's photoresponse time is a crucial parameter.

Synthesis of novel anthraquinones: Molecular structure, molecular chemical reactivity descriptors and interactions with DNA as antibiotic and anti-cancer drugs

Anthraquinones are well-known anticancer drugs. Anthraquinones anticancer drugs carry out their cytotoxic activities through their interaction with DNA, and inhibition of topoisomerase II activity. Anthraquinones (AQ5 and AQ5H) were synthesized and studied with 1,5-DAAQ by computational and experimental tools. The purpose of this study is to shade more light on mechanism of interaction between anthraquinone DNA affinic agents and different types of DNA. This study will lead to gain of information useful for drug design and development. Molecular structures were optimized using DFT B3LYP/6-31 + G(d). Depending on intramolecular hydrogen bonding interactions four conformers of AQ5 were detected within the range of about 42 kcal/mol. Molecular reactivity of the anthraquinone compounds was explored using global and condensed descriptors (electrophilicity and Fukui functions). NMR and UV–VIS electronic absorption spectra of anthraquinones/DNA were investigated at the physiological pH. The interaction of the anthraquinones (AQ5 and AQ5H) were studied with different DNA namely, calf thymus DNA, (Poly[dA].Poly[dT]) and (Poly[dG].Poly[dC]). UV–VIS electronic absorption spectral data were employed to measure the affinity constants of drug/DNA binding using Scatchard analysis. NMR study confirms qualitatively the drug/DNA interaction in terms of peak shift and broadening.

Octa-BODIPY derivative dendrimeric cyclotetraphosphazenes; photophysical properties and fluorescent chemosensor for Co2 + ions

We have designed and synthesized the first examples of fluorescent chemosensors based on octa-BODIPY decorated dendrimeric cyclotetraphosphazenes. The structures these synthesized compounds were verified by 1H, 13C, 31P NMR spectroscopies and UV–vis electronic absorption spectra. The photophysical and metal sensing properties in THF solutions of dendrimeric cyclotetraphosphazenes (OBCP 1–3) were investigated by fluorescence spectroscopy. OBCP 1–3 showed strong absorption in the 500–640nm region with high molar extinction coefficients. Additionally, octa-BODIPY decorated dendrimeric cyclotetraphosphazenes are candidate for fluorescent chemosensor for Co2+ showing high selectivity with a low limit of detection.

Manganese(IV) complex with a polydentate Schiff base ligand: synthesis, crystal structure, TDDFT calculation, electronic absorption and EPR spectral study

A six-coordinate Mn(IV) complex, [Mn(H2L)2] (1) [H4L = 2-methoxy-6-(tris(hydroxymethyl)methyliminomethyl)phenol], was synthesized and characterized by elemental analysis, single-crystal X-ray crystallography, FTIR, UV–Vis electronic absorption, and EPR spectroscopy. The single-crystal structural determination reveals that the complex crystallizes in tetragonal space group P41212 and the tridentate Schiff base ligands are arranged in mer configuration chelating manganese, which exhibits as slightly distorted octahedral coordination sphere with a N2O4 chromophore. Weak hydrogen bonding interactions of uncoordinated hydroxyl groups result in a 2-D supramolecular structure. The UV–Vis electronic absorption and IR spectral data of 1 have been compared with the results obtained by employing DFT and time-dependent density functional theory calculation using B3LYP, B3PW91, and MPW1PW91 functionals, with 6-31G (d-p) and LanL2MB basis sets. The results of these calculations are functional-dependent and, among those used, B3PW91 proved to better reproduce the experimental results.

