Electronic Energy Transfer Processes Research Articles

Multiple Pathways in the Triplet States Population for a Naphthalenediimide-C60 Dyad.

The link of an antenna dye with an electron spin converter, in this case naphthalenediimide and C60, produces a system with a rich photophysics including the detection of more than one triplet state on the long timescale (tens of µs). Beside the use of optical spectroscopies in the ns and in the fs time scale, we used time-resolved Electron Paramagnetic Resonance (TREPR) to study the system evolution following photoexcitation. TREPR keeps track of the formation path of the triplet states through specific spin polarization patterns observed in the spectra. The flexibility of the linker plays a role in favouring either electron transfer or energy transfer processes.

Vibrational Kinetics of NO and N2 in the Earth's Middle Atmosphere During GLE69 on January 20, 2005

AbstractThe mechanisms of the production of vibrationally excited NO and N2 molecules at the altitudes of the middle atmosphere of the Earth during high‐energetic proton precipitation on 20 January 2005 are considered. The study of vibrational populations N2(X1Σg+,v′ > 0) during high‐energetic proton precipitation has shown different principal mechanisms in the N2(X1Σg+,v′ > 0) excitation. First, the excitation by secondary electrons is principal for vibrational levels v′ = 1−10. Second, it is obtained that intramolecular electron energy transfer process in N2(A3Σu+)+N2 collisions dominates in vibrational excitation of high vibrational levels v′ = 20−30. It is shown that the chemical reaction of metastable atomic nitrogen with molecular oxygen is the main production mechanism of vibrationally excited NO(X2Π,v > 0) and of the radiation of 5.3 and 2.7 μm infrared emissions at these altitudes. The calculated intensities of the 5.3 μm emission are compared with experimental data from SABER instrument on TIMED spacecraft received at the time of the proton precipitation. The role of VV′‐processes in the radiation of 5.3 μm infrared emission is discussed.

A novel reddish-orange-emitting phosphor Ca3Gd7(PO4)(SiO4)5O2: Sm3+ for white light-emitting diodes

Phosphor is the decisive material in white light-emitting diodes (WLED), affecting light quality. Silica phosphate has good stability, low cost and environmentally friendly features, so it has great application potential. In this paper, a self-activated reddish-orange phosphor Ca3Gd7(PO4)(SiO4)5O2: xSm3+ was prepared by the high-temperature solid-phase method. The phase purity of the sample was verified by X-ray diffraction (XRD). The Rietveld refinement method was used to resolve further the sample structure and the location of the substitution of rare earth ions. The photoluminescence properties were studied in detail using fluorescence spectra, temperature-dependent emission spectra and other characterization methods. The electron transition and energy transfer processes of Gd3+ in Ca3Gd7(PO4)(SiO4)5O2 were analyzed. The fluorescence decay curve of the sample was obtained, which belongs to the double exponential curve, and the decay lifetime depending on the Sm3+ doping concentration was calculated. Furthermore, a WLED device was assembled, and warm white light was obtained, with a spectrum showing characteristic red emission, proving to complement the missing red component of commercial WLEDs. These results indicate that Ca3Gd7(PO4)(SiO4)5O2: xSm3+ phosphor has great potential for application.

Cavity-Modified Fermi’s Golden Rule Rate Constants from Cavity-Free Inputs

Equilibrium Fermi’s golden rule (FGR) rate constants are commonly used for modeling the kinetics of electronic energy and charge transfer processes in a wide range of molecular systems. The interaction between the electronic degrees of freedom and cavity modes can modify the coupling between electronic states when the molecular system is placed inside a cavity, and thereby alter the corresponding FGR rate constants. In this paper, we present a general-purpose framework for estimating the cavity-induced effect on equilibrium FGR rate constants. We show that cavity-modified equilibrium FGR rate constants can be estimated from inputs obtainable exclusively from a simulation of the cavity-free molecular system, thereby bypassing the need for an explicit simulation of the molecular system inside the cavity. The usefulness of this framework is demonstrated in the Marcus theory limit of equilibrium FGR, and general rules are derived for determining the optimal conditions for cavity-induced Marcus theory rate enhancement.

