Theoretical investigation of electronic structures and excitation energies of doubly N-confused porphyrin and its group 11 transition metal (III) complexes

Density functional theory is carried out to study cis-doubly N-confused porphyrin and its metal (Cu3+, Ag3+, and Au3+) complexes. The electronic structures and bonding situations of these molecules have been investigated by using the natural bond orbital analysis and the topological analysis of the electron localization function. We have studied the electronic spectra of cis-doubly N-confused porphyrin and its metal complexes with time-dependent density functional theory. The introduction of group 11 transition metals leads to blueshifts of their electronic spectra with respect to that of cis-doubly N-confused porphyrin. In particular, the absorption spectra of the copper complex show some weak Q bands that mainly arise from a combination of ligand-to-metal charge transfer and ligand-to-ligand charge transfer transitions. The relativistic time-dependent density functional theory with spin-orbit coupling calculations indicates that the effects of spin-orbit coupling on the excitation energies of the copper and silver complexes are so small that it is safe enough to neglect spin-orbit interactions for these two complexes. However, it has a significant effect on the absorption spectra of the gold complex.     

Photoredox processes in coordination compounds

Transition metal complexes display a number of charge-transfer bands in the absorption spectra. Optical excitation of the metal complexes produces a variety of products depending upon the nature of the excited state. Cobalt (III) ammine complexes on excitation in the CTTM bands produce cobalt(II) and oxidised ligand. Ruthenium(II) complexes on excitation in the cm. band leads to the oxidation of the metal centre. In certain reactions participation of the solvent in the primary photoredox reactions has also been reported. In recent years extensive investigations have been undertaken to utilize the photoredox systems of coordination compounds to convert solar energy to electricity or hydrogen.     

Density Functional Theory Study on Organic Dye Sensitizers Containing Bis-dimethylfluorenyl Amino Benzofuran

The geometries, electronic structures, polarizabilities and hyperpolarizabilities, as well as the UV-Vis spectra of the two organic dye sensitizers containing bis-dimethylfluorenyl amino benzofuran were studied via density functional theory （DFT） and time-dependent DFT. The features of electronic absorption spectra were assigned on account of the agreement between the experiment and the calculations. The absorption bands in visible region are related to photoinduced electron transfer processes, and the dimethylfluorenyl amino benzo[b]furan groups are major chromophore that contributed to the sensitization of photo-to-current conversion. The role of vinylene group in geometry, electronic structure and spectra property is analyzed according to the comparative study of the dyes.     

Femtosecond transient absorption, Raman, and electrochemistry studies of tetrasulfonated copper phthalocyanine in water solutions

Ultrafast time-resolved electronic spectra of the primary events induced in the copper tetrasulfonated phthalocyanine Cu(tsPc)4-) in aqueous solution has been measured by femtosecond pump-probe transient absorption spectroscopy. The primary events initiated by the absorption of a photon occurring within the femtosecond time scale are discussed on the basis of the electron transfer mechanism between the adjacent phthalocyanine rings proposed recently in our laboratory. The femtosecond transient absorption results are compared with the low temperature emission spectra obtained with Raman spectroscopy and the voltammetric curves.     

Infrared reflection-absorption spectra of C2H4 and C2H6 on Cu: effect of surface roughness

Infrared reflection absorption spectroscopy (IRRAS) of the highly symmetric molecules C2H4 and C2H6 adsorbed as mono- and multilayers onto copper films is studied in relation to the type of metal-film roughness. Spectra of C2H4 show Raman lines on cold-deposited Cu films but not on Cu deposited at room temperature. For C2H6, the IR spectra from both types of metal films are similar; the surface infrared selection rule holds and no Raman bands are observed. The Raman lines that appear in the IR spectra already at low exposures are attributed to species adsorbed at special defect sites, identical to the so-called active sites in surface enhanced Raman scattering (SERS). The IR excitation mechanism by transient electron transfer to the adsorbate pi* state can deliver a discrete vibrational band of a Raman-active vibration only under certain circumstances, for example, for adsorbates at the "SERS-active sites". C2H6 at these sites cannot deliver Raman bands in IRRAS, because it has no pi* state. We also discuss IRRAS measurements on Cu(111) and Cu(110) single crystals, where Raman bands of C2H4 have been observed.     

