Singlet-Singlet Electronic Excitation Energy Transfer in a Bichromophore Cooled in a Supersonic Jet

The fluorescence excitation spectra and polarization of the fluorescence of a bichromophore cooled in a supersonic jet are measured. The bichromophore consists of 2,5-diphenyloxazole (PPO) and 1-(5′-phenyl-1′, 3′-oxazole-2′-yl)-4-(5′-phenyl-1′,3′,4′-oxadiazole-2′-yl)-benzene (POPDP) connected by the methylene bridge -(CH₂)-. Based on the analysis of these components and theoretical calculations, it has been proven that the total intramolecular singlet-singlet transfer of the energy of electronic excitation from the energy donor PPO to the acceptor POPDP occurs in a time of 10⁻¹² sec. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 460–463, July–August, 2005.     

Nature of the electron-excited states and the mechanism of nonradiative energy transfer in aromatic bifluorophores

Quantum-chemical calculations have been carried out for molecules of the bifluorophores naphthalene-(CH₂)_n-anthracene. The electronic structure and molecular-orbital nature of the excited electronic states of the molecules was analyzed and the rate constants of the photophysical processes were estimated. It is shown that for molecules with n=1, 2, 3 the transfer of excitation energy from the donor fragment (naphthalene) to the acceptor (anthracene) is completely equivalent to internal conversion.The work was done under a grant from the Competition Center of St. Petersburg University.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 69–75, October, 1993.     

Long-Range Energy Transfer Combined with Isotropic or Anisotropic Diffusion

Abstract

The effect of diffusion on long-range energy transfer by dipole-dipole interaction^1,2 from electronically excited donor molecules D? to (unexcited) acceptor molecules A may be important in solutions^3–7 and in molecular crystals^7–11. In solutions usually diffusion of matter occurs (the molecules perform a random walk) whereas in molecular crystals an excitation (exciton) migrates. Exciton migration can often be described in terms of an effective exciton diffusion tensor which may be highly anisotropic^12–17. Because of the restricted space only the time dependence of the donor fluorescence after δ-excitation will be given. The extension to general excitation forms and to the acceptor flouorescence is a straightforward matter^18,19.     

Model for photosynthetic light harvesting system: Energy transfer in anthracene- and biphenyl-cholorophyll derivatives

An intramolecular energy transfer from the ultraviolet absorbing donor to the pyro-pheophorbide a moiety occurs with high efficiency in model antenna compounds composed of 4-phenylbenzoic acid or anthracenecarboxylic acid and pyropheophorbide a. The energy transfer mechanism involves a Förster tyoe dipole-dipole coupling between the donor transition dipole(s) and the acceptor transition dipole(s) represented by the Soret band of the pyropheophorbide a moiety.     

Photoinduced energy and electron transfer in oligo(<Emphasis Type="Italic">p</Emphasis>-phenylene vinylene)-fullerene dyads

The intramolecular photoinduced charge separation within an oligo(p-phenylene vinylene)–fulleropyrrolidine dyad with four phenyl rings (OPV4-C₆₀) has been investigated with femtosecond pump-probe spectroscopy in solvents of different polarity and in the solid state. In solution, photoexcitation of the OPV4 moiety of OPV4-C₆₀ results in an ultrafast (<190 fs) singlet energy transfer reaction, creating the fullerene singlet excited state. In polar solvents, the ultrafast energy transfer is followed in the picosecond time domain by an intramolecular electron transfer. In accordance with Marcus theory, the rates for forward and backward intramolecular electron transfer in OPV4-C₆₀ are influenced by the polarity of the solvent. In the solid state the photophysics of OPV4-C₆₀ is dramatically different. In thin films, the forward electron transfer proceeds within 500 fs, irrespective of which chromophore is photoexcited. The increased rate for charge separation in the solid state is attributed to a more favorable orientation of the donor and acceptor that results in an intermolecular electron transfer. In the films, energy and electron transfer processes compete at the earliest moments after photoexcitation. In the solid state, the photogenerated electrons and holes have long lifetimes as a result of migration of these charges to thermodynamically more favorable sites in the film. PACS 78.47.1+p; 34.30.+h; 33.50.-j     

Energy transfer from UO++2 → Nd3+ in barium borate glass

Radiative and non-radiative energy transfer from UO⁺⁺₂ to Nd³⁺ has been studied in barium borate glass. Probabilities, efficiencies and the mechanism of non-radiative energy transfer were determined from UO⁺⁺₂ fluorescence decay rates. At low acceptor concentrations pair-wise energy transfer involving migration among donors leads to a non-radiative transfer rate which depends linearly on the concentration of Nd³⁺. It is decided that resonant radiationless dipole-dipole transfer of energy is the dominant mechanism active in this system. However, the observations of transfer yield for high acceptor concentrations are contrary to those at low acceptor concentrations as evidenced from the P_da vs C² plot. Hence at high acceptor concentrations, the transfer could happen between a donor ion and two acceptor ions which is consistent with the view of Fong and Diestler.     