Interaction of anthraquinone anti-cancer drugs with DNA:Experimental and computational quantum chemical study

Anthraquinones form the basis of several anticancer drugs. Anthraquinones anticancer drugs carry out their cytotoxic activities through their interaction with DNA, and inhibition of topoisomerase II activity. Anthraquinones (AQ4 and AQ4H) were synthesized and studied along with 1,4-DAAQ by computational and experimental tools. The purpose of this study is to shade more light on mechanism of interaction between anthraquinone DNA affinic agents and different types of DNA. This study will lead to gain of information useful for drug design and development. Molecular structures were optimized using DFT B3LYP/6-31 + G(d). Depending on intramolecular hydrogen bonding interactions two conformers of AQ4 were detected and computed as 25.667 kcal/mol apart. Molecular reactivity of the anthraquinone compounds was explored using global and condensed descriptors (electrophilicity and Fukui functions). Molecular docking studies for the inhibition of CDK2 and DNA binding were carried out to explore the anti cancer potency of these drugs. NMR and UV-VIS electronic absorption spectra of anthraquinones/DNA were investigated at the physiological pH. The interaction of the three anthraquinones (AQ4, AQ4H and 1,4-DAAQ) were studied with three DNA (calf thymus DNA, (Poly[dA].Poly[dT]) and (Poly[dG].Poly[dC]). NMR study shows a qualitative pattern of drug/DNA interaction in terms of band shift and broadening. UV-VIS electronic absorption spectra were employed to measure the affinity constants of drug/DNA binding using Scatchard analysis.

Structure and Spectroscopy of o-anisidine Investigated by Density Functional Theory in Comparison with Experiments

The molecular structures, vibrational spectra (IR and Raman), UV-Vis electronic absorption spectra, and NMR spectra (13C and 1H) of o-anisidine have been investigated in terms of density functional theory by using B3LYP as a density functional and 6-311++G** as a basis set. Two stable and virtually degenerate conformers arising from non-planarity of the amino group of o-anisidine have been located at the room temperature. All normal modes of o-anisidine have been assigned in terms of percent contributions of the internal motions. All main electronic transitions in the UV-Vis spectrum of o-anisidine have been assigned. Solution that increases ionization potential of o-anisidine but decreases its electron affinity has been shown to affect the unoccupied orbitals of o-anisidine drastically, which shift all electronic absorption bands to longer wavelengths. The frontier molecular orbital, molecular electrostatic potential map, and atomic charge (Mulliken, ESP, and NBO) analyses have been shown useful in estimating both global and atom-inmolecule characteristics of o-anisidine. The present chemical shift calculations allow certain assignments of the experimental 13C and 1H NMR signals of o-anisidine. The high correlations between the experimental and the present computational spectral data indicate that the computational route presented in this study can be extended for the spectroscopic calculations of analogous compounds.

Structural, Spectral (IR and UV/Visible) and Thermodynamic Properties of Some 3d Transition Metal(II) Chloride Complexes of Glyoxime and Its Derivatives: A DFT and TD-DFT Study

Metal complexes bearing vic-dioxime ligands have been extensively used as analytical and biochemical reagents, and are well-known antimicrobial agents. Herein is reported a DFT study on the molecular structures, thermodynamic properties, chemical reactivity and spectral properties of some 3d metal(II) chloride complexes of glyoxime. The functionals B3LYP and CAM-B3LYP have each been used in conjunction with LANL2DZ for the metal(II) ions (Fe2+, Co2+, Ni2+ and Cu2+) and the Poplestyle basis set 6-31G+(d,p) for the rest of the elements, to perform theoretical calculations. The metal complexation abilities of the glyoxime ligands studied in this work have been evaluated on the basis of metal-ligand binding energies. These ligands were found to have high affinities towards Ni(II) and Fe(II) ions, and all complexation reactions were found to be thermodynamically feasible. Ligand-to-metal electron donations in the complexes studied have been revealed by natural population analysis. The fully optimized geometries of the complexes have adopted square planar structures around the central metal ions. On the basis of orbital composition analysis, the UV-Vis electronic absorption bands of these molecules have been attributed mainly to MLCT, LMCT and d-d electronic transitions involving metal-based orbitals.

