Electronic and resonance Raman spectra of iron(II)—tetraazamacrocyclic complexes containing N-heterocyclic ligands

The adducts of the meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-1,4,8,11-tetraene iron(II) complex with N-heterocyclic ligands exhibit three characteristic absorption bands in the ranges 690-640, 505-470 and 435-340 nm. Using excitation wavelengths coinciding with the low energy band, a selective enhancement of the Raman vibrational modes of the macrocyclic ligand is observed, supporting the assignment of a metal-to-diimine charge-transfer transition. The high energy band is strongly dependent on the nature and pK_a, of the axial ligands. Excitation at this band leads to the enhancement of the N-heterocyclic vibrational modes in the Raman spectra, indicating a metal-to-(N-heterocycle) charge-transfer transition. The intermediate band exhibits weak resonance Raman activity. Its intensity depends on the proximity of the high energy band and is consistent with the occurrence of an intensity stealing mechanism.     

A thermochemical study of dissociative ionization of 4,4-dimethyl-1-thia-4-silacyclohexane and 2,3,3-trimethyl-1-thia-3-silacyclopentane. Decomposition pathways to produce a dimethylsilanethione ion-radical [Me2SiS]+•

The dissociative ionization of 4,4-dimethyl-1-thia-4-silacyclohexane (I) and 2,3,3-trimethyl-1-thia-3-silacyclopentane(II) has been studied by electron photoionization (PI) mass spectrometric methods. The molecular ion fragmentation is mainly related to the loss of ethylene and results in a [Me₂SiSC₂H₄]^+? (m/z 118) ion-radical (A). Further loss of ethylene from A produces a dimethylsilanethione [Me₂SiS]^+? (m/z 90) ion-radical (B). The latter is the most abundant ion in the mass spectra of I and II at 70 eV.The ionization energies (IE) of I (8.22 ± 0.07 eV) and II (8.06 ± 0.03 eV) and the appearance energies (AE) of ion-radicals A and B have been determined. Also, the following heats of formation were calculated (kJ/mol): ΔH_f⁰(I) = ?31.1; ΔH_f⁰(II) = ?65.8; ΔH_f⁰(M_I^+?) = 762.0; ΔH_f⁰(M_II^+?)= 712.1; ΔH_f⁰(A)_aver = 780.2; ΔH_f⁰(B)_aver = 847.7.     

Perturbed sites and host—guest—host exciton cascade in the biphenyl isotopic mixed crystal phosphorescence

An interesting energy cascade is observed in the phosphorescence spectra of 1% biphenyl-h₁₀ in biphenyl-d₁₀ (2–15 K); strongly perturbed host sites, with energy levels below that of the protonated guest, quench the guest sites at higher temperatures (11–15 K). The identification of the perturbed sites is based on vibrational characteristics (both intensity and frequency), obtained with the help of phosphorescence spectra of biphenyl-h₁₀ and biphenyl-d₁₀ in an argon matrix, indicating an isotope dependent vibronic structure. A partial vibrational analysis is presented, resulting in confirmation of the first triplet state of biphenyl as orbitally ungerade. The dynamics of the triplet excitation are discussed, including several possible mechanisms explaining the non-Boltzmann nature of the low-temperature steady state.     

Effect of rotational relaxation on the intensity and polarization of fluorescence emission caused by sequential two-photo excitation

General formulas are derived for the intensity and the degree of polarization of the S_m-fluorescence emission (m ? 2) of a sample excited by the sequential two-photon excitation process (S_n ← S₁ ← S₀, n ? 2) with plane-polarized pulsed light. They show how the S_m-fluorescence intensity and anisotropy depend on the relative orientation of the relevant transition dipoles within a molecule and on the degree of rotational relaxation of molecules in the intermediate state (S₁) and in the S_m state (for the case m = n), or in the S_n → S_m process (m ≠ n).     