Spin polarization transfer during intramolecular triplet-triplet energy transfer as studied by time resolved EPR spectroscopy

Spin polarization conservation during intramolecular triplet-triplet energy transfer was studied for the phthalimide derivatives. It is shown that spin polarization transfer is useful for determining the conformation and the nature of the lowest triple (T₁) states of the donor and acceptor moieties. The polarization pattern of the acceptor triplet state was well reproduced taking into account the polarization of the donor and the mutual orientation of the donor and acceptor moieties. This technique clarified the order of the triplet sublevels in energy of the phthalimide chromophore. The T₁ states of stilbene derivatives, which have a low quantum yield of intersystem crossing under direct excitation, were also detected.     

Experimental and Theoretical Studies of the Spectroscopic Properties of Chalcone Derivatives

Newly synthesized, differently substituted chalcones (1,3-diaryl-2-propen-1-ones) have been studied using steady-state and time-resolved techniques combined with quantum-chemical modelling. To explore spectroscopic structure - property relationships the substituent (acceptor moiety) was chosen according to systematic variation in the Hammett parameter. It was shown that photophysical properties of the studied donor-acceptor (D-A) molecules can be predicted in terms of a simple model from the properties of individual chromophores (composite-model of decoupled moieties: donor (D) and acceptor (A)). The results of spectroscopic measurements also indicate that for investigated D-A fluorophores in medium-polar solvent, the initially populated, locally excited (LE) state (where the fundamental role plays donor moiety (D*-A)) reacts further to produce intramolecular charge transfer (ICT) state. Additionally, the experimental absorption (M _ge ) and fluorescence (M _eg ) transition dipole moments were calculated on the basis of spectroscopic data and compared with results of our quantum-chemical calculations. The absorption transition dipole moment was found to vary linearly with the Hammett substituent coefficient (σ).     

Energy Transfer Studies with Perylene bis-Diimide Derivatives

Abstract

Singlet energy transfer between seven derivatives of perylene diimides and cobalt ions are studied. Energy transfer quenching by cobalt ions is observed for all of the perylene diimides. The rate of bimolecular quenching is found to be about, k_q ? 10¹⁰ M^?1s^?1, only the N-naphthyl substitution lowered the rates to the range of, k_q ? 10⁹ M^?1s^?1. The critical transfer distances, R_o (5.8–10.4 A°), calculated from donor emission and acceptor absorption spectra, are attributed to a Forster resonance energy transfer process.     

Energy transfer from Tb3+ to Eu3+ ions sorbed on SrTiO3 surface

The energy transfer at room temperature between Tb³⁺ and Eu³⁺ ions sorbed onto SrTiO₃ powders is investigated, using Time-Resolved Laser-induced Fluorescence Spectroscopy (TRLFS). Several published works deal with the energy transfer between two lanthanide ions in co-doped matrices but it is the first time that transfer processes between two lanthanide ions sorbed on a solid surface is reported. The results show that the energy transfer between sorbed Tb³⁺ and Eu³⁺ ions on strontium titanate is a non-radiative process and follows a dipole–dipole type interaction. Moreover, the higher the acceptor ions Eu³⁺ concentration, the more efficient the energy transfer.It is shown that no energy migration between the Tb³⁺ donor ions occurs. A formalism based on the model of Inokuti–Hirayama is used and allows one to fit the non-exponential Tb³⁺ fluorescence decay. It is thus possible to evaluate the critical radius (R₀) of the influence sphere of the sorbed Tb³⁺ ions. According to the previous works, two sorption sites are considered for the sorbed rare-earth. The calculated radii are similar to those obtained for other couples of donor–acceptor lanthanide ions reported in the literature.     