Electronic structures and absorption properties of three kinds of ruthenium dye sensitizers containing bipyridine-pyrazolate for solar cells

The geometries, electronic structures and the electronic absorption spectra of three kinds of ruthenium complexes, which contain tridentate bipyridine-pyrazolate ancillary ligands, were studied using density functional theory (DFT) and time-dependent DFT. The calculated results indicate that: (1) the strong conjugated effects are formed across the pyrazoalte-bipyridine groups; (2) the interfacial electron transfer between electrode and the dye sensitizers is an electron injection processes from the excited dyes to the conduction band of TiO2; (3) the absorption bands in visible region have a mixed character of metal-to-ligand charge transfer and ligand-to-ligand charge transfer, but the main character of absorption bands near UV region ascribe to π→π* transitions; (4) introducing pyrazolate and -NCS groups are favorable for intra-molecular charge transfer, and they are main chromophores that contribute to the sensitization of photon-to-current conversion processes, but introducing -Cl and the terminal group -CF3 are unfavorable to improve the dye performance in dye sensitized solar cells.     

Hydrogen transfer in the reaction of p-phenylenediamine with chloranil

Stage of electron transfer between p-phenylenediamines and chloranil in methanol was studied and a strictly reversible redox conversion of reagents was observed at low temperatures of ?50 to ?90°C. At positive temperatures, the proton transfer initiates a polycondensation yielding a polyaminoquinone of brown color. The nature of the absorption bands of charge-transfer complexes in the visible spectral range is discussed. Quantum-chemical calculations of excited reaction complexes and of absorption spectra of polyaminoquinone were performed.     

Rational design principle for modulating fluorescence properties of fluorescein-based probes by photoinduced electron transfer

Fluorescence properties of fluorescein-based probes are shown to be finely controlled by the rate of photoinduced electron transfer from the benzoic acid moiety (electron donor) to the singlet excited state of the xanthene moiety (electron acceptor fluorophore). The occurrence of photoinduced electron transfer is clearly evidenced by transient absorption spectra showing bands due to the radical cation of the electron donor moiety and the radical anion of the xanthene moiety, observed in laser flash photolysis experiments. The photoinduced electron transfer rates and the rates of back electron transfer follow the Marcus parabolic dependence of electron transfer rate on the driving force. Such a dependence provides for the first time a quantitative basis for a rational design principle which has high efficiency in modulating fluorescence properties of fluorescein-based probes.     

Conjugate spacer effect on molecular structures and absorption spectra of triphenylamine dyes for sensitized solar cells: density functional theory calculations

The molecular structures and absorption spectra of triphenylamine dyes containing variable thiophene units as the spacers (TPA1-TPA3) were investigated by density functional theory (DFT) and time-dependent DFT. The calculated results indicate that the strong conjugation is formed in the dyes and the length of conjugate bridge increases gradually with the increased thiophene spacers. The interfacial charge transfer between the TiO2 electrode and TPA1-TPA3 are electron injection processes from the excited dyes to the semiconductor conduction band. The simulated absorption bands are assigned to π→π* transitions, which exhibit appreciable red-shift with respect to the experimental bands due to the lack of direct solute-solvent interaction and the inherent approximations in TD-DFT. The effect of thiophene spacers on the molecular structures, absorption spectra and photovoltaic performance were comparatively discussed and points out that the choice of appropriate conjugate bridge is very important for the design of new dyes with improved performance.     

Determination of the spectroscopic properties and chromatographic sensitivities of substituted quinones by hexachlorate(IV) oxidation of hydroquinones

HPLC studies of the oxidation of substituted hydroquinones show that the corresponding quinones can, in most cases, be produced quantitatively by two electron transfer to hexachloroiridate(IV). As a consequence the chromatographic and spectroscopic properties of substituted quinones that are not readily available can be determined without the necessity of preparation of an isolatable sample. Absorption spectra and extinction coefficients of bromoquinone, chloroquinone, hydroxyquinone and carboxyquinone anion at pH 7 are reported as illustrative examples. All have intense absorption bands at approximately 250nm that are characteristic of quinones. Oxidation of carboxyhydroquinone at low pH is, however, anomalous in that a hydroxylated carboxyquinone is produced as the result of four electron transfer to hexachloroiridate.     