Bimolecular reactivity of 3d metal-centered excited states (Cr, Mn, Fe, Co)

Metal-centered (MC) excited states (ESs) of 3d transition metal complexes (TMCs) often possess rather low energies so that these represent the lowest energy ESs. Additionally, MC states are often strongly distorted, hence they efficiently decay non-radiatively to the ground state. As bimolecular photoinduced electron transfer (PET) and energy transfer (EnT) processes require contact to the substrate, the metal confinement of the ES wavefunction of MC states makes these processes challenging. Consequently, MC states are considered less useful as compared to long-lived charge transfer states of higher energy with wavefunctions extending onto the ligands. Despite these supposed drawbacks, some classes of TMCs can successfully engage in bimolecular PET and EnT processes with MC states being the photoactive states. We discuss these initial examples of MC ES reactivity covering chromium, manganese, iron, and cobalt complexes with the aim to gain a deeper understanding of these processes and to identify the decisive key parameters. Finally, we present catalytic photoredox and energy transfer processes using photosensitizers with suitable MC ESs.

Multiple Interpenetrating Metal-Organic Frameworks with Channel-Size-Dependent Behavior for Selective Gossypol Detection and Perovskite Quantum Dot Encapsulation.

An interpenetrating structure endows metal-organic frameworks (MOFs) with many exciting applications, such as fluorescence detection and host-guest chemistry. Herein, two unique structure-interpenetrating In-MOFs (In-pdda-1 and In-pdda-2; H2pdda = 4,4'-(pyridine-2,5-diyl)dibenzoic acid) are constructed by different coordination configurations. The four-connected In3+ center shows a triangular-pyramidal configuration or a 2D rectangle, forming an unc topology for In-pdda-1 and a sql network for In-pdda-2, respectively. Two different interpenetrating modes created by linear rigid ligands and metal clusters are observed in the two MOFs (In-pdda-1, 8-fold interpenetrating mode; In-pdda-2, [2D + 2D] interpenetrating mode), which determine the channel-size-dependent properties in fluorescence applications. During the quantitative detection process of gossypol, the small rhombic channels divided by interpenetrating molecular planes of In-pdda-2 greatly limit the distance between the analyte and the probe, promoting electron transfer and energy transfer processes and thus resulting in a low detection limit (28.6 nM). In addition, the pore size effect of In-pdda-1 encouraged us to explore an in situ perovskite quantum dot encapsulation strategy to obtain a MAPbBr3@MOF material with tunable and stable luminescence properties. Both of the above channel-size-dependent fluorescence properties may provide inspiration for the structural design and specialized applications of MOF materials.

The pathways of electronic excitation back energy transfer processes (BET) in novel Eu3+ heterocyclic 1,3-diketonates bearing a perfluorinated moiety

A series of novel brightly emitting Eu3+ coordination compounds with 1,3-diketones bearing a thiophene moiety and a linear CnF2n+1 chain (n = 1–8) were synthesized and fully characterized. The dependence of back energy transfer (BET) processes on the fluorinated chain length of the ligand environment was investigated in detail. The rates of radiative, non-radiative, and BET processes were estimated by a complete set of spectroscopic methods, including temperature stimulated luminescence measurements. It was demonstrated that fluorination provided a remarkable increase in the photoluminescence quantum yield up to 58% along with an increase in sensitization efficiency from 45 to 86%. It was explained by the reduction of non-radiative relaxation on molecular oscillators. The probability of the BET process has a trend to decrease from 500 to 100 s−1 upon an extension of the diketone fluorinated chain. Moreover, the back energy transfer process occurs from the resonant level of Eu3+ ion to ligand triplet state T1 through activation energy barrier ΔEA between potential energy surfaces of T1 and 5D0 states. It was found that extension of the fluorinated chain in ligand alter the activation energy and frequency factor of BET. The influence of the both parameters on BET was studied. The results obtained give a fundamental basis for further rational design of highly efficient luminescent compounds of Eu3+ ions.

