Charge Transfer Excitation Research Articles

Photochemistry using a host-guest charge transfer paradigm: DMABN as a dynamical probe of ground and excited states.

Photoexciting charge transfer (CT) transitions arising from host-guest interactions in a confined environment can efficiently yield kinetically trapped radicals. In order to predispose these photogenerated radicals for diffusion limited reactions it becomes imperative to understand the nature of the host-guest CT interactions in the ground and excited states. Here we probe the heterogeneity of guest orientations and the ensuing excited state charge transfer dynamics of an electron-rich molecular probe N,N-dimethylaminobenzonitrile (DMABN) incarcerated inside an electron deficient water-soluble cationic Pd6L412+ nanohost. Using a combination of 1H-NMR, resonance Raman spectrosocopy, and pump-probe spectroscopy we highlight the necessary challenges that need to be addressed in order to use molecular cages as photocatalytic reaction vessels.

Efficient charge-transfer from diketopyrrolopyrroles to single-walled carbon nanotubes.

In this contribution, the excited state charge-transfer interactions between single-walled carbon nanotubes (SWCNTs) and a variety of phenyl, 4-bromophenyl, and thiophene substituted diketopyrrolopyrroles (DPPs), is described. Atomic force microscopy (AFM) and aberration corrected high resolution transmission electron microscopy (AC-HRTEM) corroborated the successful formation of DPP/SWCNTs. Steady-state absorption, fluorescence, and Raman spectroscopies all gave insights into the impact on their ground and excited states as well as on the nature of their electronic communication/interaction. Of great value was time-resolved transient absorption spectroscopy on the femto- and nanosecond time-scales; it assisted in deciphering the charge-transfer mechanism from the DPPs to the SWCNT and in analyzing the dynamics thereof with transfer efficiencies of up to 81%. Important confirmation for the one-electron oxidized DPPs came from pulse radiolysis assays with focus on establishing their spectral fingerprints. Our full-fledged work demonstrates that the successful preparation of stable DPP/SWCNTs represents an important step towards establishing them as a viable alternative to porphyrin-based systems in emerging applications such as solar energy conversion.

Visible-light-induced ligand to metal charge transfer excitation enabled phosphorylation of aryl halides.

We herein described a visible light induced nickel(II)-catalyzed cross-coupling of secondary phosphine oxides with aryl halides. The Ni(I) species and chlorine atom radical Cl˙ were generated via the ligand to metal charge transfer (LMCT) process of the NiCl2(PPh3)2, which allows nickel(IV)-phosphorus species in situ formation, giving various tertiary phosphine oxides under photocatalyst-free conditions.

Intramolecular charge transfer excitation induced by CH3O substitution in the 3-methoxy-1-propoxy radical.

The oxy-substituted alkoxy radicals are generated from the oxidation of ethers. Their degradation path affects ozone production and the formation of the secondary organic aerosol in the atmosphere. In this work, three alkoxy radicals with methoxy (CH3O) substitution at β, γ, and δ carbon are studied using laser-induced fluorescence (LIF) spectroscopy and theoretical calculation methods. A charge transfer (CT) excited state induced by the CH3O substitution is identified to be because of the intramolecular electron transfer from the C-O-C p orbital to the radical O p orbital. Comparison of the structure and CT transition strength between GGt and TTt conformers of the 3-methoxy-1-propoxy radical (CH3OCH2CH2CH2O) suggests that this long-range charge transfer effect is mainly a through-bond interaction. The CT excited state of CH3OCH2CH2CH2O has a conical intersection with the CO σ → O p excited state, which, hence, changes the LIF spectrum of the radical. Only the decomposition product HCHO was observed in the LIF spectrum of β substituted radical CH3OCH2CH2O. For δ substituted radical CH3OCH2CH2CH2CH2O, the substitution effect on the radical stability is negligible and its LIF spectrum is close to that of unsubstituted alkoxy radicals. The results provide information for understanding the degradation chemistry of oxygenated hydrocarbon molecules in the atmosphere.