Fluorene Compounds with Intramolecular Charge Transfer Containing Dithiolylidene and Selenathiolylidene Substituents

Abstract

Condensation of polynitrofluorenes with dithiolium and selenathiolium salts in DMF leads to 9-substituted fluorenes with intramolecular charge transfer (ICT); spectral investigations show that ICT energies and intensities of ICT bands in electron absorption spectra depend substantially on heteroatomlocation but display very few dependence on the heteroatom nature (S or Se)     

Photonics of tetramethoxy-1,4-distyrylbenzene

Photonics of tetramethoxy-1,4-distyrylbenzene in MeCN was studied by absorption, luminescence, and laser kinetic spectroscopies. Photoinduced transformations of the compound in question involve cis–trans-isomerization, intersystem crossing, fast and delayed fluorescence, and electron transfer. The ground-state structure and vibrational spectrum, as well as the energies and structures of excited singlet and triplet states were calculated by the DFT/PBE and TDDFT/PBE0 methods. The assignment of vibronic bands in the absorption spectra was made and the energies of corresponding transitions were calculated.     

Kupferkomplexe von Bisamiden,IV UV.-Banden binuclearer Koordinationsverbindungen ohne Cu-Cu-Bindung

Cupric copper and N,N′-Bis-(2-dimethylaminoethyl)-oxamid form in aqueous solution six complexes, three of them being binuclear. Potentiometric and spectrophotometric data were used to obtain stability constants and concentration of each complex, and to calculate their electronic absorption spectra. The binuclear compounds show strong absorption bands in the near UV., in analogy to the quite differently structured dimeric copper acetate. It is proposed that all these bands near to 370 nm are of charge transfer type.     

UV-vis, IR and 1H NMR spectroscopic studies of some mono- and bis-azo-compounds based on 2,7-dihydroxynaphthalene and aniline derivatives

The absorption spectra of mono- and bis-azo-derivatives obtained by coupling the diazonium salts of aromatic amines and 2,7-dihydroxynaphthalene have been studied in six organic solvents. The different absorption bands have been assigned and the effect of solvents on the charge transfer band is also discussed. The diagnostic IR spectral bands and 1H NMR signals are assigned and discussed in relation to molecular structure. Also, semi-empirical molecular orbital calculations using the atom superposition and electron delocalization molecular orbital (ASED-MO) theory have been performed to investigate the molecular and electronic structures of these compounds. According to these calculations, an intramolecular hydrogen bonding is essential for stabilization of such molecules.     

Ligand to ligand charge transfer in (hydrotris(pyrazolyl)borato)(triphenylarsine)copper(I)

Emission and UV-vis absorption spectra of (hydrotris(pyrazolyl)borato)(triphenylarsine)copper(I), (CuTpAsPh3), (hydrotris(pyrazolyl)borato)(triethylamine)copper(I), (CuTpNEt3), and (hydrotris(pyrazolyl)borato)(triphenylphosphine)copper(I), (CuTpPPh3), are reported. The spectra of the arsine complex contain low-energy bands (with a band maximum at 16,500 cm(-1) in emission and a weak shoulder centered at about 25,000 cm(-1) in absorption) that are not present in the corresponding spectra of the amine or phosphine complexes. The lowest energy electronic transition is assigned to ligand to ligand charge transfer (LLCT) with some contribution from the metal. This assignment is consistent with PM3(tm) molecular orbital calculations that show the HOMO to consist primarily of pi orbitals on the Tp ligand (with some metal orbital character) and the LUMO to be primarily antibonding orbitals on the AsPh3 ligand (also with some metal orbital character). The absorption shoulder shows a strong negative solvatochromism, indicative of a reversal or rotation of electric dipole upon excitation, and consistent with a LLCT. The trends in the energies of the electronic transitions and the role of the metal on the LLCT are discussed.     