Hybridization-Sensitive Fluorescent Probes for DNA and RNA by a Modular "Click" Approach.

Fluorescent DNA probes were prepared in a modular approach using the “click” post-synthetic modification strategy. The new glycol-based module and DNA building block place just two carbons between the phosphodiester bridges and anchor the dye by an additional alkyne group. This creates a stereocenter in the middle of this artificial nucleoside substitute. Both enantiomers and a variety of photostable cyanine–styryl dyes as well as thiazole orange derivatives were screened as “clicked” conjugates in different surrounding DNA sequences. The combination of the (S)-configured DNA anchor and the cyanylated cyanine–styryl dye shows the highest fluorescence light-up effect of 9.2 and a brightness of approximately 11,000 M–1 cm–1. This hybridization sensitivity and fluorescence readout were further developed utilizing electron transfer and energy transfer processes. The combination of the hybridization-sensitive DNA building block with the nucleotide of 5-nitroindole as an electron acceptor and a quencher increases the light-up effect to 20 with the DNA target and to 15 with the RNA target. The fluorescence readout could significantly be enhanced to values between 50 and 360 by the use of energy transfer to a second DNA probe with commercially available dyes, like Cy3.5, Cy5, and Atto590, as energy acceptors at the 5′-end. The latter binary probes shift the fluorescent readout from the range of 500–550 nm to the range of 610–670 nm. The optical properties make these fluorescent DNA probes potentially useful for RNA imaging. Due to the strong light-up effect, they will not require washing procedures and will thus be suitable for live-cell imaging.

Comparative analysis of lanthanide excited state quenching by electronic energy and electron transfer processes.

The relative sensitivities of structurally related Eu(III) complexes to quenching by electron and energy transfer processes have been compared. In two sets of 9-coordinate complexes based on 1,4,7-triazacyclononane, the Eu emission lifetime decreased as the number of conjugated sensitising groups and the number of unbound ligand N atoms increased, consistent with photoinduced electron transfer to the excited Eu(III) ion that is suppressed by N-protonation. Quenching of the Eu 5D0 excited state may also occur by electronic energy transfer, and the quenching of a variety of 9-coordinate complexes by a cyanine dye with optimal spectral overlap occurs by an efficient FRET process, defined by a Förster radius (R0) value of 68 Å and characterised by second rate constants in the order of 109 M-1 s-1; these values were insensitive to changes in the ligand structure and to the overall complex hydrophilicity. Quenching of the Eu and Tb excited states by energy transfer to Mn(II) and Cu(II) aqua ions occurred over much shorter distances, with rate constants of around 106 M-1 s-1, owing to the much lower spectral overlap integral. The calculated R0 values were estimated to be between 2.5 to 4 Å in the former case, suggesting the presence of a Dexter energy transfer mechanism that requires much closer contact, consistent with the enhanced sensitivity of the rate of quenching to the degree of steric shielding of the lanthanide ion provided by the ligand.

Zinc phthalocyanine carrying sulfenyl and sulfydryl functionalized sulfur vacancies MoS2 for enhancement of the third order nonlinear optical property

Zinc phthalocyanine carrying sulfenyl and 6-sulfydryl linkers was firstly used to functionalize with sulfur vacancies MoS2. The synthesized MoS2/ZnPc composite was further prepared to be PVA (polyvinyl alcohol) thin films by a drop coating method. The microscopic structures and photophysical properties of novel MoS2/ZnPc composite were characterized. A series of analysis results indicate that zinc phthalocyanine with sulfenyl and 6-sulfydryl linkers is loaded to sulfur vacancies of MoS2 by ligand conjugation. The third order nonlinear optical properties of MoS2/ZnPc composite were studied by an open aperture Z-scan technique at 532 nm with 4 ns laser pulses width. In comparison with individual MoS2 or ZnPc, whether MoS2/ZnPc solution or MoS2/ZnPc/PVA film sample possesses larger third order nonlinear absorption coefficients (β) and lower limiting thresholds (F50). It can be ascribed to a combination of different NLO absorption mechanisms for MoS2/ZnPc composite, including one-photon absorption, two photon absorptions and nonlinear scattering of MoS2, triplet excited state absorption of ZnPc, nonlinear scattering of MoS2/ZnPc and the photo-induced electron transfer or energy transfer (PET/ET) process between MoS2 and ZnPc moieties.

