bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesis and spectral properties of ruthenium(II) complexes with tetra-15-crown-5-phthalocyanine and N-donor ligands
Authors: Gorbunova Yuliya G. , Enakieva Yuliya Yu. , Sakharov Sergey G. , Tsivadze Aslan Yu.
Published: July 2009

The synthesis of novel bis-axially coordinated ruthenium(II) complexes with tetra-15-crown-5-phthalocyanine and N-donor ligands ( R 4 Pc ) Ru ( L 2) ( R 4Pc2- = 4,5,4',5',4'',5'', 4''',5'''- tetrakis(1,4,7,10,13-pentaoxotridecamethylene)phthalocyaninate-ion, L = pyridine (py), isoquino-line (iqnl), triethylamine ( Et 3 N )) is reported. The preparation technique involves the interaction of ( R 4 Pc ) Ru ( CO )( CH 3 OH ) with trimethylamine oxide in an N-donor solvent. The advantage of this method consists in selective carbonyl ejection from ( R 4 Pc ) Ru ( CO ) X with simultaneous substi-tution by N-donor ligands. The application of this procedure allowed us to decrease essentially the reaction time, as compared with photochemical methods, as well as to increase substantially the yield of reaction products. UV-visible, 1 H NMR, FT-IR and mass-spectrometry were used for characterization of the obtained compounds.
Theoretical AM1 study of acidity of porphyrins, azaporphyrins and porphyrazines
Authors: Stuzhin Pavel A.
Published: July 2009

The structure-acidity relationship in the series of non-substituted, meso- or β-substituted and β,β-annulated porphyrins and porpyrazines have been studied using the AM1 method with unrestricted Hartree-Fock basis set. With this purpose, heats of formation have been determined for the geometry optimized structures of the free base macrocycles and corresponding monoanions and dianions formed by deprotonation. Calculated first deprotonation enthalpy values show correlation with available experimental p K1avalues and can be used for prediction of acidity. For porphyrazines bearing electron-withdrawing substituents or π-deficient annulated heteroarens the dianions have lower heats of formation than the corresponding neutral species and such porphyrazines are easily deprotonated upon dissolution in basic solvents (pyridine, DMF). For porphyrazines with annulated 5-member heteroarens it is predicted that deprotonation of peripheral NH groups should occur more easily than deprotonation of the internal NH groups. The influence of different types of annulation of 5- and 6-membered heteroarens to the porphyrazine core on the stability of the macrocyclic system and its acidity are also discussed.
Hydrocarbon C-H bond activation by rhodium porphyrins
Authors: Cui Weihong , Wayland Bradford B.
Published: July 2009

Rhodium porphyrins provide a variety of C-H bond reactions with both aromatic and aliphatic hydrocarbons that acquire unusual selectivity in part through the steric requirements of the porphyrin ligand. Rhodium(III) porphyrins selectively react with aromatic C-H bonds by electrophilic substitution with the virtual exclusion of aliphatic C-H bond activation. Rhodium(II) porphyrins react by a metal-centered radical pathway with alkyl aromatics and alkanes selectively at the alkyl C-H bond with total exclusion of aromatic C-H bond activation. Reactions of rhodium(II) metalloradicals with alkyl C-H bonds have large deuterium isotope effects, small activation enthalpies and large negative activation entropies consistent with a near linear symmetrical four-centered transition state ( Rh ˙⋯ H ⋯ C ⋯˙Rh). The nature of this transition state and the dimensions of rhodium porphyrins provide steric constraints that preclude aromatic C-H bond reactions and give high kinetic preference for methane activation as the smallest alkane substrate. Rhodium(II) tethered diporphyrin bimetalloradical complexes convert the C-H bond reactions to bimolecular processes with dramatically increased reaction rates and high selectivity for methane activation.
Meso-aryl-ß-pyrrolic positions interactions in meso-tetraarylporphyrins: Flat arylporphyrins and building blocks for oligoporphyrins
Authors: Callot Henry J. , Ruppert Romain , Jeandon Christophe , Richeter Sébastien
Published: July 2009

Aryl groups bound to the meso positions of porphyrins often react with neighboring groups, in particular ß-acyl groups to give highly diversified monomeric and dimeric new functionalized porphyrins. The products, whose meso-aryl ring approaches coplanarity with the porphyrin macrocycle, show large shifts of UV-visible absorption bands and various potentialities for building external chelating moieties and assembling oligoporphyrins.
Short- and long-distance porphyrin heterodimers in bulk aqueous solution and nanowells
Authors: Fuhrhop Jürgen-Hinrich , Wang Tianyu , Bhosale Sheshanath , Bhosale Sidhanath
Published: July 2009

Short-distance porphyrin heterodimers may be used for very efficient titrations in water measuring fluorescence quenching in 1:1 molecular complexes between diamagnetic and paramagnetic metalloporphyrins. Radical dimers produce strong charge transfer bands near 900 nm. Long-distance heterodimers, e.g. chlorophyll-ubiquinone, play a central role in the charge separation process of biological photosynthesis. Attempts to model such dimers in form-stable nanowells are discussed and compared with corresponding molecular complexes and covalent redox systems. Heterodimers may, of course, not only be made of two porphyrins. Other acceptor molecules, which fit exactly in the nanowells, e.g. large quinones may also be applied.
Host-guest interactions of cyclodextrins and metalloporphyrins: supramolecular building blocks toward artificial heme proteins
Authors: Zhou Huchen , Groves John T.
Published: July 2009

