Charge-transfer-type fluorescence of 4-(1H-pyrrol-1-yl)benzonitrile (PBN) and N-phenylpyrrole (PP) in cryogenic matrixes: evidence for direct excitation of the CT band

The fluorescence spectrum of PBN in a neat argon matrix is excitation-wavelength-dependent: at short excitation wavelengths, it consists of dual emission assigned to a charge-transfer (CT) state and a much weaker band assigned to the locally excited (LE) state. The CT emission is broad and almost completely devoid of vibrational structure, whereas the LE band is characterized by vibrationally resolved emission. At long excitation wavelengths, only CT emission is observed, indicating that the CT state is populated directly by light absorption and not via the LE state. Comparison with jet-cooled spectra of the bare molecule allows the unambiguous assignment of the LE spectrum and the location of the 0,0 band. The matrix LE emission spectrum is blue-shifted with respect to that of the gas phase, showing that the dipole moment of the LE state is smaller than that of the ground state. The fluorescence spectrum of PBN in an argon matrix does not change appreciably when acetonitrile (AN) is added to the matrix, in contrast to the case of N-phenylpyrrol (PP) (Schweke, D.; Haas, Y. J. Phys. Chem. A 2003, 107, 9554), for which addition of AN results in the appearance of two well separated emission bands. The different photophysical behaviors of PP and PBN in an argon matrix (and in supersonic jets) are analyzed by a simple model that considers the restriction of large-amplitude motions in the matrix. The implications of these low-temperature studies for understanding the properties of these systems in liquid solution are discussed.     

Photophysics of phenylpyrrole derivatives and their acetonitrile clusters in the gas phase and in argon matrixes: simulations of structure and reactivity

Recent experiments on the dual fluorescence of phenylpyrrole (PP) and pyrrolobenzonitrile (PBN) in supersonic jets and in cryogenic matrixes are analyzed. The structures of the 1:1 clusters are calculated using ab initio, density functional theory (DFT) and molecular mechanics (MM) methods. In these calculations, the structures of PP and PBN in the ground state and in two possible minima on the charge-transfer excited state are taken from a recent theoretical analysis. The structures of PP and PBN clusters with a larger number of acetonitrile molecules are also calculated using the molecular mechanics method. It is shown that the fact that small PP:AN and PBN:AN clusters do not exhibit any charge-transfer (CT) type emission, whereas for PBN:AN(n) clusters (n > or = 4) CT emission is observed, can be understood on the basis of the calculated structures. The trapping of PP and of PBN in an argon matrix (neat and doped with acetonitrile) is simulated by a molecular dynamics procedure. The observation of locally excited (LE) fluorescence only from PP in neat argon, whereas from argon-trapped PBN both CT and LE emission bands are observed, is readily understood on the basis of these simulations. Moreover, the appearance of CT emission from PP-doped argon matrixes when acetonitrile is added is also explained, as well as the relatively small spectral shift observed upon addition of acetonitrile to PBN-doped argon matrixes.     

Spectroscopic characterization of intramolecular charge transfer of sodium 4-(N,N-dimethylamino)naphthalene-1-sulfonate

In this paper, a new dual fluorescent N,N-dimethylaminonaphthalene derivative, sodium 4-(N,N-dimethylamino)naphthalene-1-sulfonate (SDMDNS), was reported. It was found that SDMDNS emits dual fluorescence only in highly polar solvent water but not in organic solvents such as methanol, dioxane and acetonitrile. Only a single broad band emission at ca. 420 nm was observed in the short wavelength region in organic solvents. The dual fluorescence of SDMDNS in water was found at 423 and 520 nm, respectively. Introduction of organic solvent as ethanol into aqueous solution of SDMDNS leads to blue shift of the long-wavelength emission, and this was evidently supported by introduction of cyclodextrin or surfactant in the aqueous solution. It indicates that a highly polar solvent was required to bring out dual fluorescence; furthermore, the short wavelength fluorescence is emitted from locally excited (LE) state and the long wavelength fluorescence is emitted from charge transfer (CT) state. The pH dependence of the dual fluorescence of SDMDNS demonstrates that the neutral form of the molecular has a higher ratio of CT band intensity to LE band. Temperature effect on the excited state of SDMDNS was also examined and gave stabilization enthalpy (-DeltaH ) of the CT reaction 8.7 kJ mol(-1).     