Low-Frequency Vibronic Mixing Modulates the Excitation Energy Flow in Bacterial Light-Harvesting Complex II.

Oscillatory features observed in two-dimensional electronic spectroscopy (2DES) manifest coherent vibrational and electronic dynamics and even the interplay of them. Recently, we developed a 2DES technique utilizing a pair of synchronized repetition-frequency-stabilized lasers, which enables the wide dynamic range measurements of 2DES signals rapidly. Here, we apply this dual-laser 2DES technique to investigate the electronic energy transfer (EET) process in bacterial light-harvesting complex II consisting of B800 and B850 circular aggregates at ambient temperature, and the coherent vibrational wavepakcet associated with the EET between the two aggregates are measured. Examining the principal component analysis of the time-resolved 2DES signal, we found that the EET from B800 to low-lying B850 states is modulated by a low-frequency (156 cm-1) vibrational mode of the exciton donor (B800). This observation suggests that the donor transition density is modulated by this vibration, which, in turn, modulates the energy transfer dynamics.

Progress in Photoinduced Radical Reactions using Electron Donor‐Acceptor Complexes

AbstractPhotocatalyzed organic synthesis transformation is a remarkable green synthetic strategy because of the advantages of operational simplicity, high chemoselectivities, cheap, and environmental benignancy, along with the extensive applications in the fields of organic, pharmaceutical and functional material chemistry. Generally, photoredox catalysts or photosensitizers are necessary for the generation of their excited states to perform the successive oxidative or reductive reactions through the single electron transfer (SET) or energy transfer (ET) process. Furthermore, the exploration of a colored electron donor‐acceptor (EDA) complex or a charge transfer (CT) complex between an electron‐rich and an electron‐poor substrate provides the chance to deliver the excited intermediate under the irradiation of light, resulting in the formation of radical activate species through a single electron transfer to induce successive various radical reactions. These reactions were performed without the need of any external photocatalysts under mild reaction conditions. Herein, this review focuses on the recent progress on photoinduced radical addition reactions, radical borylations, reductive reactions, radical‐radical cross‐coupling reactions, degradation reactions and radical cascade cyclization via EDA complexes. We highlight these novel green synthetic methodologies and applications, as well as the mechanisms. This review will help to provide references for organic and medicinal chemists who are charmed by these green organic photochemical transformations based on EDA complexes.

Ensemble-level energy transfer measurements can reveal the spatial distribution of defect sites in semiconductor nanocrystals.

Energy transfer measurements are widely used to measure the distance between donors and acceptors in heterogeneous environments. In nanocrystal (NC)-molecule donor-acceptor systems, NC defects can participate in electronic energy transfer (EnT) in a defect-mediated EnT process. Here, we explore whether ensemble-level spectroscopy measurements can quantify the distance between the donor defect sites in the NC and acceptor molecules. We studied defect-mediated EnT between ZnO NCs and Alexa Fluor 555 (A555) because EnT occurs via emissive NC defect sites, such as oxygen vacancies. We synthesized a size series of ZnO NCs and characterized their radii, concentration, photoluminescence (PL) lifetime, and defect PL quantum yield using a combination of transmission electron microscopy, elemental analysis, and time-resolved PL spectroscopy. The ZnO defect PL decay kinetics were analyzed using the stochastic binding (SB) and restricted geometry (RG) models. Both models assume the Förster point dipole approximation, but the RG model considers the geometry of the NC donor in the presence of multiple acceptors. The RG model revealed that the emissive defect sites are separated, on average, 0.5 nm from the A555 acceptor molecules. That is, the emissive defect sites are predominantly located at or near the surface of large NCs. The SB model revealed the average number of A555 molecules per NC and the equilibrium binding constant but did not provide meaningful information regarding the defect-acceptor distance. We conclude that ensemble-level EnT measurements can reveal the spatial distribution of defect sites in NCs without the need for interrogating the sample with a microscope.