Measurement of triplet extinction coefficients of organic compounds by McClure's method

We tested McClure's method for measuring the triplet extinction coefficients ε_T of organic compounds on anthracene and pyrene, using the u.v. lines from a krypton ion cw laser as a steady-state excitation source. Our values for anthracene ε_T = 82 × 10³1/mole cm at 426 nm and pyrene ε_T = 37 × 10³l/mole cm at 413 nm agree well with values obtained by other methods. McClure derived his linear relationship from kinetic considerations. One simply measures triplet optical densities (OD_T) at a fixed wavelength (e.g. at a triplet absorption maximum) as functions of different cw laser excitation intensities (powers) I_ex. A plot of 1/OD_T against 1/I_ex yields a straight line. Extrapolating to the intersection of the ordinate (1/I_ex = 0, or I_ex = ∞) yields 1/OD^∞_T. Since, at infinite excitation intensity I_ex, the concentration of the triplet state molecules N_T is equal to the original concentration N_S of the ground state concentration, ε_T can be easily calculated from ε_T = OD^∞_T/N_Sd where OD^∞_T is the triplet optical density at infinite excitation intensity, N _S is the original concentration of molecules (at ground state), and d is the thickness of the sample. The success of this method requires the production of high concentrations of triplet state molecules N_T, as well as steady-state excitation. CW lasers fulfill all these requirements. We discuss the spectroscopic equipment employed for measuring triplet optical densities in some detail. Methods for reducing heat gradients (noise) in liquid nitrogen, laser excitation spot sizes, reduction of spherical aberrations, etc., are reviewed. We varied the cw laser illumination density (laser power/area) by setting the focusing lens at different distances from the sample, and measured 1/OD_T as a function of 1/I_ex. As long as the size of the excitation area was not below a critical size, all the straight lines obtained at different lens settings converged well into only one value of 1/OD^∞_T. Measurements were also performed at different concentrations of the solutes.     

Inter- and intra-molecular radiationless transitions of NO2 at around 454.6 nm

The continuum emission of NO₂ was investigated on the basis of time-resolved excitation and fluorescence spectra. The analysis of the observed spectra indicated the coexistence of inter- and intra-molecular relaxation processes of NO₂. The continuum emission, the relative intensity of which at longer wavelengths increases more drastically as time goes on after excitation (2–6 μs), was concluded to originate predominantly from molecular collisions in a stepwise deactivation process. A fast component of the continuum emission, with a relative intensity with respect to the discrete band (I_C/I_D) independent of time and of NO₂ pressure, appeared in collision-free conditions (<20 ns, 15 mTorr), and it was concluded to originate from radiationless transitions in isolated molecules.     

Temperature effects on fluorescence line narrowing spectra of tetracene in amorphous solid solutions. Analytical implications

Temperature effects in the highly specific vibrationally resolved fluorescence line-narrowing (FLN) spectra of tetracene as a model compound have been investigated with emphasis on analytical implications.Contrary to what is generally observed in conventional solid state methods, in FLN when excitation in the 0-0 region is employed, the lowest temperatures in most cases do not produce the largest peak heights and intensities. For excitation in the vibronic S₁ region the conventional behaviour is observed. The analytically useful temperature interval in FLN spectroscopy generally is more limited than in techniques that use crystalline matrix materials.The spectral bands in FLN have a predominantly Lorentzian shape for excitation in the 0-0 region in our experimental set-up where, at the temperatures used, the excitation source does not contribute significantly to the lineshape. For excitation in the vibronic S₁ region a stronger Gaussian contribution to the lineshape is observed. No temperature dependent shift of the narrow lines occurs, contrary to what is generally found in the conventional solid state methods. In addition, the position of the lines in FLN is not solvent dependent.To explain these observations it is crucial to realize that in FLN, high resolution is achieved via selective excitation, so that the spectral emission features are determined by the excitation as well as the emission process.     