Organic photoelectrode engineering: accelerating photocurrent generation via donor–acceptor interactions and surface-assisted synthetic approach

We construct photoelectrodes based on a conjugated organic network. The donor–acceptor interactions within the polymer structure narrow the optical bandgap and enable efficient excited charge transfer, leading to the marked improvement of the PEC activity of the electrode.

Aggregation-induced emission spectra of triphenylamine salicylaldehyde derivatives via excited-state intramolecular proton transfer revealed by molecular spectral and dynamics simulations.

Aggregation-induced emission (AIE) spectra accompanied by excited state intramolecular proton transfer (ESIPT) for two triphenylamine salicylaldehyde derivatives (namely, TS and TS-OMe) are investigated by performing molecular spectral and dynamics simulations associated with the hybrid quantum mechanics/molecular mechanics (QM/MM) at the quantum level of the time-dependent density functional theory. The simulated emission spectral peaks and Stokes' shifts are in good agreement with the experimental results for both TS and TS-OMe. Furthermore, the AIE spectral mechanisms are well explained to be associated with the ESIPT processes for both TS and TS-OMe monomers in the aggregated crystal state, while the AIE spectra mechanism for the TS-OMe (TS) dimer is accompanied by intermolecular charge-transfer excitation process. Besides, the TS dimers also contributed to the AIE mechanisms in the crystal with the intermolecular charge-transfer from one monomer to another. In addition, the TS dimers are contributed to the AIE mechanisms in the crystal with the intermolecular charge-transfer from one monomer to another. On the other hand, simulated emission spectra for both the TS and TS-OMe monomers in acetonitrile solution are involved in mixed emission with and without the ESIPT process, as interpreted by nonadiabatic molecular dynamics simulation. It is also briefly addressed that the emission spectra in the solution are weak and enhanced in the crystal. The present study provides a great physical insight into the design of highly efficient AIE compounds.

Effects of dual lanthanide ions doping on optical and electrical properties of barium stannate with Ba1–x–yLaxSmySnO3 compositions

Two kinds of trivalent lanthanide ions (Ln3+) were substitutionally doped in the cubic perovskite-type BaSnO3 and their effects on optical and electrical properties were investigated. La3+ was fixed as the first dopant because of its electron-donor nature, while the second dopant was selected from luminescent Ln3+ ions, namely, Pr3+, Sm3+, Eu3+, or Tb3+. In preliminary screening, Sm3+ was found to exhibit strong photoluminescence (PL) through an efficient O2––Sm3+ charge transfer excitation. Then, powders and sintered pellets of Ba1–x–yLaxSmySnO3 compositions (x = 0–0.04 and y = 0.001–0.06) were prepared through a polymerized complex method and their PL intensity and electrical resistivity were measured and compared among the samples. The PL intensity of the powder samples increased with the increasing Sm3+ content y at any La3+ content x. However, at the fixed Sm3+ content y, the PL intensity decreased with the increasing La3+ content x. The electrical resistivity of the pellet samples decreased with the increasing La3+ content x, while it increased considerably with the increasing Sm3+ content y. The dependence of the above physical properties on the La3+ and Sm3+ contents was discussed in association with the formal valence change of Sn4+ after the dual La3+/Sm3+ doping in BaSnO3.