Cyclodextrins are versatile building blocks for a variety of macromolecules due to the inclusion complexes that are formed with hydrophobic organic molecules. Cyclodextrin-porphyrin interactions are of particular interest since cyclodextrins can serve as a non-covalent binding pocket while metalloporphyrins could serve as the heme analogs in the construction of heme protein model compounds. Various approaches to the design and assembly of biomimetic porphyrin constructs are compared and contrasted in this minireview with a particular emphasis on self-assembled and porphyrin-cyclodextrin systems. Several recent advances from our laboratories are described in this context. A sensitive fluorescent binding probe, 6A-N-dansyl-permethylated-β-cyclodextrin (Dan-NH-TMCD), was found to form 2:1 complexes with the meso-tetraphenylporphyrins Mn(III)TCPP , Mn(III)TPPS and Mn(III)TF 4 TMAP with high binding constants. A perPEGylated cyclodextrin, heptakis(2,3,6-tri-O-2-(2-(2-methoxyethoxy)ethoxy)ethyl)-β-cyclodextrin (TPCD), has been shown by 1 H NMR spectroscopy to form a 1:1 complex with H 2 TCPP with a binding constant above 108M-1. Such a strong binding constant is the largest found for a 1:1 complex between a monomeric cyclodextrin and a guest. TPCD was also found to bind Mn(III)TCPP with a binding constant of 1.2 × 106 M -1. A novel, self-assembled hemoprotein model, hemodextrin is also described. The molecular design is based on a PEGylated cyclodextrin scaffold that bears both a heme-binding pocket and an axial ligand that binds an iron porphyrin. The binding constant for Fe (III) TPPS (iron(III) meso-tetra(4-sulfonatophenyl)porphyrin) by py-PPCD was determined to be 2 × 106 M -1. The pyridyl nitrogen of py-PPCD was shown to ligate to the iron center by observing signal changes in the Fe(II) -porphyrin 1 H NMR spectrum. This hemodextrin ensemble, a minimalist myoglobin, was shown to bind dioxygen reversibly and to form a stable ferryl species.
Molecular complexes of water-soluble porphyrins
Authors: Kano Koji
Published: July 2009

Water-soluble porphyrins tend to form self-aggregates under certain conditions. The structure of the self-aggregate (H-type dimer, H-type higher aggregate, or J-aggregate) sensitively depends on the structure of the peripheral substituents at the meso-positions of the porphyrin. Water-soluble porphyrins also form relatively stable π-stacked complexes with various aromatics. Polar effects are important in complexation of anionic porphyrins with anthraquinonesulfonates. The results suggest that the main attractive interaction for formation of π-stacked complexes of water-soluble porphyrins is the σ-π interaction as claimed by Hunter and Sanders. Meanwhile, the aryl groups at the meso-positions of the water-soluble porphyrins are included by per-O-methylated β-cyclodextrin through van der Waals interactions to form extremely stable 1:2 complexes (porphyrin:cyclodextrin). Such a character of the water-soluble porphyrins can be applied to convenient preparation of supramolecular hetero-porphyrin arrays.
Porphyrin supramolecules by complementary coordination for units constructing photosynthetic systems
Authors: Kobuke Yoshiaki
Published: July 2009

Among unique structural arrangements provided by nature, special pair and macroring antenna complexes in bacterial photosynthetic systems have been mimicked by simple organization of choromophores. The special pair was mimicked by imidazolyl-substituted porphyrinatozinc which gave a complementary coordination dimer of slipped cofacial orientation with an extremely large stability constant of 1010 M-1 in CHCl 3. When two imidazolylporphyrinatozinc units were linked directly at the meso positions, linear and continuous growth of the complementary coordination lead to porphyrin arrays of a few hundreds nanometer scale, corresponding to molecular weights of a few 105. At the same time, the porphyrin array could be dissociated into the monomeric unit by competitive coordination of solvents. This provided a way of terminating or initiating the oligomeric porphyrin array with appropriate chain terminals/initiators. Two imidazolylporphyrinatozinc complexes were then linked by a m-phenylene unit with an angle of 120°. The linear and macrocyclic oligomer mixtures initially obtained were converged smoothly by reorganization equilibrium into a mixture of hexameric and pentameric macrocycles under high-dilution conditions. The ring mimicked the structure and function of the light harvesting complexes of bacterial photosynthetic systems. The covalent linking of coordination organized porphyrins was also developed to maintain the structure even in highly coordinating solvents such as pyridine. The linear array formation and the facile introduction of specific terminal/initiator groups by complementary coordination were then applied to introduce antenna function onto solar cell. Through thiolate attachment on a gold surface, imidazolylporphyrinatozinc initiated the growth of meso-meso linked porphyrin arrays by successive complementary coordination. This methodology improved the efficiency of absorption of incident photon and increased significantly the total photocurrent generation efficiency.
π-Complex formation in electron-transfer reactions of porphyrins
Authors: Fukuzumi Shunichi , Hasobe Taku , Ohkubo Kei , Crossley Maxwell J. , Kamat Prashant V. , Imahori Hiroshi
Published: July 2009

π-Complex formation between porphyrins and their radical cations plays an important role in self-exchange electron transfer between neutral porphyrins and the radical cations, leading to negative activation enthalpies when the stabilization energy of the π-complex is larger than the activation energy for the intracomplex electron transfer in the π-complex. A number of porphyrin molecules are self-organized on three-dimensional gold nanoclusters to form monolayer-protected gold nanoclusters (MPCs) that act as an efficient photocatalyst for the uphill reduction of HV2+ by BNAH to produce 1-benzylnicotinamidinium ion (BNA+) and hexyl viologen radical cation (HV·+). Such three-dimensional architectures of porphyrin MPCs with large surface area allow supramolecular π-complexation between MPCs and HV2+, resulting in fast electron transfer from the singlet excited state of porphyrin to HV2+ on MPCs. The π-π interaction is exploited to develop efficient photovoltaic devices consisting of porphyrin and fullerene assemblies which have an enhanced light-harvesting efficiency throughout the solar spectrum together with a highly efficient conversion of the harvested light into electrical energy.
Improved routes for the synthesis of face-to-face bismacrocycles in porphyrin and corrole series
Authors: Barbe Jean-Michel , Stern Christine , Pacholska Ewa , Espinosa Enrique , Guilard Roger
Published: July 2009

