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1.
UV lamp, filtered halogen lamp (at 425 nm) and Green laser (532 nm) experiments on a series of meso-substituted tetra phenyl porphyrin, TPP, bearing methoxy peripheral groups together with a metal derivate of 3,4 dimethoxy TPP were lead to different protonation and aggregation structures. Properties of irradiated porphyrins were investigated using their absorption and emission spectra in dichloromethane solution. The results show that the optical properties of the TPP derivates depend on light irradiation source, which shows the tuning of the absorption and emission spectra of the TPP derivates. From the dynamic light scattering measurements, the size distribution of samples was estimated about 5–15 nm in solvent after irradiation. Atomic force microscopy images of deposited porphyrins on the glass surface were shown average particle size between 10 and 30 nm. Particularly, self-assembly of the porphyrin derivates was also observed when green laser was used. We suggest that the irradiation source plays an important role in the controlling of size and morphology of products, and we propose a self-organization model to explain the formation of the porphyrin nanostructures.  相似文献   

2.
Tetrapyrrole rings possess four nitrogen atoms, two of which act as Br?ndsted bases in acidic media. The two protonation steps occur on a close pH range, particularly in the case of meso-tetraphenylporphyrin (TPP) derivatives. If the cause of this phenomenon is well known--a protonation-induced distortion of the porphyrin ring--data on stepwise protonation constants and on electronic absorption spectra of monoprotonated TPPs are sparse. A multivariate approach has been systematically applied to a series of glycoconjugated and hydroxylated TPPs, potential anticancer drugs usable in Photodynamic Therapy. The dual purpose was determination of protonation constants and linking substitution with basicity. Hard-modeling version of MCR-ALS (Multivariate Curve Resolution Alternating Least Squares) has given access to spectra and distribution profile of pure components. Spectra of monoprotonated species (H(3)TPP(+)) in solution resemble those of diprotonated species (H(4)TPP(2+)), mainly differing by a slight blue-shift of bands. Overlap of H(3)TPP(+) and H(4)TPP(2+) spectra reinforces the difficulty to evidence an intermediate form only present in low relative abundance. Depending on macrocycle substitution, pK values ranged from 3.5±0.1 to 5.1±0.1 for the first protonation and from 3.2±0.2 to 4.9±0.1 for the second one. Inner nitrogens' basicity is affected by position, number and nature of peripheral substituents depending on their electrodonating character. pK values have been used to establish a predictive Multiple Linear Regression (MLR) model, relying on atom-type electrotopological indices. This model accurately describes our results and should be applied to new TPP derivatives in a drug-design perspective.  相似文献   

3.
To examine the influence of mixed substituents on the structural, electrochemical redox behavior of porphyrins, two new classes of beta-pyrrole mixed substituted free-base tetraphenylporphyrins H2(TPP(Ph)4X4) (X = CH3, H, Br, Cl, CN) and H2(TPP(CH3)4X4) (X = H, Ph, Br, CN) and their metal (M = Ni(II), Cu(II), and Zn(II)) complexes have been synthesized effectively using the modified Suzuki cross-coupling reactions. Optical absorption spectra of these porphyrins showed significant red-shift with the variation of X in H2(TPPR4X4), and they induce a 20-30 nm shift in the B band and a 25-100 nm shift in the longest wavelength band [Q(x)(0,0)] relative to the corresponding H2TPPR4 (R = CH3, Ph) derivatives. Crystal structure of a highly sterically crowded Cu(TPP(Ph)4(CH3)4).2CHCl3 complex shows a combination of ruffling and saddling of the porphyrin core while the Zn(TPP(Ph)4Br4(CH3OH)).CH3OH structure exhibits predominantly saddling of the macrocycle. Further, the six-coordinated Ni(TPP(Ph)4(CN)4(Py)2).2(Py) structure shows nearly planar geometry of the porphyrin ring with the expansion of the core. Electrochemical redox behavior of the MTPPR4X4 compounds exhibit dramatic cathodic shift in first ring oxidation potentials (300-500 mV) while the reduction potentials are marginally cathodic in contrast to their corresponding MTPPX4 (X = Br, CN) derivatives. The redox potentials were analyzed using Hammett plots, and the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap decreases with an increase in the Hammett parameter of the substituents. Electronic absorption spectral bands of H2TPPR4X4 are unique that their energy lies intermediate to their corresponding data for the H2(TPPX8) (X = CH3, Ph, Br, Cl) derivatives. The dramatic variation in redox potentials and large red-shift in the absorption bands in mixed substituted porphyrins have been explained on the basis of the nonplanarity of the macrocycle and substituent effects.  相似文献   