Computational insight into newly anomalous delayed fluorescence emitters based on D-A-A structures

In variety of skeleton structures of delayed fluorescence molecular materials, the D-A-A type has been widely concerned recently for its improved double efficiency of reverse intersystem crossing process (RISC). Based on the D-A-A structure, eight new D-TRZ-nPO molecules (D = dihydrophenazine (DHPZ), phenothiazine (PTZ), phenoxazine (PXZ) and 9,9-dimethyl-9,10-dihydroacridan (DMAC), TRZ = triphenyltriazine, n = 1 or 2) with potential performance improvement have been deeply investigated by theoretical calculations. Interestingly, these molecules with the closing energy levels of high-lying excited states and charge transfer characters may perform rare high-lying excited state delayed fluorescence. Meanwhile, the changes of RISC and the corresponding effects caused by D-A-A structure from low energy level to high energy level are analyzed in detail. Furthermore, DHPZ-TRZ-2PO with blue emission (452 nm) is expected to be a potential high-lying excited state delayed fluorescence material candidate.

Photophysics of Ruthenium(II) Complexes with Thiazole π-Extended Dipyridophenazine Ligands.

Transition-metal-based donor-acceptor systems can produce long-lived excited charge-transfer states by visible-light irradiation. The novel ruthenium(II) polypyridyl type complexes Ru1 and Ru2 based on the dipyridophenazine ligand (L0) directly linked to 4-hydroxythiazoles of different donor strengths were synthesized and photophysically characterized. The excited-state dynamics were investigated by femtosecond-to-nanosecond transient absorption and nanosecond emission spectroscopy complemented by time-dependent density functional theory calculations. These results indicate that photoexcitation in the visible region leads to the population of both metal-to-ligand charge-transfer (1MLCT) and thiazole (tz)-induced intraligand charge-transfer (1ILCT) states. Thus, the excited-state dynamics is described by two excited-state branches, namely, the population of (i) a comparably short-lived phenazine-centered 3MLCT state (τ ≈ 150-400 ps) and (ii) a long-lived 3ILCT state (τ ≈ 40-300 ns) with excess charge density localized on the phenazine and tz moieties. Notably, the ruthenium(II) complexes feature long-lived dual emission with lifetimes in the ranges τEm,1 ≈ 40-300 ns and τEm,2 ≈ 100-200 ns, which are attributed to emission from the 3ILCT and 3MLCT manifolds, respectively.

Vibronic exciton model for low bandgap donor-acceptor polymers.

A vibronic exciton model is introduced to describe the excited state band structure and associated absorption spectra of low bandgap donor-acceptor conjugated polymers. The Hamiltonian is represented in a diabatic basis consisting of Frenkel-like donor and acceptor fragment excitations as well as charge-transfer (CT) excitations between neighboring fragments. States are coupled to each other through electron and hole transfer as well as Coulombically, through interacting fragment transition dipole moments. Local vibronic coupling involving the prominent aromatic-quinoidal vibrational mode, which is responsible for pronounced vibronic progressions in most conjugated oligomers and polymers, is also included. The DAD repeat unit is shown to behave like a J-aggregate trimer, driven by both the sizable in-phase electron and hole transfer integrals between donor and acceptor fragments as well as negative Coulomb coupling between donor and acceptor fragment excitations. The J-aggregate behavior is enhanced in the polymer limit through inter-repeat unit coupling, with the 0-0 vibronic peak significantly enhanced in the lowest-energy near-IR band. In addition, the radiative rate is enhanced by the number of coherently connected repeat units. The near-IR band is shown to possess roughly equal admixtures of CT and Frenkel-like excitations. Applications are made to the polymer PffBT4T-2DT, with the simulated absorption spectrum quantitatively capturing the salient features of the measured spectrum.

Charge transfer excitations, pair density waves, and superconductivity in moiré materials