Fluorescence characteristics of protonated form of 6-hydroxyquinoline in Nafion film

Fluorescence characteristics of 6-hydroxyquinoline (6-HQ) have been studied at room temperature in Nafion(R) film by steady state and nano-second time-resolved fluorescence spectroscopy. The fluorescence spectrum exhibits single emission band corresponding to the protonated form of 6-HQ in this matrix. However, the decay fits with two or three exponential functions depending on the emission wavelength monitored. At blue edge of the emission, the decay fits to three-exponential function, whereas at longer wavelengths, the decay fits to bi-exponential function. Two tentative mechanisms have been proposed to explain the experimental data, viz. a closely lying charge transfer state (CT) or an excited state proton transfer (ESPT) process. The photophysical parameters appear to be sensitive to the change in microstructure due to swelling of the membrane by the solvents.     

The crystal structure and vibrational spectra of two molecules emitting dual fluorescence: 4-(1H-Pyrrol-1-yl)benzonitrile (PBN) and 5-cyano-2-(1pyrrolyl)-pyridine (CPP)

Crystal structures and vibrational spectra are reported for the two title molecules which exhibit dual fluorescence due to the existence of a low lying charge transfer excited state. The data show that in the ground state PBN is twisted whereas CPP is planar, and the crystal structures are quite different. The experimental spectra are in very good agreement with quantum mechanical calculations, which also predict considerable differences between the vibrational spectra of CPP in the ground state and in the charge transfer excited state.     

Study on the fluorescence properties of a new intramolecular charge transfer compound 1,5-diphenyl-3-(N-ethylcarbazole-3-yl)-2-pyrazoline

The fluorescence properties of a newly synthesized compound, 1,5-diphenyl-3-(N-ethylcarbazole-3-yl)-2-pyrazoline (DEP) have been studied. On excitation at 352 nm, the fluorescence spectrum exhibits a large red shift with an increase in the polarity of solvents. The intensity of the band is different in different solvents as well. The change in the dipole moment in various solvents at room temperature has been characterized by the absorption and steady state fluorescence techniques and calculated based on the Lippert-Mataga equation. DEP has an increase of dipole moment of 2.83 D units on excitation to the lowest singlet state. It is concluded that photo-induced charge transfer from N (1) to C (3) actually exists in the excited state of the pyrazoline moiety. Its fluorescence property is relative to viscosity and temperature of solvents. The phi(f) of DEP in neutral medium or basic medium is higher than acidic medium. In addition, when the concentration of DEP is higher than 10(-3) M, its fluorescence is quenched by the collision of each molecule. The red shift of the maximum emission of DEP attributes to the formation of aggregates and the conjugate system is strengthened.     

Photophysics and Inverted Solvatochromism of 7,7,8,8-Tetracyanoquinodimethane (TCNQ)

We report absorption, fluorescence, and Raman spectroscopy of 7,7,8,8-tetracyanoquinodimethane (TCNQ) in a variety of solvents. The fluorescence quantum yields (QYs) of linear alkane solutions are similar to one another, but QY is shown to acutely decrease in other solvents with increasing polarities. The slope of the solvatochromic plot of absorption maxima is inverted from negative to positive with an increase in solvent polarity. A significant change in the frequency of carbon-carbon double bond stretching modes is not observed in Raman spectra of TCNQ in different solvents. The molar absorption coefficient is determined to calculate the oscillator strength of the absorption band. The radiative decay rate constant calculated from the oscillator strength is approximately ten times larger than that elucidated from the fluorescence lifetime and QY. These spectroscopic parameters reveal that the relaxation occurs from a Franck-Condon excited state to a distinct fluorescence emissive state with a smaller transition dipole moment.     