4.
The nonlinear absorption of two porphyrin diacids (H4TPP2+ and H2DSP2+), the diprotonated forms of free base tetraphenylporphyrin (H2TPP) and dithiaporphyrin (DSP), were studied in the wavelength range of 500-650 nm. The two porphyrin diacids exhibited perturbed static and dynamic characteristics and enhanced nonlinear absorption properties relative to their parent neutral complexes in solution. Furthermore, for the dithiaporphyrin diacid, the introduction of S-atoms into the porphyrin core makes it a better candidate for optical limiting relative to the simple porphyrin. Their photophysical parameters such as ground and excited states absorption cross-sections, together with fluorescence lifetime and intersystem crossing time, were determined.  相似文献   

5.
6.
The photophysical characterization of the two tautomers (1e and 1i) of 5,10,15,20-tetraphenyl N-confused free-base porphyrin, as well as the tautomer-locked 2-methyl 5,10,15,20-tetraphenyl N-confused free-base porphyrin, was carried out using a combination of steady state and time-resolved optical techniques. N-Confused porphyrins, alternatively called 2-aza-21-carba-porphyrins or inverted porphyrins, are of great interest for their potential as building blocks in assemblies designed for artificial photosynthesis, and understanding their excited-state properties is paramount to future studies in multicomponent arrays. Femtosecond resolved transient absorption experiments reveal spectra that are similar to those of tetraphenylporphyrin (H2TPP) with either Soret or Q-band excitation, with an extinction coefficient for the major absorbing band of 1e that was about a factor of 5 larger than that of H2TPP. The lifetime of the S1 state was determined at a variety of absorption wavelengths for each compound and was found to be consistent with time-resolved fluorescence experiments. These experiments reveal that the externally protonated tautomer (1e) is longer lived (tau = 1.84 ns) than the internally protonated form (1i, tau = 1.47 ns) by approximately 369 ps and that the N-methyl N-confused porphyrin was shorter lived than the tautomeric forms by approximately 317 ps (DMAc) and approximately 396 ps (benzene). Steady-state fluorescence experiments on tautomers 1e and 1i and the N-methyl analogues corroborate these results, with fluorescence quantum yields (Phi(Fl)) of 0.046 (1e, DMAc) and 0.023 (1i, benzene), and 0.025 (DMAc) and 0.018 (benzene) for the N-methyl N-confused porphyrin. The lifetime and quantum yield data was interpreted in terms of structural changes that influence the rate of internal conversion. The absorption and transient absorption spectra of these porphyrins were also examined in the context of DFT calculations at the B3LYP/6-31G(d)//B3LYP/3-21G(d) level of theory and compared to the spectra/electronic structure of H2TPP and tetraphenyl chlorin.  相似文献   

7.
The structure of THF-coordinated [2,3,7,8,12,13,17,18-octafluoro-5,10,15,20-tetraphenylporphinato]zinc, Zn(F(8)TPP).THF, and photophysical studies of 2,3,7,8,12,13,17,18-octafluoro-5,10,15,20-tetraphenylporphyrin, F(8)TPP, Zn(F(8)TPP), 2,3,7,8,12,13,17,18-octafluoro-5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, F(28)TPP, and [2,3,7,8,12,13,17,18-octafluoro-5,10,15,20-tetrakis(pentafluorophenyl)porphinato]zinc, Zn(F(28)TPP), in benzonitrile, are reported. A key point from these studies is that the octafluorinated F(8)TPP and perfluorinated F(28)TPP porphyrins possess similar absorption spectra, but dissimilar X-ray crystal structures and disparate photophysical characteristics. These data cannot be easily accommodated within currently accepted theories which relate macrocycle distortion and optoelectronic properties.  相似文献   