Transition metal dichalcogenide (TMD) bilayers are a new class of tunable moir\'e systems attracting interest as quantum simulators of strongly-interacting electrons in two dimensions. In particular, recent theory predicts that the correlated insulator observed in WSe$_2$/WS$_2$ at half filling is a charge-transfer insulator similar to cuprates and, upon further hole doping, exhibits a transfer of charge from anion-like to cation-like orbitals at different locations in the moir\'e unit cell. In this work, we demonstrate that in this doped charge-transfer insulator, tightly-bound charge-2e excitations can form to lower the total electrostatic repulsion. This composite excitation, which we dub a trimer, consists of a pair of holes bound to a charge-transfer exciton. When the bandwidth of doped holes is small, trimers crystallize into insulating pair density waves at a sequence of commensurate doping levels. When the bandwidth becomes comparable to the pair binding energy, itinerant holes and charge-2e trimers interact resonantly, leading to unconventional superconductivity similar to superfluidity in an ultracold Fermi gas near Feshbach resonance. Our theory is broadly applicable to strongly-interacting charge-transfer insulators, such as WSe$_2$/WS$_2$ or TMD homobilayers under an applied electric field.

Transitioning from Intraligand π,π* to Charge-Transfer Excited States Using Thiophene-Based Donor-Acceptor Systems.

A series of electron donor-acceptor compounds are reported in which both the donor and acceptor strengths are systematically altered using mono-, bi-, and terthiophene as donors and benzo[c][1,2,5]thiadiazole (btd), dipyrido[3,2-a:2',3'-c]phenazine (dppz), and the corresponding rhenium(I) complex, [ReCl(CO)3(dppz)], as acceptors. The electronic properties of the compounds are characterized using electrochemistry, electronic absorbance and emission spectroscopies, and transient absorption spectroscopy. The effect of donor and acceptor strengths on frontier molecular orbital localization and on the charge-transfer (CT) character of optical transitions is modeled using density functional theory (DFT) calculations. The electronic absorption spectra of the compounds investigated are dominated by intraligand charge-transfer (ILCT) transitions, where the CT character is shown to increase across the series from mono- to bi- to terthiophene but not significantly across the acceptor series. Emission is shown to originate from the absorbing state. Long-lived nonemissive states have been observed using transient absorption spectroscopy and assigned using triplet-state DFT calculations, which indicate that the lowest energy excited state has more thiophene-localized π,π* character with an increasing number of appended thiophenes.

Chemical enhancement effects on protoporphyrin IX surface‐enhanced Raman spectra: Metal substrate dependence and a vibronic theory analysis

AbstractSurface‐enhanced Raman spectra (SERS) of protoporphyrin IX (PPIX) and analogous metal‐containing PPIX compounds excited at 785 nm exhibit robust, strongly enhanced (~5 × 109) spectra that are highly dependent on the nanostructured metal (Au or Ag). Although the relative intensities of the 785‐nm SERS vibrational spectral features are very similar for all observed PPIX‐based compounds, the relative intensities are dramatically different on Au and Ag SERS substrates. Time‐dependent density functional theory (TDDFT) calculations are carried out for Au2/Ag2–PPIX complexes to understand the origins of this chemical enhancement contribution to the observed SERS spectra. The observed metal dependence of the SERS spectra in the heme ring stretching region (1,500–1,620 cm−1) are reproduced by calculated resonance Raman intensities due to low‐lying metal (σ) to molecule (π*) charge transfer excitations of the metal dimer–PPIX complexes when the metal dimer is near a porphyrin ring Cβ position. The nuclear coordinate dependence of electronic transition moments is essential for capturing the effects of these CT excitations. A simple method for determining the importance of the transition moment normal mode dependence relative to Franck–Condon factors (A term) is described and implemented. The consequences of this vibronic analysis for the observation of overtone/combination bands in SERS spectra are discussed.

Dynamics of electron transfer in melanin-trinitrofluorenone system

The kinetics of photoluminescence (PL) and time-resolved emission spectra (TRES) of melanin solutions with an effective electron acceptor 2,4,7-trinitrofluorenone (TNF) have been studied. Based on the analysis of the kinetic decay curves and TRES, the fast and slow PL decay components can be distinguished, which characterize the processes of a relaxation of excited states and charge transfer in the melanin-TNF molecular system. In this paper, the observed dependences have been analyzed and the model to explain such behavior of PL dynamic characteristics has been proposed.