Photophysical studies of 7-hydroxy-4-methyl-8-(4′-methylpiperazin-1′-yl) methylcoumarin: A new fluorescent chemosensor for zinc and nickel ions in water

The title compound, a new coumarin based fluorophore having a piperazine moiety as the photoinduced electron transfer (PET) switch was prepared and its photophysical properties studied in various solvents and under different pH. Solvatochromic shift in the fluorescence spectrum revealed an increase in the dipole moment in the lowest excited singlet state compared to that in the ground state. The compound also showed an interesting intramolecular photoinduced proton transfer phenomenon in the excited state under neutral pH. It was effectively utilized as a new Chelation-enhanced fluorescence (CHEF) based chemosensor for zinc and nickel ions in water.     

A matrix isolation study of 2-isopropylidenecyclopentane-1,3-diyl (Berson-type diradical)

The photodenitrogenation of diazene 5 in an argon matrix at 10 K permitted the first observation of an IR spectrum of 2-isopropylidenecyclopentane-1,3-diyl 2 (a Berson-type diradical). A comparison of the IR spectrum with a vibrational simulation at the B3LYP/6-31G(d) level of theory revealed that the diradical 2 has a planar structure. The oxygen-trapping reaction of 2 produced regioselectively fused peroxide 6 in an oxygen-doped argon matrix at 10 K. Irradiation of the diradical 2 afforded enyne 8 in an argon matrix at 10 K.     

Ultrafast photoinduced intramolecular charge transfer in push-pull distyryl furan and benzofuran: solvent and molecular structure effect

The excited state deactivation pathways of push-pull distyryl furan and benzofuran derivatives in several organic solvents were investigated in detail by using time-resolved transient absorption and fluorescence spectroscopies, with nano- and femto-second time resolution. Solvent polarity was found to play a key role in determining the efficiencies of fluorescence, intersystem crossing and internal conversion. The triplet yield gradually decreased, while the internal conversion increased upon increasing the solvent dielectric constant. However the fluorescence showed a different solvent polarity effect in the low and high solvent polarity region, with a reversal of the trend of fluorescence properties (quantum yield and lifetime). This fact points to an emitting state of a different nature (smaller and larger dipole moments) in the two cases, as also suggested by the huge fluorosolvatochromism. In fact the ultrafast spectroscopic investigation evidenced the presence of two transients characterized by peculiar spectral shapes assigned to a locally excited (LE) and a charge transfer (CT) state. In the more polar solvents the CT state was the longer lived, fluorescent one and an intramolecular charge transfer process was found to be operative and to become faster (up to ～200-250 fs) in the higher polarity media. On the contrary, distyrylfuran, which exhibits the same molecular skeleton without the push-pull character showed a similar excited state dynamics in solvents of different polarities.     

富勒烯化聚环氧丙基咔唑的合成与表征

通过Ｆｒｉｅｄｅｌ－Ｃｒｒａｆｔｓ反应制备了富勒烯化的聚环氧丙基咔唑，聚合物中Ｃ６０的含量最高可达７．６ｗｔ％。通过凝胶渗透色谱法测定了聚合物分子量，并采用＾上Ｈ和＾１３Ｃ－ＮＭＲ，ＩＲ，热分析及光谱等手段对其结构进行了分析与表征。     

The electronic origin of the dual fluorescence in donor-acceptor substituted benzene derivatives

The origin of the dual fluorescence of DMABN (dimethylaminobenzonitrile) and other benzene derivatives is explained by a charge transfer model based on the properties of the benzene anion radical. It is shown that, in general, three low-lying electronically excited states are expected for these molecules, two of which are of charge transfer (CT) character, whereas the third is a locally excited (LE) state. Dual fluorescence may arise from any two of these states, as each has a different geometry at which it attains a minimum. The Jahn-Teller induced distortion of the benzene anion radical ground state helps to classify the CT states as having quinoid (Q) and antiquinoid (AQ) forms. The intramolecular charge transfer (ICT) state is formed by the transfer of an electron from a covalently linked donor group to an anti-bonding orbital of the pi-electron system of benzene. The change in charge distribution of the molecule in the CT states leads to the most significant geometry change undergone by the molecule which is the distortion of the benzene ring to a Q or AQ structure. As the dipole moment is larger in the perpendicular geometry than in the planar one, this geometry is preferred in polar solvents, supporting the twisted intramolecular charge transfer (TICT) model. However, in many cases the planar conformation of CT excited states is lower in energy than that of the LE state, and dual fluorescence can be observed also from planar structures.     