Effect of a protein on the light energy conversion in dual fluorophore-nitroxide probes studied by ESR and fluorescence spectroscopy

Probing biological environment with dual fluorophore-nitroxide (FN) molecules in which fluorophore is tethered with nitroxide, a fluorescence quencher, opens unique opportunities to study molecular dynamics and micropolarity of the medium which affect intramolecular fluorescence quenching (IFQ), electron transfer, photoreduction and light energy conversion. In such molecules, the excited fragment of the chromophore can serve as an electron donor, and the nitroxide fragment as an electron acceptor. The same groups allow monitoring of molecular dynamics and also make it possible to measure micropolarity of the medium in the vicinity of the donor (by fluorescence technique) and acceptor (by electron spin resonance [ESR]) moieties. In the present work, two dual dansyl-nitroxide probes were incorporated in a binding site of bovine serum albumin. Their interactions with the protein, mobility, and photoreduction, as well as micropolarity of the media, have been studied by ESR and fluorescence methods. IFQ and spectral relaxation shift of the dansyl fragment have been monitored by time-resolved fluorescence technique. In parallel, computational studies on intramolecular dynamics of the FN probe were performed. On the basis of the Marcus model of the electron transfer between the excited dansyl fluorophore (donor) and nitroxide group (acceptor) and our experimental data, the mechanism of the electron transfer in the dual molecules incorporated into bovine serum albumin was established. It was shown that dual FN molecules in the protein meet main requirements for an efficient light energy conversion system.     

Intermolecular energy transfer in mixed laser dyes: photophysical properties of triplet states

Triplet-singlet energy transfer in laser dyes have been studied in EPA at 77K using N₂ laser as an excitation source. Phosphorescence of the donor (D) and the delayed fluorescence of the acceptor (A) and their lifetimes have been measured for coumarin 102 (D)-rhodamine B(A) and 9(10H)-acridone (D)-rhodamine 6G(A) dye systems as a function of acceptor concentration. These data yield energy transfer rate constants of ∼10³ dm³ mol⁻¹ s⁻¹ for the donor acceptor combinations, consistent with the Forster mechanism. The phosphorescence quantum efficiency and other spectral parameters are also reported.     

Förster-type energy transfer mechanism in PF2/6 to MEH-PPV conjugated polymers

Energy transfer mechanism between Poly[9,9-di-(2′-ethylhexyl)fluorenyl-2,7-diyl] (PF_2/6) as a donor and poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) as an acceptor in different solvents has been studied using steady-state emission measurements. Four different solvents namely, tetrahydrofuran (THF), toluene, chlorobenzene (C.B) and benzene have been used in this study. The absorption and luminescence behaviors of the samples are measured at a fixed concentration of donor (0.1 μM) while the concentrations for acceptor are kept in the range of 0.1–1.0 μM. Based on these measurements, the energy transfer properties namely quenching rate constant (k_SV), energy transfer rate constant (k_ET), energy transfer probability (P_DA), transfer efficiency (η) and critical distance of energy transfer (R_o) are calculated. The use of THF resulted in the highest energy transfer. Long range dipole–dipole interaction between the excited donor and ground state acceptor molecules is the dominant mechanism responsible for the energy transfer as proven by the large values of R_o.     

Non-radiative energy transfer from Sm3+→Nd3+ in sodium borate glass

A study of energy transfer from optically excited Sm³⁺ to Nd³⁺ in borate glass has been performed. Contrary to the observations made by Cabezas and DeShazer, the Sm³⁺ → Nd³⁺ energy transfer has been observed as non-radiative. Energy transfer probabilities (P_da) and transfer efficiencies (η_T) have been calculated from our measurements of donor fluorescence intensity and decay times. The mechanism governing the transfer is electrostatic dipole-dipole in nature, contrary to the conclusions made by Nakazawa and Shionoya. At low acceptor (Nd³⁺) concentrations a linear dependence of P_da on acceptor concentration (C) has been observed which suggests the migration of excitation energy among donors. At high acceptor (Nd³⁺) concentration a plot of P_da vs (C_o + C)², where C_o is donor ion concentration, presents a linear dependence which is consistent with the Fong-Drestler theory of dipole-dipole energy transfer mechanism and interaction of one donor (Sm³⁺) with two acceptors (Nd³⁺).     

Distance distributions and dynamics of a zinc finger peptide from fluorescence resonance energy transfer measurements

Time-resolved fluorescence resonance energy transfer (FRET) measurements were used to measure distance distributions and intramolecular dynamics (site-to-site diffusion) of a 28-residue single-domain zinc finger peptide in the absence and presence of zinc ion. Energy transfer was measured between TRP₁₄ and a N-terminal DNS group. As expected, the TRP-to-DNS distance distribution for zinc-bound peptide is shorter and narrower (R _av=11.2 Å,hw=2.8 Å) than the metal-free peptide (R _av=20.1 Å,hw=14.5 Å). The degree of mutual donor-to-acceptor diffusion (D) was also determined for these distributions. For zinc-bound peptide there is no detectible diffusion (D0.2 Ų/ns), whereas for metal-free peptide a considerable amount of motion is occurring between the donor and the acceptor (D=12 Ų/ns). These results indicate that the zinc-bound peptide folds into a unique, well-defined conformation, whereas the metal-free conformation is flexible and rapidly changing. The absence of detectible mutual site-to-site diffusion between the donor and the acceptor in the metal-bound zinc finger peptide indicates that intramolecular motion is essentially frozen out, on the FRET time scale, as a consequence of zinc coordination.Dedicated to the memory of Barbara D. Wells.     