Synthesis and characterization of aluminum nitroxide complexes

We report the synthesis of aluminum complexes of pyridyl nitroxide (RpyNO−) ligands. The dimeric complexes {(μ-pyNO−)Al(CH3)2}2 (1) and {(μ-CH3pyNO−)Al(CH3)2}2 (2) were prepared through the 1:1 reaction between the pyridyl hydroxylamine ligand precursors RpyNOH and trimethylaluminum. Both compounds were characterized by 1H and 13C NMR spectroscopies. X-ray structural analysis revealed that 1 and 2 are isostructural, with the dimer structure resulting from an Al2O2 core. Reaction of pyNOH with two equivalents of trimethylaluminum yielded the aluminum complex (pyNO−)AlMe2·AlMe3 (3), which was also characterized by 1H and 13C NMR spectroscopies and single-molecule X-ray diffraction. The electronic structure of the {(μ-pyNO−)Al(CH3)2}2 and {(μ-CH3pyNO−)Al(CH3)2}2 complexes were interrogated using UV–Vis electronic absorption spectroscopy and electrochemistry. The cyclic voltammograms of the complexes show two separate oxidation processes, the potentials of which are both dependent on the substitution pattern of the RpyNO− ligands.

Synthesis and Characterization of Aluminum Complexes of Redox-Active Pyridyl Nitroxide Ligands.

The aluminum complexes ((R)pyNO(-))2AlCl ((R)pyNO(-) = N-tert-butyl-N-(2-pyridyl)nitroxyl; R = H (1), CH3 (2), CF3 (3)) were prepared in 80-98% yield through the protonolysis reaction between the pyridyl hydroxylamine ligand precursors (R)pyNOH and dimethylaluminum chloride. Complex 1 was also prepared using a salt metathesis route in 92% yield. Complexes 1-3 were characterized using (1)H and (13)C NMR spectroscopies. Single-crystal X-ray diffraction analysis of the complexes revealed that 1-3 are isostructural, with the Al(III) cation in all cases being five coordinate with distorted square pyramidal geometries. The geometry of complex 1 was studied using DFT, which showed primarily ligand-based frontier molecular orbitals. Reaction of 1 with NaOt-Bu gave (pyNO(-))2AlOt-Bu (4), while reaction of 1 with AgBPh4 gave [(pyNO(-))2Al(THF)2][BPh4] (5) in 54% and 87% yields, respectively. Compounds 4 and 5 were both characterized using (1)H and (13)C NMR spectroscopies and compound 5 by X-ray diffraction. Complexes 1-5 were also characterized by UV-vis electronic absorption spectroscopy and electrochemistry. The cyclic voltammograms of the complexes show two separate oxidation process, the potentials of which are dependent on both the substitution pattern of the (R)pyNO(-) ligands and the anion that completes the aluminum coordination sphere. A correlation was determined between the chemical shift of the t-Bu of the (R)pyNO(-) ligand in the (1)H NMR spectroscopy and the potentials of the redox events for complexes 1-4.

Monofunctional amines substituted fluorenylidene bridged cyclotriphosphazenes: ‘Turn-off’ fluorescence chemosensors for Cu2+ and Fe3+ ions

In the present work, the reaction of 2,2,4,4-tetra(anilino)-6,6-dichlorocyclotriphosphazene (4) and 2,2,4,4-tetra(2-naphthylamino)-6,6-dichlorocyclotriphosphazene (5) with 4,4′-(9-fluorenylidene)diphenol, FDP, (6) and 4,4′-(9-fluorenylidene)dianiline FDA (7) were studied in THF and new aniline (8 and 9) and 2-naphthylamine (10 and 11) substituted FDP-bridged cyclotriphosphazenes and aniline (12) and 2-naphthylamine (13) substituted FDA-bridged cyclotriphosphazene derivatives were obtained. All newly synthesized monofunctional amines substituted fluorenylidene bridged cyclotriphosphazenes (8–13) were fully characterized by elemental analysis, 1H and 31P NMR spectroscopies, MALDI-TOF mass spectrometry and UV–Vis electronic absorption spectra. The florescence properties of the synthesized new compounds were studied. The chemosensory behavior of the compounds against to metal ions was also investigated. The obtained fluorenylidene bridged 2-naphthylamine substituted cyclotriphosphazenes (10, 11 and 13) showed fluorescence chemosensor behavior with high selectivity for Fe3+ and Cu2+ ions in the solution.