Visible‐light‐mediated Synthesis of Bromo‐containing Azaspirotrienediones from N‐phenylpropynamides

AbstractA visible‐light‐mediated reaction of N‐phenylpropynamides with diethyl 2,2‐dibromomalonate for the synthesis of bromo‐substituted azaspirotrienediones has been developed. This method allows the formation of C−Br, C−C and C=O bonds in one pot via a cascade radical addition/ipso‐cyclization/oxidation process. A possible radical mechanism involving single electron transfer and energy transfer processes is proposed based on control experiments, cyclic voltammetry determination and Stern‐Volmer quenching experiments.

Orthogonally aligned cyclic BODIPY arrays with long-lived triplet excited states as efficient heavy-atom-free photosensitizers.

In photosensitizers, long triplet excited state lifetimes are key to their efficient electron transfer or energy transfer processes. Herein, we report a novel class of cyclic trimeric BODIPY arrays which were efficiently generated from easily accessible meso-mesityldipyrrinone and arylboronic acids in one pot. Arylboronic acid, for the first time, was used to provide a boron source for BODIPY derivatives. Due to the well-defined and orthogonally aligned BODIPY cores as verified by X-ray crystallography, these BODIPY arrays show strong exciton coupling effects and efficient intersystem crossings, and are novel heavy-atom-free photosensitizers with a long-lived triplet excited state (lifetime up to 257.5 μs) and good reactive oxygen species generation efficiency (up to 0.72) contributed by both 1O2 and O2−˙ under light irradiation.

Enhanced Near-Infrared Emission from Eight-Coordinate vs Nine-Coordinate YbIII Complexes Using 2-(5-Methylpyridin-2-yl)-8-hydroxyquinoline.

Enhanced near-infrared (NIR) luminescence from two structurally related heterobinuclear NaIYbIII eight-cooridnate and heterobinuclear YbIIINaI eight-coordinate (CN = 8) complexes is reported and compared to a nine-coordinate (CN = 9) homoleptic complex. For the heteroleptic complex, [Yb(MPQ2)(acac)], the YbIII cation is coordinated to two tridentate 2-(5-methylpyridin-2-yl)-8-quinolinate (MPQ) anions, with a bidentate acetylacetonate (acac) anion completing the coordination sphere. Instead, the heterobinuclear [NaYb(MPQ)4] complex comprises a total of four anionic MPQ ligands, two of which exhibit κ3-coordination to the YbIII cation. The remaining two MPQ anions are unidentate toward the lanthanide and form μ2-bridges via the deprotonated quinolinate oxygens to a bound NaI cation which is also coordinated to the remaining nitrogen donor atoms. The structural properties of these complexes were evaluated by single-crystal X-ray diffraction (SXRD), continuous shape measure (CShM) analysis, and 1H NMR spectroscopy using a diamagnetic LuIII analogue. The corresponding photophysical properties were examined in CH2Cl2 solution by using absorption and emission spectroscopy. For both the complexes, characteristic YbIII emission is observed at ca. 980 nm, with recorded photoluminescence quantum yields (Φobs) and NIR luminescence lifetimes (τobs) of 2.0% and 14.0 μs vs 1.5% and 11.6 μs for the [NaYb(MPQ)4] and [Yb(MPQ)2(acac)] complexes, respectively. Interestingly, the eight-coordinate YbIII complexes both have higher photoluminescence quantum yields when compared to the homoleptic [Yb(MPQ)3] complex, which has a reported quantum yield of 1.0% and a NIR lifetime determined herein of 13.3 μs under identical conditions. These results have been rationalized by considering the overall efficiency of the ligand-centered sensitization process (ηsens = Φisc × Φeet), together with subsequent radiative (kr) and nonradiative (knr) deactivation of the YbIII cation. Moreover, the efficiency of the intersystem crossing (Φisc) and electronic energy transfer (Φeet) processes involved in the antennae effect have been quantified for the new complexes using a combination of nanosecond and femtosecond transient absorption techniques and have been compared to our previous results using [Ln(MPQ)3] complexes with Ln = Yb and Lu.