Face-to-face bismacrocycles involving porphyrinoid species are still of great interest owing to their versatile properties. Despite the fact that their syntheses generally involve several steps, numerous modifications have been made in their synthetic pathways thus allowing their preparation in gram quantities. Here we report on recent improvements we could propose especially for the synthesis of bisporphyrin, biscorrole and porphyrin-corrole derivatives.
Nonlinear optical properties of lutetium bisphthalocyanine and its application for an optical switch
Authors: Liu Lung-Chang , Tai Chia-Hon , Hu Andrew Teh , Wei Tai-Huei
Published: July 2009

The nonlinear optical (NLO) properties of lanthanide bisphthalocyanine (Lu(TBPc)Pc), including first hyperpolarizability, second hyperpolarizability and reverse saturable absorption (RSA), have been investigated. Furthermore, Lu(TBPc)Pc has also been applied for optical switch based on its RSA performance.
Ab initio and 1H NMR study of the Zn(II) complexes of a nido- and a closo-carboranylporphyrin
Authors: Bobadova-Parvanova Petia , Oku Yuko , Wickramasinghe Anura , Hall Randall W. , Vicente M. Graça H.
Published: July 2009

An ab initio study of a promising nido-carboranylporphyrin for the boron neutron capture therapy of tumors, and of its closo precursor is reported. Base-induced deboronation of neutral ZnDCP , believed to exist as a mixture of 3 stereoisomers, produces the tetraanionic ZnDCP 4- as a complex mixture of isomers. 1 H NMR data and ab initio calculations support these findings. The position of the axial pyridine ligand in ZnDCP 4- and the orientation of the endo hydrogen atoms on the open faces of the nido-carborane cages significantly influence the total energy of the ZnDCP 4- structures. It is suggested that the "cocktail" of isomers possibly enhances the biological activity of tetra(nido-carboranyl)porphyrins, such as ZnDCP 4-.
Synthesis, structure, and properties of new phthalocyanines
Authors: Kobayashi Nagao , Leznoff Clifford C.
Published: July 2009

Many low symmetry and/or deformed phthalocyanines (Pcs) have been synthesized, separated, and their spectroscopic and electrochemical properties elucidated in the last decade, mainly because of improvement in separation techniques of reaction mixtures and development of instruments and computers. In this overview, some advances in the chemistry of Pcs are surveyed. In recent years, many types of alkynyl Pcs, various isomers of low symmetry Pcs, severely sterically deformed Pcs, and chiral Pcs have been prepared and some of their properties are reproduced by quantum mechanical calculations, which have not been achieved previously. Also, in the field of Pc sandwich complexes, properties of hetero double- and triple-decker complexes can be compared, since many types of compounds are now available. Some hetrodinuclear planar dimers have also been reported in the last decade.
Metalloporphyrin catalysts for organic synthesis
Authors: Simonneaux Gérard , Tagliatesta Pietro
Published: July 2009

Novel chiral systems for the catalytic asymmetric oxidation and cyclopropanation of olefins based on metalloporphyrins containing iron, ruthenium and manganese, have been recently introduced. High catalyst turnover numbers and sometimes high enantiomeric excess were observed. New catalytic reactions with metalloporphyrins have recently been reported; these are the olefination of aldehydes and cyclotrimerization of terminal alkynes. Dendrimers and polymers containing metalloporphyrins, have also been found to be efficient catalysts for oxidation and carbene transfer.
Synthesis, electrochemical, photovoltaic, and photo-physical properties on the lanthanide(III) complexes of acetylacetonate and meso-tetraalkyltetrabenzoporphyrin with electric-field induction
Authors: Qi Ming-Hui , Liu Guo-Fa
Published: July 2009

Lanthanide(III) complexes with acetylacetonate and meso-tetraalkyltetrabenzoporphyrin (TATBP) having the general formula Ln ( TATBP )acac (where Ln = Tb , Dy , Ho , Er , Tm , Yb ; A = C 12 H 25; Hacac = acetylacetone) are reported. These compexes have been studied by elemental analyses, ultraviolet visible spectra, infrared spectra, molar conductance, 1 H NMR spectra, cyclic voltammetry, surface photovoltage spectroscopy (SPS), and luminescence spectroscopy. The infrared spectral bands of the ligand and complexes were assigned. In dimethylformamide (DMF), 0.1 M tetrabutylammonium perchlorate (TBAP), the synthesized TATBP exhibit two one-electron reversible redox reactions, and Ln(TATBP)acac shows three redox reactions respectively, within the accessible potential window of the solvent. The absorption bands of the complexes appear in the range 431-433 (Soret band), 578-580 (Q band) and 627-631 (Q band) nm. The photovoltaic properties and charge transfer process of these compounds were investigated by surface photovoltage spectroscopy (SPS) and electric-field-induced surface photovoltage spectroscopy (EFISPS) techniques, which reveal that the ligand TATBP and the complexes Er(TATBP)acac are p-type semiconductors. The spectral bands of TATBP correspond to π → π* transitions. Quantum yields of the S 1 → S 0 fluorescence are in the region 0.25-0.27 and the fluorescence lifetimes are in the region 0.014-0.022 ms at room temperature. The phosphorescence bands of the complex at 77 K appears 714 nm.
Selective meso-monobromination of 5,15-diarylporphyrins via organopalladium porphyrins
Authors: Kato Aiko , Hartnell Regan D. , Yamashita Masahiro , Miyasaka Hiroshi , Sugiura Ken-ichi , Arnold Dennis P.
Published: July 2009