Synthesis of nanostructured framework of novel ZnBaO2 nanopowder via wet chemical approach and hepatocytotoxicity response

Wet synthetic process is an effective and facile method at low cost, environmentally benign process for easy scaling-up and then used for fabrication of multi-utility devices. Self-assembling of nanobrick leads to architecture framework with new functional properties which help to make its vast applications as nanodevices with their intrinsic shape, size and functional properties. The bimetallic oxide nanostructure with phase structure was characterized by FTIR, UV–visible electronic absorption, XRD, thermal studies, SEM, TEM, DLS and fluorescence. Nanocrystalline ZnBaO2 powder can be used due to its chemical stability and excellent transmission in the visible region. It was observed that the annealing rate plays an important role to redefine the structural and other physicochemical properties which finally help to change gel into crystalline functional properties with porosity. Wet chemical approach can be used for the synthesis of other metal oxide nanopowders which can be easily scale up for production level. Along with synthesis and characterization, we also assessed biological responses of human hepatocytes exposed to ZnBaO2 nanopowder. Cell membrane permeability and ammonia detoxification were investigated against various concentrations of nanoparticles on in vitro cultured hepatocytes. Our results suggest that low concentrations (<40 μg/ml) of ZnBaO2 nanopowder have no cytotoxic effect on hepatocytes viability, proliferation and detoxification, whereas concentrations above 40 μg/ml depict significant toxicity on cells.

Effects of solvent polarity on the absorption and fluorescence spectra of chlorogenic acid and caffeic acid compounds: determination of the dipole moments.

The effects of solvent polarity on absorption and fluorescence spectra of biologically active compounds (chlorogenic acid (CGA) and caffeic acids (CA)) have been investigated. In both spectra pronounced solvatochromic effects were observed with shift of emission peaks larger than the corresponding UV-vis electronic absorption spectra. From solvatochromic theory the ground and excited-state dipole moments were determined experimentally and theoretically. The differences between the excited and ground state dipole moment determined by Bakhshiev, Kawski-Chamma-Viallet and Reichardt equations are quite similar. The ground and excited-state dipole moments were determined by theoretical quantum chemical calculation using density function theory (DFT) method (Gaussian 09) and were also similar to the experimental results. The HOMO-LUMO energy band gaps for CGA and CFA were calculated and found to be 4.1119 and 1.8732 eV respectively. The results also indicated the CGA molecule is more stable than that of CFA. It was also observed that in both compounds the excited state possesses a higher dipole moment than that of the ground state. This confirms that the excited state of the hydroxycinnamic compounds is more polarized than that of the ground state and therefore is more sensitive to the solvent.

Synthesis, spectroscopic and electrochemical properties of new covalent assemblies between TTF and various acceptors

Five new acceptor-π–TTF-π-acceptor (A–D–A) triads that contain pyridine, quinoline, nitrophenyl or nitrofuryl groups as acceptor unit have been synthesized by two-fold Wittig olefination reactions and their electrochemical behavior has been studied by cyclic voltammetry (CV). The intramolecular charge transfer (ICT) band in these molecules was characterized by UV–visible electronic absorption spectroscopy and these studies were completed by DFT calculations in the gas phase. These materials appear to be good candidates for the preparation of electroactive discrete metal complexes or coordination polymers as well as for the preparation of radical cations salts.