Effect of terbium and silver co-doping on the enhancement of photoluminescence in CaSO4 phosphors

Abstract In this work, the photoluminescence properties of CaSO4 crystals co-doped with terbium and silver from silver oxide or silver nanoparticles (NPs) in different concentrations are investigated. Phosphors are obtained by means of a slow evaporation route and calcined at 600 °C for 1 h. X-ray diffraction analysis shows the formation of a single-phase anhydrite structure with orthorhombic symmetry. The photoluminescence properties are investigated using vacuum ultraviolet, ultraviolet and X-ray excitation. All luminescent measurements reveal the characteristic emissions of Tb3+. The analyses using excitation with ultraviolet light show that the Ag NPs are able to generate structural defects more satisfactorily compared to CaSO4:Tb with silver oxide. We also observe that higher concentrations of Ag increase the Tb3+ emission intensity, while higher concentrations of Ag NPs decrease it. The good stability of CaSO4 results in an efficient energy transfer from the host lattice to the activator under X-ray excitation, with the NPs contributing to the increase in luminescent intensity. Investigation of the terbium valence in the CaSO4 host shows a complete reduction of the Tb4+ present in Tb4O7 to Tb3+, as indicated by the X-ray absorption near edge structure. The vacuum ultraviolet excitation spectra reveal three broad bands, attributed to the charge-transfer excitations within SO42− complexes and to the 4f8 → 4f75d1 transitions on Tb3+. Our results also reveal that silver particles are responsible for generating deeper capture centers.

Fate of Low-Lying Charge-Transfer Excited States in a Donor:Acceptor Blend with a Large Energy Offset.

In an effort to gain a comprehensive picture of the interfacial states in bulk heterojunction solar cells, we provide a combined experimental-theoretical analysis of the energetics and dynamics of low-lying electronic charge-transfer (CT) states in donor:acceptor blends with a large frontier orbital energy offset. By varying the blend composition and temperature, we unravel the static and dynamic contributions to the disordered density of states (DOS) of the CT-state manifold and assess their recombination to the ground state. Namely, we find that static disorder (conformational and electrostatic) shapes the CT DOS and that fast nonradiative recombination crops the low-energy tail of the distribution probed by external quantum efficiency (EQE) measurements (thereby largely contributing to voltage losses). Our results then question the standard practice of extracting microscopic parameters such as exciton energy and energetic disorder from EQE.

Electronic couplings for photo-induced processes from subsystem time-dependent density-functional theory: The role of the diabatization.

Subsystem time-dependent density-functional theory (sTDDFT) making use of approximate non-additive kinetic energy (NAKE) functionals is known to be capable of describing excitation energy transfer processes in a variety of applications. Here, we show that sTDDFT, especially when combined with projection-based embedding (PbE), can be employed for the entire range of photo-induced electronic couplings essential for modeling photophysical properties of complex chemical and biological systems and therefore represents a complete toolbox for this class of problems. This means that it is capable of capturing the interaction/coupling associated with local- and charge-transfer (CT) excitons. However, this requires the choice of a reasonable diabatic basis. We therefore propose different diabatization strategies of the virtual orbital space in PbE-sTDDFT and show how CT excitations can be included in sTDDFT using NAKE functionals via a phenomenological approach. Finally, these electronic couplings are compared to couplings from a multistate fragment excitation difference (FED)-fragment charge difference (FCD) diabatization procedure. We show that both procedures, multistate FED-FCD and sTDDFT (with the right diabatization procedure chosen), lead to an overall good agreement for the electronic couplings, despite differences in their general diabatization strategy. We conclude that the entire range of photo-induced electronic couplings can be obtained using sTDDFT (with the right diabatization procedure chosen) in a black-box manner.

An ab initio exciton model for singlet fission.