Relaxation pathways of excited N-(triphenylmethyl)salicylidenimine in solutions

Excited state relaxation of N-(triphenylmethyl)-salicylidenimine (MS1) in protic and aprotic solvents has been investigated by means of absorption pump-probe spectroscopy with femtosecond time resolution and fluorescence spectroscopy with picosecond time resolution. Short-lived excited states and long-lived photoproducts have been identified from the differential absorption spectra. Excited states and photoproducts were different under excitation of enol-closed and cis-keto tautomers. As a result, the commonly accepted excited state relaxation model of aromatic anils, which assumes an ultrafast transformation of excited enol-closed tautomers into cis-keto tautomers, has been modified. Performed quantum chemical calculations suggest that hydrogen-bonded ethanol molecules facilitate formation of cis-keto tautomers and are responsible for their different relaxation pathways in comparison with relaxation of excited enol-closed tauromers. Fluorescence decay on a nanosecond time scale was attributed to aggregated MS1 molecules.     

Geometry and solvent-polarity dependences of the relaxation dynamics of the singlet excited state of center-to-edge phosphorus(V) porphyrin heterodimers

Para- and meta-isomers of center-to-edge phosphorus(V) porphyrin heterodimers (p- and m-Pm-PCl2) composed of a phosphorus(V) tetraphenylporphyrin (P) and a phosphorus(V) tetrakis(4-methoxyphenyl)porphyrin (Pm) were synthesized to investigate the geometry and solvent-polarity dependences of the relaxation dynamics of the lowest singlet excited state (S1) of the porphyrin dimer. The geometrical difference between m- and p-Pm-PCl2 in solution was confirmed by 1H NMR on the basis of the porphyrin ring current model. By the photoexcitation of the dimers, only the fluorescence from 1Pm*-P was observed in both dimers because of the efficient singlet energy transfer from the higher energy 1P* to the lower energy 1Pm*. However, the 1Pm*-P fluorescence had features that differ from the typical fluorescence from monomeric 1Pm*, especially for the solvent-polarity dependence of the quantum yields. Furthermore, all the fluorescence decay curves of 1Pm*-P were double-exponential. The special fluorescence features of 1Pm*-P are due to the equilibrium between 1Pm*-P and the charge-transfer (CT) excited state of the dimer ((Pm-P)CT). By the excited-state equilibrium, 1Pm*-P is efficiently quenched through (Pm-P)CT in highly polar solvents. The contribution of (Pm-P)CT to the decay process of 1Pm*-P is more remarkable in m-Pm-PCl2 than in p-Pm-PCl2, depending on the interaction between the two porphyrin -systems in the heterodimer.     

Hydrogen bond formation between 4-(dimethylamino)pyridine and aliphatic alcohols

The photophysics of 4-(dimethylamino)pyridine (DMAP) has been investigated in different solvents in the presence of aliphatic and fluorinated aliphatic alcohols, respectively. For most systems, consecutive two-step hydrogen-bonded complex formation is observed in the presence of alcohols. Equilibrium constants are determined from UV spectroscopic results for the formation of singly and doubly complexed species. The resolved absorption and fluorescence spectra for the singly and doubly complexed DMAP are derived by means of the equilibrium constants. Exceptionally large hydrogen bond basicity values are found for the ground and singlet excited DMAP molecules. In n-hexane, as a consequence of complex formation, the intramolecular charge transfer (ICT) emission becomes dominant over of the locally excited fluorescence; the fluorescence and triplet yields increase considerably with complexation. In polar solvents, both the fluorescence and triplet yields of the complex are much smaller than that of the uncomplexed DMAP. The dipole moments derived for the singly complexed species from the Lippert-Mataga analysis are much larger than those of the uncomplexed molecules. However, for the relaxed ICT excited-state one obtains different dipole moments in apolar and polar solvents. This may be explained by a conformational change of the molecule in the ICT excited state from planar geometry in apolar solvent to the perpendicular structure (characterized with bigger dipole moment) in polar solvent.     