The selective meso-monobromination of 5,15-diarylporphyrins is difficult to achieve and extensive chromatography is required to obtain pure products. A sequence of (i) dibromination, (ii) selective monoinsertion of Pd ( dppe ) (dppe = 1,2-bis(diphenylphosphino)ethane) and (iii) hydrodepalladation using methanolic base affords pure monobromoporphyrins in typically ≥ 60% overall yield without isolation of the organopalladium porphyrin. Monobromo derivatives of even highly lipophilic 5,15-diarylporphyrins are thus readily available without tedious, expensive and environmentally undesirable chromatography.
Synthesis of phthalocyanines with two carboxylic acid groups and their utilization in solar cells based on nano-structured TiO2
Authors: Yanagisawa Masaru , Korodi Ferenc , Bergquist Jonas , Holmberg Anna , Hagfeldt Anders , Åkermark Björn , Sun Licheng
Published: July 2009

A way of anchoring unsymmetrical phthalocyaninato-metal complexes (metal ion: zinc and ruthenium) is described. The synthesis and characterization of these complexes are presented. In case of the zinc complex, the obtained product is an aggregate, while only the monomer is obtained in the case of the ruthenium derivative. Both complexes could be attached onto the TiO 2 surface by using the reported method. Both dyes are expected to form monolayers with dye molecules standing on the surface of nano-structured TiO 2, forming higher-order aggregates with the zinc but not with the ruthenium complex. A highest monochromatic incident photo-to-current conversion efficiency (IPCE) of 1.6% at 690 nm was obtained for a solar cell based on the Pc-Zn sensitized nano-structured TiO 2 electrode, while an IPCE of 23% at 630 nm was obtained for the Pc-Ru sensitized electrode. Overall conversion efficiencies (η) at a simulated AM 1.5 (100 W.m-2) of 0.03% and 0.40% for the zinc and ruthenium complexes were achieved, respectively. The difference in efficiencies could be due to the formation of face-to-face aggregation in the former case. This work shows that the ruthenium complex, with two axial methylpyridine ligands, does not form aggregates in solution nor on the surface of TiO 2, making it possible for further construction of supramolecular systems with such types of phthalocyanine.
A colormap analysis method for visual presentation of the skeletal deformations of phthalocyanine derivatives
Authors: Fukuda Takamitsu , Kobayashi Nagao
Published: July 2009

A two dimensional colormap analysis program customized for phthalocyanines and related macrocyclic compounds has been developed in order to effectively visualize the atomic displacements from the mean plane. Eleven known phthalocyanine structures, including super- and subphthalocyanines, have been analysed as examples using the program, and the distribution of the skeletal deformations within the molecules surveyed.
Kinetics and mechanism of gold(III) incorporation into tetrakis(1-methylpyridium-4-yl)porphyrin in aqueous solution
Authors: Habib Ahsan , Tabata Masaaki , Wu Ying Guang
Published: July 2009

The kinetics of the reaction of the tetrakis(1-methylpyridium-4-yl)porphyrin tetracation, [ H 2( TMPyP )]4+, with gold(III) ions were studied along with equilibria of gold(III) species in aqueous medium at 25°C, I = 0.10 M ( NaNO 3). The equilibrium constants for the formation of [ AuCl 4-n( OH ) n ]- ( n = 0,…,4), defined as β n = [ AuCl 4- n ( OH ) n ]- [ Cl -] n / [ AuCl 4-][ OH -] n were found to be that log β1 = 7.94 ± 0.03, log β2 = 15.14 ± 0.03, log β3 = 21.30 ± 0.05 and log β4 = 26.88 ± 0.05. The overall reaction was first order with respect to each of the total [ Au (III)] and [ H 2 TMPyP 4+]. On the basis of pH dependence on rate constants and the hydrolysis of gold(III), the rate expression can be written as d [ Au ( TMPyP )5+]/ dt = ( k 1[ AuCl 4-] + k2[ AuCl 3( OH )-] + k3[ AuCl 2( OH )2-] + k4[ AuCl ( OH )3-])[ H 2 TMPyP 4+], where k1, k2, k3 and k4 were found to be (2.16 ± 0.31) × 10-1, (6.56 ± 0.19) × 10-1, (1.07 ± 0.24) × 10-1, and (0.29 ± 0.21) × 10-1 M -1. s -1, respectively. The kinetic data revealed that the trichloromonohydroxogold(III) species, [ AuCl 3( OH )]-, is the most reactive. The higher reactivity of [ AuCl 3( OH )]- is explained by hydrogen bonding formation between the hydroxyl group of [ AuCl 3( OH )]- and the pyrrole hydrogen atom of [ H 2( TMPyP )]4+. Furthermore, applying the Fuoss equation to the observed rate constants at different ionic strengths, the apparent net charge of [ H 2( TMPyP )]4+ was calculated to be +3.5.
Synthesis of novel lipophilic porphyrin-cardanol derivatives
Authors: Attanasi Orazio A. , Del Sole Roberta , Filipponea Paolino , Mazzetto Selma E. , Mele Giuseppe , Vasapollo Giuseppe
Published: July 2009

The synthesis of new lipophilic meso-tetraarylporphyrins bearing cardanol is described; cardanol is both a dangerous pollutant and renewable, widely available, relatively low-cost natural material obtained as a byproduct of the cashew industry for the edible use of cashew kernel. Such compounds exhibited unusual chemical and physico-chemical properties.
A career in phthalocyanine chemistry – the Linstead Award 2002
Authors: Lever A. B. P.
Published: July 2009

A stroll through memory lane highlighting the author's contributions to phthalocyanines, including synthetic aspects especially of binuclear species, manganese oxygen breathing chemistry, mixed valence species, solution and surface electrochemistry, electrocatalysis, two-electron concerted processes, charge transfer spectroscopy, ligand electrochemical parameter applications and phthalocyanine design.
Introducing the Staudinger phosphazene reaction to porphyrin chemistry
Authors: Huyen Nga Hoang , Jannsen Ulrike , Mansour Hanaa , Jux Norbert
Published: July 2009