We present an ab initio exciton model that extends the Frenkel exciton model and includes valence, charge-transfer, and multiexcitonic excited states. It serves as a general, parameter-free, yet computationally efficient and scalable approach for simulation of singlet fission processes in multichromophoric systems. A comparison with multiconfigurational methods confirms that our exciton model predicts consistent energies and couplings for the pentacene dimer and captures the correct physics. Calculations of larger pentacene clusters demonstrate the computational scalability of the exciton model and suggest that the mixing between local and charge-transfer excitations narrows the gap between singlet and multiexcitonic states. Local vibrations of pentacene molecules are found to facilitate singlet-multiexcitonic state-crossing and hence are important for understanding singlet fission. The exciton model developed in this work also sets the stage for further implementation of the nuclear gradients and nonadiabatic couplings needed for first principles nonadiabatic quantum molecular dynamics simulations of singlet fission.

Long-Lived Local Triplet Excited State and Charge Transfer State of 4,4'-Dimethoxy Triphenylamine-BODIPY Compact Electron Donor/Acceptor Dyads.

The spin-orbit charge transfer intersystem crossing (SOCT-ISC) and the formation of a long-lived charge transfer (CT) state were studied with a series of 4,4'-dimethoxy triphenylamine-BODIPY compact electron donor/acceptor dyads. Different torsion freedoms were applied in the dyads to tune the electronic coupling between the donor and acceptor, and a red-shifted CT absorption band was observed for one dyad. The dyads show solvent polarity-dependent singlet oxygen photosensitizing ability (quantum yields 3%-79%). Nanosecond transient absorption spectra of the dyad in nonpolar solvent confirm the formation of triplet states. The intrinsic triplet state lifetime is up to 383 μs (in fluid solution), which is much longer than that accessed with the heavy atom effect (276 μs). Intermolecular triplet photosensitizing of the dyads in a polar solvent produces a long-lived 3CT state (lifetime, τCT = 8.0 μs supported by the electron spin density surface analysis). The triplet state lifetime of the dyads doped in a Clear Flex 50 polymer film is exceptionally long (7.6-11.4 ms), and formation of a long-lived CT state (37 μs) was observed. Triplet-triplet annihilation upconversion was performed with the electron donor/acceptor dyads used as the triplet photosensitizer and perylene used as the triplet acceptor; the upconversion quantum yield is up to 15.8%.

Dual-channel ratiometric recognition of Al3+ and F- ions through an ESIPT-ESICT signalling mechanism.

An optical probe 1 has been synthesized comprising naphthalimide unit conjugated with Schiff base, exhibiting excited state intramolecular proton transfer and intramolecular charge transfer as a potential sensor for Al3+ and F- ions using standard spectroscopic techniques. The probe 1 exhibited local and charge-transfer excitation at 340nm and 460nm, respectively. On excitation at 460nm, probe 1 displayed two emission bands at 510nm and 610nm, accompanied by Stokes' shift of 50nm and 150nm, respectively. The solvatochromic effect and theoretical calculation depicted that the representative emissions resulted from the ESICT/ESIPT phenomenon. Upon addition of Al3+ ions, the charge transfer excitation at 460nm was enhanced ratiometrically to local excitation at 340nm and showed a color change from orange to yellow. Similarily, probe 1.Al3+ displayed emission enhancement at 540nm in H2O/CH3CN (1:9; v/v) and showed a color change from yellow to blue-green emission. Following the detection of Al3+ ions, hydrolysis of probe 1 to its reacting precursors was observed. The detection of Al3+ ions was also demonstrated in surfactant-containing water. The limit of detection (LOD) of probe 1 (H2O/CH3CN (1:9; v/v)) towards Al3+ ions was measured to be 3.2×10-8 M. The probe 1 displayed a ratiometric absorption response towards F- ions with a new peak at 570nm and showed a color change from orange to purple. The probe 1.F- displayed a decrease in emission at 635nm. The LOD of probe 1 (CH3CN) towards F- ions was measured to be 7.5×10-7 M.