Photoinduced Electron Transfer and Energy Transfer Processes in a Flexible BODIPY-C60 Dyad.

A new donor-acceptor dyad composed of a BODIPY (4,4'-difluoro-4-bora-3a,4a-diaza-s-indacene) donor and a fullerene C60 acceptor has been synthesized and characterized. This derivative has been prepared using a clickable fullerene building block that bears an alkyne moiety and a maleimide unit. The post-functionalization of the maleimide group by a BODIPY thiol leads to a BODIPY-C60 dyad, leaving the alkyne moiety for further functional arrangement. On the basis of the combination of semi-empirical and density functional theory (DFT) calculations, spectroelectrochemical experiments, and steady-state and time-resolved spectroscopies, the photophysical properties of this new BODIPY-C60 dyad were thoroughly studied. By using semi-empirical calculations, the equilibrium of three conformations of the BODIPY-C60 dyad has been deduced, and their molecular orbital structures have been analyzed using DFT calculations. Two short fluorescence lifetimes were attributed to two extended conformers displaying variable donor-acceptor distances (17.5 and 20.0 Å). Additionally, the driving force for photoinduced electron transfer from the singlet excited state of BODIPY to the C60 moiety was calculated using redox potentials determined with electrochemical studies. Spectroelectrochemical measurements were also carried out to investigate the absorption profiles of radicals in the BODIPY-C60 dyad in order to assign the transient species in pump-probe experiments. Under selective photoexcitation of the BODIPY moiety, occurrences of both energy and electron transfers were demonstrated for the dyad by femtosecond and nanosecond transient absorption spectroscopies. Photoinduced electron transfer occurs in the folded conformer, while energy transfer is observed in extended conformers.

Stable Luminescent Radicals and Radical-Based LEDs with Doublet Emission

Radical-based light-emitting diodes are an innovative type of organic light-emitting diodes (OLEDs), which adopt luminescent radicals as emitters, aiming at improving the external quantum efficienc...

In Situ-Generated Halogen-Bonding Complex Enables Atom Transfer Radical Addition (ATRA) Reactions of Olefins.

Although organic-based photocatalysts provide an inexpensive, environmentally friendly alternative, many are incapable of absorption within the visible wavelength range; this ultimately influences their effectiveness. Photocatalytic reactions usually proceed via single electron transfer (SET) or energy transfer (ET) processes from the photoexcited molecules to the various substrates. In our study, the carbohalogenation of olefins was accomplished by combining CBr4 and 4-Ph-pyridine under irradiation. The atom transfer radical addition reaction of olefins was catalyzed by an in situ-formed photocatalyst via halogen bonding to afford a variety of products in moderate to good yields. Essential to the reaction is the formation of a CT complex with the haloalkene, which triggers charge separation processes and, ultimately, leads to the formation of the C-centered radical. While taking advantage of relatively inexpensive, readily available, and environmentally friendly reagents, the indirect activation of the substrate via the photoexcited catalyst paves the way for more efficient routes, especially for otherwise challenging chemical syntheses.

Electron-Vibrational Spectra and Dynamics of the Lutein Molecule.

The carotenoid molecules such as lutein play an important role in the absorption of light and the following transfer of energy during photosynthesis. However, the study of these processes by the experimental methods only is quite difficult because some of the transitions between the electronic states of carotenoids are optically forbidden and the effect of vibrational states change also must be taken into account. In the present work, electronic-vibrational states of the lutein molecule in the LHCII complex of higher plants and in the diethyl ether solution were described using the ab initio methods. For lutein of LHCII, the electronic energy transfer processes were modeled. The role of the "hot" S1 states of lutein was shown to be of great importance.