Spectra,lifetimes and energy transfer for uranyl species in solution

The lifetimes for various uranyl species formed under varying conditions of solvents, pH, etc., have been measured. A large variation in lifetimes from about 10 μs for hydrolytic UO²⁺₂ (UO₂)_n species to about 900 μs for anion complexed UO₂(NO₃)₂ species is observed. The lifetime data are shown to be in agreement with the calculated values when care is taken to isolate the contribution to absorption due to the F series only. The samples in which more than one species are present in emission, show energy transfer from the higher energy species to the one having lower energy of excitation. As a result of this the lifetime of the donor is decreased and that of the acceptor is increased. The donor decay is found to be exponential. A rise time is also observed in acceptor emission. The energy transfer mechanism is found to be of the Stern-Volmer type transfer.     

Study of energy transfer in a solution of coumarin 460 and rhodamine 6G by time-resolved laser-induced fluorescence spectroscopy

A multi-photon fast analog technique has been used to study nonradiative energy transfer from coumarin 460 to rhodamine 6G molecules. At low acceptor concentrations (<10^-2 mol/1) the fluorescence decay from coumarin deviates markedly from monoexponential behavior. The complex decay of the donor fluorescence reflects the time-dependent population of donor-acceptor pairs. Various energy transfer kinetics were investigated. The donor decay was found to be consistent with Förster kinetics and the critical energy transfer radius was found to be (5.46±0.10) nm.     

Effect of chain length and donor–acceptor substitution on the electrical responsive properties of conjugated biphenyls: a DFT-based computational study

The effect of donor–acceptor (D-A) substituent and chain length on the electrical polarisabilities and first hyper polarisability of cis and trans biphenyl oligomeric compounds have been investigated using density functional theory-based hybrid functional CAM-B3LYP with 6-311G (2d,2p) basis set. Our extensive computational study reveals that both average polarisability and first hyper polarisability of the studied compounds increase with the increasing ethylene spacer chain length. Again the substitution of donor (NMe₂) and acceptor (C≡N) at the para position of the phenyl rings to each oligomer shows order of magnitude increase of both α_av and β_av value compared to the unsubstituted one. This increased α_av and β_av values have been explained due to increasing charge transfer contribution resulting from decreasing optical energy gap (ΔE?=?S₁???S₀) upon D-A substitution. It is also observed that the charge transfer contribution to first hyperpolarisability (β_CT) is more than the polarisability (α_CT) for the studied molecules. The electronic spatial extent (<R²>) which is a measure of electron density volume around the molecule is found to play a major role along with the intramolecular charge transfer character to explain the non-linear variation of first hyperpolarisability (β_av) as a function of ethylene spacer chain length (n) and D-A substitution.     

Effectiveness of charge separation from the long-lived second excited state of donors

In molecular zinc-porphyrin-based donor–acceptor systems, the electron transfer from the second singlet excited state S₂ is accompanied by ultrafast recombination into the first excited state, resulting in a low quantum yield of the thermalized charge-separated state (20%). It is demonstrated that the quantum yield of ultrafast charge separation in donor–acceptor triads D–A₁–A₂ can be close to 100% in molecular systems with lifetimes of the S₂ state longer than 150 ps. As prototypes of such systems, donor–acceptor diads D–A₁ and triads D–A₁–A₂ are considered, wherein the xanthione molecule plays the role of a donor. The ranges of the model parameters are determined in which the efficiency of charge separation is high. The twostage photoinduced charge transfer is studied within the framework of a multichannel stochastic model that takes into account the reorganization of a polar solvent and a high-frequency intramolecular vibrational mode.     

Studies on Curcumin and Curcuminoids. XXXIX. Photophysical Properties of Bisdemethoxycurcumin

The steady-state absorption and fluorescence, as well as the time-resolved fluorescence properties of bisdemethoxycurcumin dissolved in several solvents differing in polarity and H-bonding capability were measured. The photodegradation quantum yield of the compound in acetonitrile and methanol was determined. The bisdemethoxycurcumin decay mechanisms from the S ₁ state were discussed and compared with those of curcumin. The differences in S ₁ dynamics observed between bisdemethoxy-curcumin and curcumin could be ascribed to a difference in H-bond acceptor/donor properties of the phenolic OH and a difference in strength of the intramolecular H-bond in the keto-enol moiety within the two molecules.