The syntheses, characterizations and transformations of three tetraphenylporphyrins derived from methoxymethylated benzaldehyde 3 are described. Benzaldehyde 3 reacted with pyrrole under Lewis acid catalysis to give dipyrromethane 4 which was used as precursor in porphyrin syntheses. Porphyrins 6, αα-7 and αβ-7 were obtained using conditions for sterically encumbered benzaldehydes, with αα-7 and αβ-7 being atropisomers. The methoxymethyl groups of 6, αα-7 and αβ-7 were transformed into bromomethyl substituents (porphyrins 8, αα-9 and αβ-9) which were easily modified by nucleophilic reaction with the azide anion. Porphyrin azide 10 was subjected to a Staudinger phosphazene formation with triphenylphosphine. Subsequent reaction of the porphyrin phosphazene 12 with carboxylic acids gave acetamide 13, benzamide 14, and ferrocene carboxamide 15, respectively. Kornblum oxidation of monobromomethyl porphyrin 8 gave the formyl derivative 16.
Asymmetrically fused heterocyclic phthalocyaninato nickel(II) adducts: synthesis and characterization
Authors: Youssef Tamer E. , Hanack Michael
Published: July 2009

Reaction of the asymmetrically hexa(2-ethylhexyloxy) substituted nickel phthalocyanine PcNi 1 with the pyridine N-oxides 2a-c to afford the nickel phthalocyanine adducts 3a-c containing furopyridine-type ring is described. The adducts are formed via 1,3-cycloaddtion followed by 1,5-sigmatropic rearrangement.
Long wavelength absorbing cationic Zn(II)-phthalocyanines as fluorescent contrast agents for B16 pigmented melanoma
Authors: Mantareva Vanya , Petrova Daniela , Avramov Latchezar , Angelov Ivan , Borisova Ekaterina , Peeva Margarita , Wöhrle Dieter
Published: July 2009

Three cationic zinc phthalocyanines ( ZnPcs ), tetrakis-(3-methylpyridyloxy)-, tetrakis-(3-hexyl-pyridyloxy)-, and tetrakis-(3-dodecylpyridyloxy)phthalocyaninezinc ( ZnPc Me, ZnPc He and ZnPc Do) have been studied as advanced fluorescent contrast agents for pigmented melanoma tumor. UV-vis spectroscopic properties of the monomers were investigated. Their photophysical behavior as a substantial part of dye-induced fluorescence was evaluated. The selective accumulation and labeling capacity towards B16F0 pigmented melanoma tumor were determined. Melanin containing cells were isolated and incubated with ZnPcs at several time intervals (1, 1.5 and 6 h) following the kinetics of cellular uptake. The highest accumulation was found for ZnPcHe . A lower uptake was detected for the more lipophilic ZnPcDo and more hydrophilic ZnPcMe . The fluorescence diagnostic potential of ZnPcs towards pigmented melanoma by using an argon-dye laser detection set-up was demonstrated.
Spectroscopic studies of the interaction of cationic water-soluble iron(III) meso-tetrakis(4-N-methylpyridiniumyl)porphyrin (FeTMPyP) with ionic and nonionic micelles
Authors: Santiago Patrícia S. , Gandini Shirley C. M. , Tabak Marcel
Published: July 2009

Interactions of cationic FeTMPyP with ionic and nonionic micelles have been studied by optical absorption, resonance light scattering (RLS) and 1 H NMR spectroscopies. The equilibrium behavior of FeTMPyP as a function of pH is described by several species in aqueous solution. The presence of phosphate anions leads to the existence of additional species in the acid p H region, probably due to the coordination of phosphates to the iron. FeTMPyP solution as a function of pH in the presence of anionic SDS showed a simplified equilibrium in acidic pH region, favoring the transition to the dimeric species. Titration of FeTMPyP as a function of SDS surfactant concentration showed the presence of three different porphyrin species: free metalloporphyrin monomers (or dimers depending on pH), metalloporphyrin monomers (or dimers) bound to the micelles, and nonmicellar metalloporphyrin/surfactant aggregates. In the case of zwitterionic LPC and HPS, and nonionic TRITON X-100 the nonmicellar metalloporphyrin/surfactant aggregates were not observed. Binding constants were calculated from optical absorption data and have values of 2 × 103 M −1 for SDS being much smaller for HPS (58 M −1), LPC and TRITON X-100. Comparison with our previous data for anionic FeTPPS 4 shows that both the electrostatic factor and hydrophobic forces are relevant in the porphyrin-surfactant interaction: for FeTPPS 4 binding constants to cationic CTAC and zwitterionic HPS are of the same order of magnitude, 1-3 × 104 M −1; for FeTMPyP the delocalization of the positive charges from the periphery substituents into the macrocycle ring leads to reduction of both electrostatic attraction to the micelle as well as hydrophobic character of the porphyrin ring, leading to a 10-fold reduction of binding to the micelles of opposite charge to the porphyrin. NMR data indicated that FeTMPyP is bound to the micelles as an equilibrium of two forms of monomer at pH 2.0, and at pH 9.0 the bound aggregated form (possibly dimers) is observed predominantly with some amount of a monomeric form.
Effects of central metal on the photophysical and photochemical properties of non-transition metal sulfophthalocyanine
Authors: Ogunsipe Abimbola , Nyokong Tebello
Published: July 2009

The photophysical and photochemical properties and quenching (by 1,4-benzoquinone) of metallophthalocyanine sulfonates of aluminium ( AlPcSmix), zinc ( ZnPcSmix), silicon ( SiPcSmix), germanium ( GePcSmix) and tin ( SnPcSmix) are presented. The quantum yield values of fluorescence (ΦF), triplet state (ΦT), singlet oxygen (ΦΔ) and photodegradation (Φd) were determined and the observed trends in their variation among the complexes discussed in terms of aggregation and the heavy atom effect. 1,4-benzoquinone effectively quenched the fluorescence of the complexes. Quenching analyses gave positive deviations from Stern-Volmer behavior, suggesting the existence of static quenching in addition to dynamic quenching. The static and dynamic components of the quenching were separated using a modified Stern-Volmer equation and the “sphere of action quenching model”. The quenching constant was found to be a function of the radius of the central metal ion.
Synthesis of novel pyropheophorbide a-fullerene conjugates
Authors: Helmreich Matthias , Hirsch Andreas , Jux Norbert
Published: July 2009