Photoinduced intramolecular charge transfer in 4-(dimethyl)aminobenzonitrile--a theoretical perspective

Recent advances in time-dependent density functional theory (TDDFT) have led to computational methods that can predict properties of photoexcited molecules with satisfactory accuracy at comparably moderate cost. We apply these methods to study the photophysics and photochemistry of 4-(dimethyl)aminobenzonitrile (DMABN). DMABN is considered the paradigm of photoinduced intramolecular charge transfer (ICT), leading to dual fluorescence in polar solvents. By comparison of calculated emission energies, dipole moments, and vibrational frequencies with recent results from transient spectroscopy measurements, a definitive assignment of the electronic and geometric structure of the two lowest singlet excited states of DMABN is possible for the first time. We investigate the mechanism of the ICT reaction by means of minimum energy path calculations. The results confirm existing state-crossing models of dual fluorescence. Our study suggests that analytical TDDFT derivative methods will be useful to predict and classify emissive properties of other donor-acceptor systems as well.     

On the nature of the fluorescent state of methylated indole derivatives

A quantitative study has been made of the solvent effects on the fluorescence properties of 1- and 3-methyl indole, with the aim of further understanding the origin of the unusually large Stokes shift in polar solvents. For the derivatives considered here the fluorescence transition probability is decreased in solvents of moderate and high polarities, and the spectrum shifts to the red. The data (in two-component, solute and solvent, systems) can be interpreted on the basis of the stabilisation, by solvent-solute relaxation, of a state with an increased charge-transfer character, relative to the initially excited state. Å consideration of the decay data for other indole derivatives suggests that this state has its origin in the ¹L₄ state (S₂ in non-polar media). Thus we conclude that the appropriate label of the fluorescent state of many substituted indoles in polar solvents is ¹L_a/CT. This is consistent with the observed solvent, temperature, time and substituent dependence of the decay kinetics of these derivatives.     

2-氨基苯并噻唑的结构及激发态质子转移动力学

通过傅里叶变换红外光谱（FTIR）、傅里叶变换拉曼（FT-Raman）和488 nm拉曼光谱,结合密度泛函理论（DFT）计算研究了2-氨基苯并噻唑（ABT）在晶态和溶剂中的二聚体结构,并解释了质子性溶剂中ABT二聚体与溶剂分子间的氢键作用.电子光谱实验揭示了ABT二聚体的光物理和光化学反应;紫外吸收和荧光发射光谱结果表明,溶剂、激发波长和pH值对ABT二聚件激发态衰变具有调控作用;含时密度泛函理论（TD-DFT）解释了ABT二聚体双荧光现象,提出了高激发态的质子转移机理.     

Comprehensive Photophysical Behaviour of Ethynyl Fluorenes and Ethynyl Anthracenes Investigated by Fast and Ultrafast Time‐Resolved Spectroscopy

Detailed investigations by time‐resolved transient absorption and fluorescence spectroscopies with nano‐ and femtosecond time resolutions are carried out with the aim of characterising the lowest excited singlet and triplet states of three ethynyl fluorenes ( 1 – 3 ) and three ethynyl anthracenes ( 4 – 6 ) in solvents of different polarity. The solvent is found to modify the deactivation pathways of the lowest excited singlet state of compounds 1 – 4 , thus changing their fluorescence, intersystem crossing and internal conversion efficiencies. The fluorescence and triplet yields gradually decrease, while the internal conversion quantum yield increases upon increasing the solvent dielectric constant. These experimental results, coupled with the marked fluorosolvatochromic effect, point to the involvement of an emitting state with a charge‐transfer (CT) character, strongly stabilised by polar solvents. This is proved by ultrafast spectroscopic studies in which two transients, distinguished by characteristic spectral shapes assigned to locally excited (LE) and CT states, are detected, the CT state being the longer lived and fluorescent one in highly polar solvents. The intramolecular LE→CT process, operative in highly polar media, becomes particularly fast (up to ≈300 fs) in the case of the NO₂ derivative 1 . No push–pull character is found for 5 and 6 , which exhibit different photophysical behaviour; indeed, the solvent polarity does not modify significantly the dynamics of the lowest excited singlet states. Quantum mechanical calculations at the TDDFT level are also used to determine the state order and nature of the lowest excited singlet and triplet states and to rationalise the different photophysical behaviour of fluorine and anthracene derivatives, particularly concerning the intersystem crossing process.