8.
Abstract— The absorption and emission spectra, fluorescence quantum yields and lifetimes and triplet state properties of a boronated porphyrin, the tetrakiscarborane carboxylate ester of 2,4-(α,β-dihydroxyethyl) deuteroporphyrin IX (BOPP), have been determined. This compound is an alternative photodynamic therapy (PDT) agent that exhibits highly selective tumor localization, with the potential to be used in conjunction with boron neutron capture therapy. The photophysical characteristics of BOPP are similar to other porphyrins and it exhibits marked aggregation and acid-base speciation under typical physiological conditions. In particular, protonation of the porphyrin imino (-N=) nitrogens occurs in the pH 5–7 region and influences the photophysical properties. Time-resolved confocal fluorescence imaging of the intracellular distribution of BOPP in C6 glioma cells indicates distinct subcellular localization and heterogeneity of emission. The results are interpreted and discussed in terms of the possible mechanisms for cellular uptake and localization.  相似文献   

9.
Diarylethene derivatives are a class of fascinating photochromic materials because of their open and closed isomers with different absorption spectra and many other characteristics.To reveal the detailed structure and optoelectronic properties as well as the effect of metal centres and substituents on them,a systematic study on a series of diarylethene derivatives and their Re(I),Pt(II),and Ir(III) complexes was performed via theoretical calculation.The optimized geometries,electronic properties,frontier molecular orbitals,ionization potentials,electron affinities,reorganization energies,and absorption spectra for both of their open-and closed-isomers have been calculated and analyzed.Metal-coordination and substituents exhibit great influence on the photophysical,charge-injection and-transporting characteristics.In addition,the binding of F-with the boron atom of dimesitylboryl group through Lewis acid/base interactions also induces great changes of structural,photophysical and electronic properties for these diarylethene derivatives,and consequently the compound with the substituent of dimesitylboryl group can be used as selective near-infrared phosphorescent F-probe.  相似文献   

10.
Atomic force microscopy (AFM) of porphyrin aggregates formed on silica from acidic aqueous solution is used to investigate the basis for the previously reported counterion dependence of the optical spectra of aggregates of H(2)TCPP(2+), the diacid form of tetra(p-carboxyphenyl)porphyrin (TCPP). Resonance light scattering confirms the presence of excitonically coupled porphyrin aggregates in solutions of H(2)TCPP(2+) in both aqueous HCl and HNO(3). Aggregates formed in aqueous HNO(3) solutions show resonance light scattering (RLS) at wavelengths within both the H and J aggregate absorption bands and are imaged on the surface of silica as nanorods about 3 to 4 nm in height. H(2)TCPP(2+) aggregates in aqueous HCl solution exhibit RLS when excited within the blue-shifted Soret band (H band) and produce AFM images on silica of ring-shaped structures ranging from about 200 to 2000 nm in diameter. Fluorescence excitation and emission spectra reveal quenching of the Q-band emission in the aggregates at a pH less than 1 and confirm the existence of a single species, assigned to a dimer, at a pH just above 1. The morphology of the nanostructures as revealed by AFM provides insight into the structural basis for the counterion-dependent optical properties of H(2)TCPP(2+) aggregates.  相似文献   

11.
Five amphiphilic meso-disubstituted porphyrins bearing one polar group were synthesized, and their monolayer films were prepared. Their limiting molecular areas obtained from pi-A isotherms were 0.5-0.6 nm2, which were smaller than those of the corresponding meso-tetrasubstituted porphyrins. At the air-water interface, the disubstituted porphyrins showed a broad band in visible absorption spectra compared with the solution state, and the red shift of the Soret band exhibited a significant dependence on the kind of hydrophilic groups at the meso positions. Interestingly, the monolayer of the disubstituted porphyrin bearing a carboxyphenyl group (1-CO2H) showed a blue shift of the Soret band by adding cadmium chloride to the subphase, and the spectra varied upon multilayer deposition. The observed phenomena were interpreted by using the exciton theory. The effect of hydrophilic substituents on the absorption spectra of disubstituted porphyrin monolayers is discussed.  相似文献   