The line profiles of single rotational lines of the H 2 B - X(3, 0) band in an intense infrared light field

The first investigation of the lineshape of single rotational lines of the H ₂ B - X(3, 0) band in an intense infrared light field (λ = 1064 nm) at intensities between 10¹⁰ W/cm² and 10¹² W/cm² is reported. The B - X(3, 0) band is excited with low intensity vacuum ultraviolet radiation (λ ≈ 106 nm). B-state excitation is observed by multiphoton ionization and dissociation of H ₂ with H ⁺ as final product. The lineshapes of the B-X(3, 0) band behave differently in both decay channels. This indicates that they branch before the molecule is photoionized. The intensity dependence of the lineshapes seems to show that at certain intensities in the focused infrared light beam the AC-Stark effect induces transient resonances into the multiphoton excitation process starting at the B(v = 3, J) rotational levels. A qualitative analysis of the states which may influence the B(v = 3, J) multiphoton excitation rate is given.     

Analysis of collisional alignment and orientation studied by scattering of spin-polarized electrons from laser excited atoms

A general framework using density matrices is developed for the analysis of atomic excitation by spin-polarized electrons. This framework is applied to the specific case of the 3S _1/2→3P _3/2 transition in Na, as studied by the time-reversed, superelastic process. The scattering is characterized in terms of physical parameters describing the collisionally excitedp-state, i.e., its angular momentum (L _⊥), linear polarization (P _lin), and alignment angle (γ), with these parameters defined separately for singlet and triplet excitation. An expression for the scattering intensity is derived which is valid for arbitrary electron polarization and atomic state preparation. Specific examples are discussed with a view toward complete determination of the relevant scattering amplitudes and phases. Recent experimental results are reevaluated for comparison with theoretical calculations, and suggestions are made for future experiments.     

Energy transfer in collisions of Ar(3P0,2 metastable atoms with H(2S) atoms. I. Total rate constant and mechanism

The Ar(4s,³P₂) + H(1S,²S) reaction, which gives excited H(n=2) atoms, has been studied. The room temperature rate constant for Lyman-α (2p-1s) excitation was measured as 2.4 × 10^?10 cm³ mol^?1 s^?1. The method was based upon comparison of the Lyman-α emission intensity with the Kr resonance emission intensity produced from Ar(³P₂) + Kr, which has a known rate constant. The H atom excitation, which has a large energy defect of 1.3 eV, is discussed in terms of a curve crossing mechanism.     

Ab initio configuration interaction calculations of the NIs (NO2) core-hole states of p-nitroaniline

The NIs (NO₂) core-hole states of p-nitroaniline are calculated by a Cl procedure that takes account of both orbital relaxation and correlation effects. A satellite peak arising from the excitation 4b₁(Π) → 5b₁(Π) is calculated to occur 26 eV from the main ionization peak, with a relative intensity of 66%. These results are compared with gas-phase photoelectron spectra.     

Luminescence Properties of Terbium-, Cerium-, or Europium-Doped α-Sialon Materials

New interesting luminescent α-sialon (M_(m/val+)^val+ Si_12-(m+n) Al_(m+n)OnN_(16−n)) (M=Ca, Y) materials doped with Ce, Tb, or Eu have been prepared and their luminescence properties studied. These show that Tb and Ce are in the 3+ and Eu in the 2+ state. Low-energy 4f↔5d transitions are observed as compared to the luminescence of these ions doped in oxidic host-lattices. This is partially explained by the nitrogen-rich coordination of the rare-earth ion and partially by the narrow size of the lattice site. The latter gives rise to a strong crystal-field splitting of the 5d band and a rather large Stokes shift for Ce³⁺ and Eu²⁺ (6500-7500 and 7000-8000 cm⁻¹, respectively). For (Y,Tb)-α-sialon the Tb³⁺ 4f→5d excitation band (∼260 nm) is in the low-energy host-lattice absorption band (?290 nm), giving rise to a strong absorption for 254-nm excitation, but a low quantum efficiency. The latter is due to photoionization processes or selective excitation of Tb³⁺ at the defect-rich surface, resulting in radiationless transitions. Ce- and Eu-doped Ca-α-sialon show bright long-wavelength luminescence (maxima at 515-540 and 560-580 nm for Ce and Eu, respectively) with a high quantum efficiency and high absorption for 365- and 254-nm excitation. The Eu²⁺ emission intensity and absorption increases for increasing m, which is explained by the Eu²⁺ richer α-sialon composition. The position of the Eu^2α emission does not shift with changing composition of the host-lattice (m, n values), indicating that the local coordination of the Eu²⁺ ion is hardly dependent on the matrix composition.     