Two pyropheophorbide a units were attached via a malonate addition reaction to the [60]fullerene core to give a trichromophoric system. Also, in a different approach two pyropheophorbide a moieties were coupled to a hexasubstituted [60]fullerene diol. The mono-adduct was very light and oxygen sensitive whereas the corresponding hexaadduct showed a much higher stability.
Electrochemical and spectroelectrochemical properties of building blocks for molecular arrays: reactions of quinoxalino[2,3-b]porphyrins containing metal(II) ions
Authors: Ou Zhongping , E Wenbo , Shao Jianguo , Burn Paul L. , Sheehan Craig S. , Walton Robin , Kadish Karl M. , Crossley Maxwell J.
Published: July 2009

Quinoxalino[2,3-b]porphyrins are laterally-extended porphyrins with aromatic ring systems fused to the β,β'-positions of a pyrrolic ring of the macrocycle. They are building blocks for coplanar laterally-extended oligoporphyrins with applications in molecular electronics. The electrochemistry and spectroelectrochemistry of four such quinoxalinoporphyrins containing metal(II) ions and one free-base quinoxalinoporphyrin dissolved in nonaqueous media have been investigated and the data are compared to that seen for the same derivatives of the parent macrocycle lacking the fused quinoxaline ring. The investigated compounds are represented as (P)M and (PQ)M, where P = 5 ,10,15,20-tetrakis(3,5-di-tert-butylphenyl)porphyrin, PQ = 5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)quinoxalino[2,3-b]porphyrin and M = 2 H , Zn , Cu , Ni or Pd . The complexes all undergo two ring-centered reductions and one or two ring-centered oxidations in PhCN , CH 2 Cl 2, pyridine or THF . Additional redox reactions are also seen for the quinoxaline group in THF . The fusion of an electroactive quinoxaline group to the porphyrin macrocycle results in an 80 to 270 mV shift of E 1/2 towards easier reductions and the appearance of a third reduction which is assigned as a quinoxaline-centered redox process. The average HOMO-LUMO gap for the ( P ) M and ( PQ ) M derivatives is 2.26 ± 0.09 V and 2.14 ± 0.08 V , respectively. Both values are smaller than the average separation of 2.33 ± 0.13 V for the corresponding derivatives of tetraphenylporphyrin. The electrochemistry and UV-visible spectroelectrochemcal data indicate that moderate communication exists between the quinoxaline unit and the porphyrin π-ring system.
Normal and abnormal heme biosynthesis Part 4: Molecular dynamics simulations of coproporphyrinogen-III and related di- and tricarboxylic acids
Authors: He Jingyuan , Kaprak Todd A. , Jones Marjorie A. , Lash Timothy D.
Published: July 2009

The first cyclic tetrapyrrolic intermediates in the heme biosynthetic pathway are generated as porphyrinogens (hexahydroporphyrins), but unlike the aromatic porphyrin nucleus these structures must take on highly distorted conformations. Although this structural requirement is self-evident, these intermediates are often represented as flat structures. In order to gain a better understanding of the enzyme coproporphyrinogen oxidase, which is responsible for the conversion of coproporphyrinogen-III to protoporphyrinogen-IX, conformational studies were performed using molecular dynamics simulations. These studies were carried out on the natural substrate and six synthetic analogues using a Silicon Graphics workstation and the BIOGRAF 3.1 program (Molecular Simulations Inc.). The dynamics were run for 50 ps using the Verlet algorithm and Dreiding force field for each porphyrinogen with 500 quenching steps at 300 and 500 K. The five lowest energy conformations were then used as starting structures for simulations of 200 ps. The data show that the propionic acid side chains critically affect the conformations by hydrogen bonding interactions, and the chair and saddle forms are the most stable conformations. In many cases the B ring propionate moiety, which is known to be crucial for substrate recognition for coproporphyrinogen oxidase, is found to be free of intramolecular hydrogen bonds. However, simulations in the presence of water molecules gave chaise longe conformations and intermolecular interactions overwhelmed other effects for solvated porphyrinogens. Although the local environment will influence the preferred conformations, these MD simulations provide insights into how natural porphyrinogens can behave under physiological conditions.
Synthesis and photophysical properties of a covalently linked porphyrin-phthalocyanine conjugate
Authors: Zhao Zhixin , Ogunsipe Abimbola O. , David Maree M. , Nyokong Tebello
Published: July 2009

The synthesis of a phthalocyanine-porphyrin heteropentamer (zinc(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin)) zinc(II) phthalocyanine, ( ZnPc -( ZnTPP )4), containing four units of zinc tetraphenylporphyrin linked to a central zinc phthalocyanine macrocycle via an ether linkage is reported. The photophysical parameters of the pentamer are reported in toluene and dimethyl sulfoxide ( DMSO ). The observed differences in the fluorescence behavior of the pentamer in the two solvents is explained in terms of emission from different states; charge transfer state in DMSO and locally excited state in toluene. The rate constants for fluorescence, intersystem crossing, internal conversion, and of charge and energy transfer are reported for the pentamer. Quantum yields for fluorescence, internal conversion, triplet state and of charge and energy transfer are also reported for the pentamer, ZnPc -( ZnTPP )4 and the mixture of ZnPc and ZnTPP . The latter two parameters are higher in the pentamer compared to a mixture containing ZnPc and ZnTPP .
Synthesis and characterization of the iron(III) complexes of tetra-(β,β'-tetramethylene)tetraphenylporphyrin, (TC6TPP)FeCl and (TC6TPP)FeONO2
Authors: Yatsunyk Liliya A. , Ann Walker F.
Published: July 2009