12.
In the present article, tetraphenylporphyrin a new ratiometric fluorescence sensitizer for zinc ion has been proposed. Electronic absorption, emission and (1)H NMR spectral characteristics of meso-tetraphenylporphyrin (TPP) have been studied in acetonitrile medium in the presence of zinc perchlorate. Absorption spectral studies indicate the formation of a new complex between zinc ion and the porphyrin moiety in the ground state as distinguished from the characteristics of metalo(zinc) porphyrin compound. The energy of maximum fluorescence of porphyrin shifts towards blue with the addition of Zn(ClO(4))(2). Steady state emission studies point to the existence of two emitting species viz, the solvated and the complexed porphyrin in equilibrium. The fluorescence emission of tetraphenylporphyrin at 651-nm bands decreases while that at 605 nm increases upon zinc ion interaction in acetonitrile. Thus, the TPP can behave as a ratiometric fluorescent sensor. This fluorescence modulation of TPP should be applicable to dual-wavelength measurement of various biomolecules or enzyme activities. (1)H NMR spectra of the porphyrin suffered a radical change with the addition of zinc perchlorate which points to the formation of a new porphyrin complex. This change is due to the difference in the electron-donating ability of the pyrrolic nitrogens before and after complexation with Zn(2+). The values of equilibrium constant for the binding process have been determined in acetone and acetonitrile, in both ground and excited states.  相似文献   

13.
A series of meso-to-meso ethynyl-bridged multiporphyrin arrays have been synthesized using Sonogoshira palladium-catalyzed cross-coupling reactions involving the appropriate ethynylporphyrin and iodoporphyrin precursors. The absorption spectra of these multiporphyrins show splitting of the Soret bands and significant red shifts of the Q bands as compared to the combination of the corresponding components. These conjugated multiporphyrins also show red shifts in their emission spectra as the pi-conjugation is expanded. In the electrochemical measurements, the porphyrins dimer 7 shows two 1 - e- oxidations at E(1/2) = +0.63 and +0.76 V for the first electron abstraction from the two porphyrin rings, indicating electronic communication between the two porphyrin units. The porphyrin trimer 4 exhibits the first and second 1 - e- oxidations at E(1/2) = +0.68 and +0.77 V, respectively, which correspond to the two outer porphyrins. The cyclic voltammogram of pentamer 5 shows two overlapping 1 - e- couples at E(1/2) = +0.56 and +0.66 V, and one 2 - e- couple at E(1/2) = +0.86 V, for the four outer porphyrin units. These results demonstrate that in the porphyrin trimer and pentamer the individual peripheral porphyrin units are electrochemically coupled via a central porphyrin core. The UV-Vis-NIR spectra of the oxidized species of these multiporphyrins exhibit a broad intervalence charge transfer (IVCT) band in the region from 1200 to 3000 nm. The present work shows that a central porphyrin unit appended with ethynyl bridges affords strong electronic interactions between the peripheral porphyrin rings over a distance of about 15 A.  相似文献   

14.
This study investigated the protonation of nitrogen atoms in porphyrins with meso-phenyl p-substituted by an electron-withdrawing group using N 1s X-ray photoelectron spectroscopy (XPS), the N K X-ray absorption near-edge structure (XANES), and the discrete variational (DV)-Xalpha molecular orbital (MO) method. Both tetraphenylporphyrin (TPP) and tetrakis(p-sulfonatophenyl)porphyrin (TSPP) have a single structure: the former has two protonated and two non-protonated N atoms in the porphine ring; the latter has four protonated N atoms in the porphine ring. In contrast, a combination of XPS, XANES, and DV-Xalpha MO calculations shows that tetrakis(p-carboxyphenyl)porphyrin (TCPP) has a dual structure: one structure has two protonated and two non-protonated N atoms; the other has four protonated N atoms. Furthermore, this result was also considered based on the protonation constants of N atoms in the porphyrins. The correlation between the strength of electron-withdrawing groups and protonation to N atoms in porphyrins can be described using the spectral patterns of the N 1s XPS and N K XANES spectra.  相似文献   