On the determination of short lifetimes of vibronic states from resonance Raman excitation profiles

The relaxational width (Γ) of an excited state and the solvent-induced broadening (σ) produce a considerable and non-additive effect on the intensity distribution inside the resonance Raman excitation profiles. An approach based on the generating function method is proposed which makes it possible to separate these effects and determine the Γ and σ values. It is shown that the first moment M₁ of an excitation profile depends on Γ alone. The variance of the profile is a sum of σ² and a function of Γ alone. a theoretical dependence of M₁ (ρ) derived under very general assumptions is shown to be a sharp and monotonous function of Γ. This dependence makes it possible to determine the value of Γ from experimentally available value of M₁. The requirements are formulated that should be met by experimental data for a practical realization of the proposed approach.     

Development of a new fluorescent probe for transition metal cations based upon fluorescence resonance energy transfer

A novel fluorescent probe for metal cations, which has a large Stokes shift, was synthesized from the reaction of N-(3-carboxy-2-naphthyl)-ethylenediamine-N,N′,N′-triacetic acid (CNEDTA) with 4-(N,N-dimethylaminosulfonyl)-7-(2-aminoethylamino)-2,1,3-benzoxadiazole (DBD-ED). The large Stokes shift is due to the FRET phenomenon between a donor (CNEDTA) and an acceptor (DBD-ED) fluorophore. When the fluorescent probe, DBD-ED-CNEDTA, was excited at 240, 340 and 440 nm, an emission maximum was observed only at 560 nm. However, the fluorescence (FL) at 480 nm, based upon the CNEDTA moiety, was not detected with excitation at 340 nm. The FL intensity of DBD-ED-CNEDTA was dependent upon the acidity of the medium and highest at pH 4.1. DBD-ED-CNEDTA reacted with metal cations, i.e., Zn, Cd, Al, Y, and La, in aqueous medium to form chelates. The spectral change of FL excitation and emission was small before and after the addition of the metal ions. However, the FL intensity was dependent upon the concentrations of the metal ions. In the case of Zn²⁺, the molar ratio bound with DBD-ED-CNEDTA was calculated as 1:1. The FL intensities after chelate formation of Zn/DBD-ED-CNEDTA (1:1) were enhanced by 3.8-fold (excitation at 340 nm, emission at 560 nm), 4.2-fold (excitation at 440 nm, emission at 560 nm), and 5.9-fold (excitation at 240 nm, emission at 560 nm), respectively. The FL probe was applied to the determination of Zn in a food supplement.     

Singlet exciton interactions in crystalline naphthalene

The decay of prompt fluorescence in crystalline naphthalene at 300 K, excited by a picosecond 266 nm pulse, has been studied as a function of excitation intensity. Experimental decay curves can be fitted only when the exponential distribution in depth of excitation and the radial (gaussian) intensity profile of the excitation are both taken into account. From an analysis of the decay at early time (?5 ns) a best fit value of the singlet—singlet annihilation rate constant is found γ_SS = (4 ± 1) × 10^?10 cm³ s^?1. If the reaction is diffusion-limited, this rate implies an average singlet diffusivity D_S = (2 ± 1) × 10^?4 cm² s^?1.     

EDX depth profiling by means of effective layers

A new approach is described for depth profiling in stratified multilayer samples by recording energy dependent characteristic x-ray EDX(E ₀ ) curves in a scanning electron microscope. An effective layer technique replaces the x-ray excitation function of the heterogeneous target by an equivalent function of a homogeneous sample. First results of thickness determination are shown and compared to direct measurements of film thickness monitoring (FTM) and atomic force microscopy (AFM).     