The synthesis, NMR and EPR spectroscopic investigation as well as two crystal structures of ( TC 6 TPP ) FeX , where X - = chloride and nitrate are reported. The crystal structure of ( TC 6 TPP ) FeCl reveals an almost equal mixture of saddled and ruffled distortion of the porphyrin as judged by the coefficients of the lowest-frequency vibrational modes (calculated from Normal-Coordinate Structural Decomposition), while ( TC 6 TPP ) FeONO 2 is mainly saddled and more distorted overall. This difference in core structure indicates high conformational flexibility of the TC 6 TPP porphyrin ligand. Overall, both ( TC 6 TPP ) FeX structures have smaller deviation from planarity as compared to five coordinate ( OMTPP ) FeCl and ( OETPP ) FeCl . Therefore, the nature and number of peripheral substituents as well as the axial ligand(s) control geometry and conformation of the porphyrins and fine-tune their spectroscopic properties. EPR data (4.2 K) indicate a predominantly high-spin ( S = 5/2, 97.3%) ground state for ( TC 6 TPP ) FeCl and less pure high-spin state ( S = 5/2, 80%) for ( TC 6 TPP ) FeONO 2. The NMR results support an ideally saddled structure or rapid switching between saddled and ruffled conformations of ( TC 6 TPP ) FeX in solution. The flexibility of the porphyrin core was addressed by using dynamic NMR spectroscopy. The following kinetic parameters for ring inversion were obtained: Δ H ‡ = 24(1) kJ . mol −1, Δ S ‡ = −37(3) J . mol −1. K −1 and Δ H ‡ = 36(1) kJ . mol −1, Δ S ‡ = 20(4) J . mol −1. K −1 for ( TC 6 TPP ) FeCl and ( TC 6 TPP ) FeONO 2, respectively. This results in low free energies of activation, Δ G 298‡ = 35(2) and 30(2) kJ.mol−1, respectively, indicating extremely high flexibility of the porphyrin core in solution (kex298 > 4.2 × 106 and 3.8 × 107 s−1).
Axial ligand exchange reaction on ruthenium phthalocyanines
Authors: Yang Xichuan , Kritikos Mikael , Åkermark Björn , Sun Licheng
Published: July 2009

Bis(4-methylpyridine)phthalocyaninato ruthenium(II) has been synthesized. It was proved by single-crystal X-ray diffraction that the central Ru(II) atom is bonded to six N atoms in an elongated octahedral configuration, and the axial ligands have a significantly longer Ru - N bond distance, 2.101(4) Å, than the independent pyrrol Ru - N bond, 1.99 Å. Therefore, the axial ligands can be exchanged by other ligands. The ligand exchange reactions with diethyl pyridyl-4-phosphonate and diethyl pyridylmethyl-4-phosphonate were studied in high boiling-point solvents at elevated temperatures, ca 160 °C. Mono-ligand as well as double-ligand replaced complexes were obtained. The complexes have been isolated by column chromatography. These complexes have potential applications, such as in dye sensitized solar cells.
Synthesis of new carboran-based phthalocyanines and study of their activities in the photooxidation of citronellol
Authors: Tsaryova Olga , Semioshkin Andrej , Wöhrle Dieter , Bregadze Vladimir I.
Published: July 2009

The synthesis and characterization of novel phthalocyanines containing o-carborane groups are described. These new tetrasubstituted phthalocyanines are of interest for the use in cancer therapy. The activities of the carboranyl substituted phthalocyanines were evaluated by the photooxidation of (S)-(−)-citronellol to give a high oxygen consumption comparable to the photosensitizers tetrasulfophthalocyanine zinc complexes.
Fluorescence anisotropy and transient absorption of halogenated silicon(IV) phthalocyanines with axial poly(ethylene-glycol) substituents
Authors: Zeug Andre , Meyer Matthias , Lo Pui-Chi , Ng Dennis K. P. , Röder Beate
Published: July 2009

Herein we report the utilization of fluorescence anisotropy to give rough hints on the conformation of three halogenated silicon-phthalocyanines with axially substituted polyethyleneglycol chains in solution. To deconvolute decay data sets from the instrumental response function a scanning fit algorithm was used, which facilitates the visualization of fitting accuracy and correlation of parameters of the assumed decay function. Moreover, to extend our investigation of photophysical properties in the nonlinear domain, the transient absorption in the picosecond range was measured and thus excited state absorption spectra are presented.
Aza-substitution effect on the Q-band excitations of free-base porphin, chlorin, and bacteriochlorin: SAC-CI theoretical study
Authors: Hasegawa Jun-ya , Kimura Takayuki , Nakatsuji Hiroshi
Published: July 2009

Electronic structure of the excited states and absorption spectra of free-base azaporphins, azachlorin, and azabacteriochlorin were systematically investigated by SAC-CI calculations. Aza-substitution at the meso position affects the orbital energy of the next-HOMO, and the transition dipole moment enlarges as the number of the substitution increases. Some of the aza-substitutions dramatically affect the direction of the transition dipole, due to reduction of the molecular symmetry, which was studied in detail by a decomposition analysis of the transition dipole moment. Tetraza-substitution in chlorin and bacteriochlorin increases the oscillator strength more than that of tetrazaporphin. The mechanism underlying these changes originates mainly from the relaxation of near-degeneracy in the main configurations. These findings would be useful for the application to the molecular design of the excited states.
Photochemical and photophysical properties of pentoxy- and naphthaloxy appended magnesium and zinc phthalocyanines
Authors: Maqanda Wesiwe , Nyokong Tebello , Maree M. David
Published: July 2009