A study on the photophysical properties of anthracene in zeolite

The photophysical behaviours of anthracene in zeolite Y were investigated using various steady state spectroscopic methods and a picosecond time-resolved fluorescence spectroscopic technique. A ¹²⁹Xe nuclear magnetic resonance (NMR) study shows that anthracene molecules can be optimally intercalated into the supercages of Na⁺- and Cu²⁺-exchanged zeolite Y at 570 and 520 K respectively. Anthracene introduced into the supercage of Na⁺-exchanged zeolite Y shows excimeric fluorescence with a lifetime of several nanoseconds, as well as monomeric fluorescence with a lifetime of 300 ps. The excimer forms immediately on absorption of a photon. Cu²⁺-exchanged zeolite Y with anthracene intercalation shows electron spin resonance (ESR) signals and absorption bands attributable to the stable, ground state anthracene cation radical, the Cu⁺ ion and the trapped electron in the copper ion cluster, indicating charge transfer from anthracene to the Cu²⁺ ion or copper ion cluster. The excitation energy of anthracene is quenched rapidly by the presence of copper ion.     

Effect of pyridine on infrared absorption spectra of copper phthalocyanine

Infrared absorption spectra of copper phthalocyanine in KBr pellet and pyridine solution in 400-1625 and 2900-3200 cm(-1)regions are reported. In the IR spectra of solid sample, presence of weak bands, which are forbidden according to the selection rules of D4h point group, is explained on the basis of distortion in the copper phthalocyanine molecule caused by the crystal packing effects. Observation of a new band at 1511 cm(-1) and change in intensity of some other bands in pyridine are interpreted on the basis of coordination of the solvent molecule with the central copper ion.     

Surface enhanced Raman spectra of isomeric acetylpyridines adsorbed on silver sol

Raman spectra of 2-, 3- and 4-acetylpyridines (AP) are obtained in bulk phase, in aqueous solution and in the adsorbed state on colloidal silver particles. Addition of the acetylpyridines on the Ag-sol results in aggregation of the silver particles showing characteristic charge transfer (CT) bands. Significant surface enhancement of the Raman bands are observed. Both the estimated enhancement factor and the absorption maxima of the CT bands are in inverse parallel relationship with the electron density on the nitrogen atom as reflected by the Hammett σ values of the substituents. It is inferred that the charge transfer interactions between the adsorbates and the metal particles contribute to the enhancement mechanism. This is further substantiated by the concentration dependence of enhancement. A classical electromagnetic contribution is demonstrated by the Raman excitation frequency dependence of SERS. The results further show that the molecules are adsorbed on the metal surface through the nitrogen atom. Appearance of some out-of-plane modes in the SERS spectra suggests that the pyridyl ring planes are not perpendicular to the metal surface, but are tilted.     

锰、铑原卟啉IX-二甲酯配合物共振拉曼光谱研究

合成了MnPPCl,RhPPCl,RhPPN3,RhPP(CO)Cl四种配合物 (PP =ProtophyrinIXDimethy1Ester) ,用元素分析、红外吸收光谱及紫外吸收光谱确定了配合物的组成 ,测定了它们的共振拉曼光谱 ,对特征谱带进行了归属。分析了拉曼谱带和电子吸收谱带变化的原因 ,提出了谱带频率的变化受金属离子外层d电子和轴配体的影响。     

有机染料敏化剂JK16和JK17的几何结构、电子结构及相关性质

运用密度泛函理论中的杂化泛函B3LYP研究了高效太阳能电池新型染料敏化剂JK16和JK17的几何结构、电子结构、极化率和超极化率, 并用含时密度泛函理论(TDDFT)研究了电子吸收谱. 基于含时密度泛函理论计算结果和实验结果的定性符合, 指认了在可见和近紫外区的吸收属于π→π*跃迁. 计算结果还表明JK16和JK17激发能最低的三个跃迁都与光诱导电荷转移过程有关, 而且二-二甲基芴氨基苯并噻吩基团对光电转换过程的敏化起主要作用, 发生于染料敏化剂JK16、JK17和TiO2界面之间的电荷转移是由染料分子激发态向半导体导带的电子注入过程. 此外, 通过对JK16和JK17的比较, 分析了亚乙烯基对几何结构、电子结构和谱学特性的影响.