Spectroscopic and semiempirical investigation of the structural features of hetarylazo-5-isoxazolones tautomerism

3-Methyl-4-hetarylazo-5-isoxazolones (I–IV) have been synthesized and investigated on the basis of Fourier transform infrared (FT-IR), UV–visible (UV–Vis), proton nuclear magnetic resonance (1H NMR) spectroscopic techniques and elemental analysis. The measured FT-IR and 1H NMR spectra together with the theoretical calculations (semiempirical) showed that the investigated compounds exist in the hydrazone-keto form in the solid state and chloroform. However, the measured UV–Vis electronic absorption spectra in solutions clarified that the hetarylazo-5-isoxazolone dyes possess equilibrium between hydrazone-keto and common anion forms depending upon the nature of the medium. Furthermore, these dyes display a broad absorption band in the visible region (between 370 and 435nm) which could be assigned to π–π∗ transition with a considerable intramolecular charge transfer (CT) character.

8-HaloBODIPYs and Their 8-(C, N, O, S) Substituted Analogues: Solvent Dependent UV–Vis Spectroscopy, Variable Temperature NMR, Crystal Structure Determination, and Quantum Chemical Calculations

The UV-vis electronic absorption and fluorescence emission properties of 8-halogenated (Cl, Br, I) difluoroboron dipyrrin (or 8-haloBODIPY) dyes and their 8-(C, N, O, S) substituted analogues are reported. The nature of the meso-substituent has a significant influence on the spectral band positions, the fluorescence quantum yields, and lifetimes. As a function of the solvent, the spectral maxima of all the investigated dyes are located within a limited wavelength range. The spectra of 8-haloBODIPYs display the narrow absorption and fluorescence emission bands and the generally quite small Stokes shifts characteristic of classic difluoroboron dipyrrins. Conversely, fluorophores with 8-phenylamino (7), 8-benzylamino (8), 8-methoxy (9), and 8-phenoxy (10) groups emit in the blue range of the visible spectrum and generally have larger Stokes shifts than common BODIPYs, whereas 8-(2-phenylethynyl)BODIPY (6) has red-shifted spectra compared to ordinary BODIPY dyes. Fluorescence lifetimes for 6, 8, and 10 have been measured for a large set of solvents and the solvent effect on their absorption and emission maxima has been analyzed using the generalized Catalán solvent scales. Restricted rotation about the C8-N bond in 7 and 8 has been observed via temperature dependent (1)H NMR spectroscopy, whereas for 10 the rotation about the C8-O bond is not hindered. The crystal structure of 8 demonstrates that the short C8-N bond has a significant double character and that this N atom exhibits a trigonal planar geometry. The crystal structure of 10 shows a short C8-O bond and an intramolecular C-H···π interaction. Quantum-chemical calculations have been performed to assess the effect of the meso-substituent on the spectroscopic properties.

Spectroscopic studies, fluorescence quenching by molecular oxygen and amplified spontaneous emission of 1,4-bis [2-(2-pyridyl) vinyl] benzene (P2VB) diolefinic laser dye

The UV–visible electronic absorption spectra, molar absorptivity, fluorescence spectra, fluorescence quantum yield and excited state lifetime of 1,4-bis [2-(2-pyridyl) vinyl] benzene P2VB were measured in different solvents. The fluorescence quenching of P2VB by molecular oxygen was also studied using lifetime measurements. A 2×10−4moldm−3 solution of P2VB in dimethyl formamide (DMF) gave amplified spontaneous emission (ASE) in blue spectral region with emission maximum at 420nm upon pumping by 337.1 nitrogen laser pulse. The photochemical quantum yields (ϕc) of trans–cis photoisomerization of P2VB were calculated in different organic solvents. The photoreactivity of P2VB are also studied PMMA matrix.