15.
Extensive photophysical properties of isomeric tetra-2-pyridylporphyrin (TpyP(2)), tetra-3-pyridylporphyrin (TpyP(3)), and tetra-4-pyridylporphyrin (TpyP(4)) have been studied in the presence of a series of phenols of increasing hydrogen bonding power in dichloromethane solution by employing UV/vis spectroscopy; steady-state, time-resolved fluorescence spectroscopy; and transient absorption spectroscopic techniques. The change of absorption spectra of all three porphyrins as a function of different phenol concentrations established the preference of hydrogen bonded complex formation to the peripheral pyridyl nitrogen rather than the pyrrole nitrogen of the porphyrin macrocycle. The fluorescence behaviors of the porphyrins which were observed upon addition of different phenols point to a marked dependence on the nature of the added phenols. Phenols with an electron withdrawing group do not quench the fluorescence of porphyrins, whereas phenols with an electron donating group quench the singlet porphyrin both in static and dynamic pathways. A remarkable difference in quenching behaviors of singlet excited porphyrin by 4-methylphenol (4-MePhOH) and 4-MeOPhOH/4-EtOPhOH (4-EtOPhOH = 4-ethoxyphenol) are observed. The quenching of singlet excited porphyrins by 4-MePhOH is attributed to be purely static in nature, and the H-bond provides a strong nonradiative channel to singlet excited porphyrins. However, the quenching of singlet excited porphyrins by 4-MeOPhOH/4-EtOPhOH is mostly dynamic, and it is ascribed to be the reductive quenching of single excited porphyrins. Picosecond transient absorption study with TpyP(2) and 4-MeOPhOH provides the evidence of porphyrin radical anion and phenol radical cation of equal lifetime, which indicates the fact that electron transfer occurs from phenol to singlet excited porphyrin. The temperature effect on dynamic quenching by 4-MeOPhOH/4-EtOPhOH and kinetic deuterium isotope effect established the reaction to be a photoinduced concerted proton coupled electron transfer.  相似文献   

16.
The synthesis and photophysical properties are described for a series of porphyrin, phthalocyanine and pyrazinoporphyrazine derivatives which bear four or eight peripheral fluorenyl substituents as antennae. Representative examples are 5,10,15,20-tetra(9,9-dihexyl-9H-fluoren-2-yl)porphyrin (2), 5,10,15,20-tetrakis[4-(9,9-dihexyl-9H-fluoren-2-yl)phenyl]porphyrin (3), 2,3,9,10,16,17,23,24-octakis(9,9-dihexyl-9H-fluoren-2-yl)-29H,31H-phthalocyanine (8) and 2,3,9,10,16,17,23,24-octakis[4-(9,9-dihexyl-9H-fluoren-2-yl)phenyl]-29H,31H-tetrapyrazinoporphyrazine (9). Palladium-mediated Suzuki-Miyaura cross-coupling reactions have been key steps for attaching the substituents. The compounds are deep-red emitters: lambda(max)(em)=659 (3), 737 (8) and 684 nm (9). Their absorption and emission spectra, their fluorescence lifetimes and quantum yields are correlated with the structures of the macrocycles and the substituents. The solution fluorescence quantum yields of porphyrin derivatives substituted with fluorene (2-4) and terphenyl substituents (7) (Phi(f)=0.21-0.23) are approximately twice that of tetraphenylporphyrin. For phthalocyanine derivative 8, Phi(f) was very high (0.88). Specific excitation of the fluorene units of 8 produced emission from both of them (lambda(max)=480 nm) and also from the phthalocyanine core (lambda(max)=750 nm), indicating a competitive rate of energy transfer and radiative decay of the fluorenes. Organic light-emitting devices (OLEDs) were made by spin-coating techniques by using a polyspirobifluorene (PSBF) copolymer as the host blended with 3 (5 wt. %) in the configuration ITO/PEDOT:PSS/PSBF copolymer:3/Ca/Al. Deep-red emission (lambda(max)=663 nm; CIE coordinates x=0.70, y=0.27) was observed with an external quantum efficiency of 2.5 % (photons/electron) (at 7.5 mA cm(-2)), a low turn-on voltage and high emission intensity (luminance) of 5500 cd m(-2) (at 250 mA/ m(2)).  相似文献   