Photochemical and photophysical measurements were conducted on pentoxy and naphthaloxy appended zinc and magnesium phthalocyanines. We describe in this paper the synthesis as well as unexpected photodegradation behavior of naphthaloxy appended magnesium phthalocyanines. General trends are described for quantum yields of photodegradation, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds.
Synthesis, spectral and electrochemical characterization of non-aggregating α-substituted vanadium(IV)-oxo phthalocyanines
Authors: Jiang Zhou , Ou Zhongping , Chen Naisheng , Wang Jundong , Huang Jinling , Shao Jianguo , Kadish Karl M.
Published: July 2009

Two α-substituted vanadium-oxo phthalocyanines, [( OC 6 H 3(t- Bu )2)4Pc] VO and [( OC 8 H 17)4Pc] VO , where OC 6 H 3(t- Bu )2 is 2,4-di-tert-butylphenoxy and OC 8 H 17 is 2,2,4-tri-methyl-3-pentoxy, were synthesized and characterized by elemental analysis, mass spectrometry, UV-visible, IR, ESR spectroscopy and electrochemistry. Both complexes have good solubility and do not aggregate in polar or non-polar solvents. Three reductions and two oxidations can be observed in DMF containing 0.2 M TBAP. A HOMO-LUMO gap of ~1.4 V is seen for both complexes. The first two one-electron reductions and first oxidation are reversible diffusion controlled electrode processes under the given experimental conditions. The effects of solvent and phthalocyanine macrocycle substituents on the Q bands of the electronic absorption spectra are discussed.
Cyclic voltammetry of water-soluble manganese porphyrins in the presence of cyclodextrins
Authors: Ramirez-Gutierrez Oscar , Claret Josep , Ribo Josep M.
Published: July 2009

The addition of cyclodextrins (α-CD, β-CD, 2-hydroxopropyl-β-CD and γ-CD) to aqueous solutions of representative cationic ( MnTMPyP ) and anionic ( MnTPPS 4) water-soluble Mn porphyrins only substantially affect the behavior of the Mn (III)/ Mn (II) couple when inclusion complexes (i.e. for MnTPPS 4) are formed. The voltammetric responses were interpreted under the assumption that the inclusion complexes are electroactive, which occurs after their adsorption on the electrode surface. In addition, the results point to a higher affinity of the cyclodextrins for Mn II TPPS 4 than for Mn III TPPS 4.
A short route to chlorin-α-diones
Authors: Wicks Matthew N. , Burn Paul L.
Published: July 2009

Chlorin-α-diones and tetraones are useful intermediates for the formation of porphyrin arrays. We have developed a simple three-step route to chlorin-α-diones and tetraones. It was found that meso-tetraarylchlorins could be converted to hydroxychlorins when adsorbed on silica. The hydroxychlorins could then be oxidized with the Dess-Martin Periodinane to the corresponding chlorin-α-diones and tetraones. The parent 5,10,15,20-tetrakis(3,5-di-t-butylphenyl)porphyrin could be transformed to 17,18-dioxo-5,10,15,20-tetrakis(3,5-di-t-butylphenyl)chlorin in the three steps in an overall yield of 54% while a tetraazaanthracene linked bis-bacteriochlorin could be transformed to the bis-bacteriochlorin-tetraone in a yield of 16%.
Preparation and properties of sulfur-containing tetraazaporphyrin iron supported on anion-exchange resin
Authors: Lei Yuping , Sun Jie , Yang Changjun , Deng Kejian , Wang Duoyuan
Published: July 2009

An anion-resin carrying the catalyst iron(II) tetra(1,4-dithin)porphyrazine, ( Fe (II) Pz ( dtn )4/resin), may effectively interact with the lone-pair electron of the sulfur in the Fe (II) Pz ( dtn )4 to keep the absorption for the catalyst molecule, which can efficiently activate molecular oxygen coordinated with iron(II) on the axial orientation of Fe (II) Pz ( dtn )4 through electron transfer in a heterogeneous process. On the other hand, the hydrophilic property of the resin also facilitates adsorption of the anion-substrates in the aqueous solution onto the unoccupied resin surface to increase the substrate concentration around the Fe (II) Pz ( dtn )4 and the contact probability between the substrate with activated molecular oxygen to promote the oxidative degradation of these adsorbed substrates. The stability and repeatability of the Fe (II) Pz ( dtn )4/resin were determined by some control experiments. The results indicate that Fe (II) Pz ( dtn )4 was stable enough in the presence of active oxygen species under irradiation of visible light and could degrade recalcitrant organic pollutants such as rhodamine B and p-nitrobenzoic acid. It can be reused at least 5 cycling runs without losing activity.
Bathochromic shift of the Q-bands of octakis(p-t-butylbenzyloxy)phthalocyanines with magnesium(II), nickel(II) and copper(II) in a solvent mixture of chloroform and acetic acid
Authors: Kasuga Kuninobu , Yashiki Katsuyori , Sugimori Tamotsu , Handa Makoto
Published: July 2009

1,4,8,11,15,18,22,25-octakis(p-t-butylbenzyloxy)phthalocyanine complexes of magnesium(II), nickel(II) and copper(II) were prepared by refluxing the propanol solution of 3,6-di(p-t-butylbenzyloxy)phthalonitrile in the presence of magnesium turnings. The complexes showed intense Q-bands between 740 and 750 nm in chloroform. The magnesium(II) complex showed an additional weak band at 807 nm in chloroform, while the nickel(II) and copper(II) did not. The Q-band of the magnesium(II) species was red-shifted with increase of acetic acid in the solvent mixture of chloroform and acetic acid; 745, (765, 807) and (810, 868 nm) in chloroform, 0.1% (v/v) acetic acid and 60% (v/v) acetic acid, respectively. The magnesium(II) complex has bands at 900 and 999 nm in trifluoroacetic acid. In the solvent mixture of 1% (v/v) acetic acid, the red-shift of the Q-band was larger for the magnesium(II) derivative, a little for the nickel(II) and scarcely for the copper(II), respectively. The shift was explained by protonation of the external nitrogen atoms of the phthalocyanine ring.