Easy Synthesis of High-Purity BiFeO3Nanoparticles: New Insights Derived from the Structural, Optical, and Magnetic Characterization

Synthesis of high-purity BiFeO3 is very important for practical applications. This task has been very challenging for the scientific community because nonstoichiometric Bi(x)Fe(y)O(z) species typically appear as byproducts in most of the synthesis routes. In the present work, we outline the synthesis of BiFeO3 nanostructures by a combustion reaction, employing tartaric acid or glycine as promoter. When glycine is used, a porous BiFeO3 network composed of tightly assembled and sintered nanocrystallites is obtained. The origin of high purity BiFeO3 nanomaterial as well as the formation of other byproducts is explained on the basis of metal-ligand interactions. Structural, morphological, and optical analysis of the intermediate that preceded the formation of porous BiFeO3 structures was accomplished. The thorough characterization of BiFeO3 nanoparticles (NPs) included powder X-ray diffraction (XRD); scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM); thermogravimetric analysis (TGA); UV-vis electronic absorption (diffuse reflectance mode), Raman scattering, Mössbauer, and electron paramagnetic resonance (EPR) spectroscopies; and vibrating sample magnetometry (VSM). The byproducts like β-Bi2O3 and 5 nm Bi2Fe4O9 NPs were obtained when tartaric acid was the promoter. However, no such byproducts were formed using glycine in the synthesis process. The average sizes of the crystallites for BiFeO3 were 26 and 23 nm, for tartaric acid and glycine promoters, respectively. Two band gap energies, 2.27 and 1.66 eV, were found for BiFeO3 synthesized with tartaric acid, obtained from Tauc's plots. A remarkable selective enhancement in the intensity of the BiFeO3 A1 mode, as a consequence of the resonance Raman effect, was observed and discussed for the first time in this work. For glycine-promoted BiFeO3 nanostructures, the measured magnetization (M) value at 20,000 Oe (0.64 emu g(-1)) was ∼5 times lower than that obtained using tartaric acid. The difference between the M values has been associated with the different morphologies of the BiFeO3 nanostructures.

Hydrothermal synthesis and characterization of straw bundle-like lithium sodium disilicate (silinaite) micro-rods

Abstract Highly mono-shaped straw bundle-like silinaite micro-rods have been synthesized using an aqueous mixture of silicic acid, lithium sulfate, and sodium hydroxide under hydrothermal conditions at 180°C. The synthesized materials were characterized by powder X-ray diffraction technique and Fourier transform infrared spectroscopy. The morphologies of the synthesized materials were studied by field emission scanning electron microscopy technique. The synthesized micro-rods are composed of long, fine nanosheets. Electronic absorption and photoluminescence spectra of the synthesized materials were also studied. With increasing reaction time, a blueshift was observed in the UV–vis electronic absorption and emission spectra of the synthesized materials.

UV—vis spectroscopy of the coupling products of the palladium-catalyzed C—H arylation of the BODIPY core

The steady-state, UV-vis electronic absorption and fluorescence emission properties of a large set of 3-aryl and 3,5-diaryl substituted difluoroboron dipyrromethene dyes obtained via direct, palladium-catalyzed C-H (het)arylation of the BODIPY core are reported. The spectra display the narrow absorption and fluorescence emission bands and the generally quite small Stokes shifts characteristic of classic difluoroboron dipyrrins. As a function of the solvent, the spectral maxima are located within a very narrow wavelength range and are slightly red-shifted with increasing solvent polarizability, which is shown to be the crucial parameter influencing the wavelength position of the maxima. The extended π-conjugation in the 3,5-diaryl products always leads to bathochromically shifted absorption and emission spectra compared to those of the 3-aryl analogues. The derivative with a 3-mesityl substituent has blue-shifted spectra in comparison to its 3-phenyl substituted analogue, reflecting the diminished π-conjugation in the former due to steric strain. The nature of the meso-aryl has only a small effect on the spectral positions but affects the fluorescence quantum yield Φ. The majority of the dyes have high Φ (>0.85), except the compounds with meso-phenyl and meso-(p-nitrophenyl) substituents. Quantum-chemical calculations were performed to evaluate the differences in spectroscopic properties upon substitution of the BODIPY core and to compare them with the corresponding experimental results.