17.
We prepared a series of 1,3,6,8-tetrakis(arylethynyl)pyrenes with donor or acceptor substituents and investigated their photophysical properties. Solvent polarity hardly affected on the UV/vis spectra of all of the tetrakis(arylethynyl)pyrenes used in this study. On the other hand, electron-donating groups, NMe2 and NPh2 groups imparted fluorescence solvatochromicity to the skeleton by intramolecular charge transfer in the excited state. Furthermore, a tetrakis(arylethynyl)pyrene showed better lightfastness upon exposure to laboratory weathering using a xenon long arc lamp than coumarin.  相似文献   

18.
Polyglutamic dendritic porphyrins of the general formula H2PophGlu(N)OR (H2Porph = free-base meso-tetra-4-carboxyphenylporphyrin (H2TCPP), Glu=dendrimer layer composed of L-glutamates, N= 1-3: dendrimer generation number, R = terminal group (All, H)) were synthesized and characterized with NMR and MALDI-TOF mass spectroscopy. The free-acid terminated compounds were found to be highly soluble in water, with both their absorption and fluorescence spectra dependent on pH. The value of the porphyrin mono-protonation constant, measured by fluorescence rationing, increased monotonously in the studied series of dendrimers (pK3=6.31. 6.70, and 6.98, for N=1, 2, 3, respectively). For the largest dendrimer, H2PorphGlu(3)OH, pK3 was found shifted by almost two pH units relative to the non-modified H2Porph. The second protonation constant (K4) was much less affected by the dendritic substituents. At pH values less than 3.5 there were noticeable changes in fluorescence intensity and quantum yield even for the highly soluble H2PorphGlu(3)OH. This suggests that interactions between individual dendritic molecules in solution are favored by full protonation of the peripheral glutamic carboxyls. The "dendrimer-protected" porphyrins are convenient fluorescent pH sensors in the biological pH range.  相似文献   

19.
20.
Magnetic circular dichroism (MCD) spectroscopy provides valuable information about electronic excited states in molecules. The interpretation of spectra is however difficult, often requiring additional theoretical calculations to rationalize the observed signal. Recent developments in time-dependent density functional theory (TDDFT) bring hope that the applicability of MCD spectroscopy for chemical problems may be significantly extended. In this study, two modern analytical TDDFT implementations are compared and used to understand experimental MCD spectra of a model porphyrin system upon protonation. Changes in porphyrin geometry and electronic structure are related to MCD intensities by comparing the spectra of 5,10,15,20-tetraphenyl-21H,23H-porphyrintetrasulfonic acid (TPPS) measured at different pH values with the TDDFT calculations. Although the theoretical results slightly depended on the chosen exchange-correlation functional, the computations provided MCD curves that could well rationalize the experimental data. The protonation of the porphyrin core causes marked changes in the MCD spectrum, whereas the role of the substituents is limited. Also, different conformations of the porphyrin substituents cause relatively minor changes of the MCD pattern, mostly in the Soret region, where the porphine and phenyl electronic transitions start to mix. The solvent environment simulated by the dielectric model caused a shift (~20 nm) of the absorption bands but only minor variations in the absorption and MCD spectral shapes. The study thus demonstrates that the recently available first-principles interpretations of MCD spectra significantly enhance the applicability of the technique for molecular structural studies.  相似文献   

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