The luminescent properties of polyethylene films with admixtures of luminophores based on europium compounds

Polyethylene films activated with europium(III) complexes with carboxylic acids and Eu(L)₃ · nD · xH₂O + ANT compositions, where L is the trifluoroacetic, toluyl, or cinnamic acid anion and ANT is anthranilic acid, were prepared. The intensity of luminescence of the polymeric compositions depended on the content of luminophores (molar ratio between europium compounds and anthranilic acid). An analysis of the excitation spectra showed that, in polymer—Eu(L)₃ · nPhen · xH₂O + ANT compositions, there was effective energy transfer from phenanthroline to anthranilic acid levels.     

Edge excitation red shift and energy migration in quinine bisulphate dication

Photoinduced excited state dynamical processes in quinine sulphate dication (QSD) have been studied over a wide range of solute concentrations using steady state and nanosecond time-resolved fluorescence spectroscopic techniques. The edge excitation red shift (EERS) of emission maximum, emission wavelength dependence of fluorescence lifetimes and the time dependence of emission maximum are known to occur due to the solvent relaxation process. With increase in solute concentration, the emission spectrum shifts towards the lower frequencies accompanied with decrease in fluorescence intensity, however, absorption spectrum remains unchanged. A decrease in EERS, fluorescence lifetimes, time dependent fluorescence Stokes shift (TDFSS), fluorescence polarization and the solvent relaxation time (τ_r) is observed with the increase in solute concentration. The process of energy migration among the QSD ions along with solvent relaxation has been found responsible for the above experimental findings.     

The polarized electronic spectra and electric field spectra of benzo-diazoles. II. 2,1,3-benzothiadiazole

The S₁ ← S₀ absorption spectra of 2,1,3-benzothiadiazole (BTD) have been measured at 4.2 K in four different host crystals: naphthalene, durene, p-dichlorobenzene (DCB) and p-dibromobenzene. Detailed vibrational analyses are given for BTD imbedded in napthalene and DCB. The polarization measurements show that the S₁ state has B₂ symmetry, like its selenium analogue (BSD). The transition is dominated by a single totally symmetric mode - 484 cm^?1. The Herzberg-Teller coupling contributes only a very small fraction of the total intensity. The Stark measurements of a DCB sample containing both BTD and BSD enabled us to compare the charge distribution of BTD and BSD in the state S₁. The Stark splittings of BTD are 17% greater than the splittings of BSD. Reorganization of the σ-core during the excitation is used to explain the difference. The drastic change in dipole moment upon excitation implies that the S₁←S₀ transitions of BTD and BSD are not localized in the six-membered ring as suggested by previous workers. Weak phosphorescence of BTD in napthalene and DCB and singlet-triplet absorption spectrum of neat BTD have been observed. The heavy atom effect of spin-orbit coupling is to explain the ST absorption intensity of BTD and BSD.     

Novel powellite-based red-emitting phosphors: CaLa1−xNbMoO8:xEu for white light emitting diodes

We report the photoluminescence properties of a novel powellite-based red-emitting phosphor material: CaLa_1−xNbMoO₈:xEu³⁺ (0.01, 0.03, 0.05, 0.1) for the first time. The photoluminescence investigations indicated that CaLa_1−xNbMoO₈:xEu³⁺ emits strong red light at 615 nm originating from ⁵D₀→⁷F₂ (electric dipole transition) under excitation either into the ⁵L₀ state with 394 nm or the ⁵D₂ state with 464 nm, that correspond to the two popular emission lines from near-UV and blue LED chips, respectively. When compared with emission intensity from a CaMoO₄:Eu³⁺, the emission from CaLaNbMoO₈:Eu³⁺ showed greater intensity values under the same excitation wavelength (394 nm). The enhanced red emission is attributed to the enhanced f-f absorption of Eu³⁺. These materials could be promising red phosphors for use in generating white light in phosphor-converted white light emitting diodes (WLEDs).