Long-lived Charge Transfer State Research Articles

High-Spin State of a Ferrocene Electron Donor Revealed by Optical and X-ray Transient Absorption Spectroscopy.

Ferrocene is one of the most common electron donors, and mapping its ligand-field excited states is critical to designing donor-acceptor (D-A) molecules with long-lived charge transfer states. Although 3(d-d) states are commonly invoked in the photophysics of ferrocene complexes, mention of the high-spin 5(d-d) state is scarce. Here, we provide clear evidence of 5(d-d) formation in a bimetallic D-A molecule, ferrocenyl cobaltocenium hexafluorophosphate ([FcCc]PF6). Femtosecond optical transient absorption (OTA) spectroscopy reveals two distinct electronic excited states with 30 and 500 ps lifetimes. Using a combination of ultraviolet, visible, near-infrared, and short-wave infrared probe pulses, we capture the spectral features of these states over an ultrabroadband range spanning 320 to 2200 nm. Time-dependent density functional theory (DFT) calculations of the lowest triplet and quintet states, both primarily Fe(II) (d-d) in character, qualitatively agree with the experimental OTA spectra, allowing us to assign the 30 ps state as the 3(d-d) state and the 500 ps state as the high-spin 5(d-d) state. To confirm the ferrocene-centered high-spin character of the 500 ps state, we performed X-ray transient absorption (XTA) spectroscopy at the Fe and Co K edges. The Fe K-edge XTA spectrum at 150 ps shows a red shift of the absorption edge that is consistent with an Fe(II) high-spin state, as supported by ab initio calculations. The transient signal detected at the Co K-edge is 50× weaker, confirming the ferrocene-centered character of the excited state. Fitting of the transient extended X-ray absorption fine structure region yields an Fe-C bond length increase of 0.25 ± 0.1 Å in the excited state, as expected for the high-spin state based on DFT. Altogether, these results demonstrate that the high-spin state of ferrocene should be considered when designing donor-acceptor assemblies for photocatalysis and photovoltaics.

Tailoring the Position of Ester Group on N-Alkyl Chains of Benzotriazole-based Small Molecule Acceptors for High-Performance Organic Solar Cells.

Side chain engineering plays a vital role in exploring high-performance small molecule acceptors (SMAs) for organic solar cells (OSCs). In this work, we designed and synthesized a series of A-DA'D-A type SMAs by introducing different N-substituted alkyl and ester alkyl side chains on benzotriazole (BZ) central unit and aimed to investigate the effect of different ester substitution positions on photovoltaic performances. All the new SMAs with ester groups exhibit lower the lowest unoccupied molecular orbital (LUMO) energy levels and more blue-shifted absorption, but relatively higher absorption coefficients than alkyl chain counterpart. After blending with the donor PM6, the ester side chain-based devices demonstrate enhanced charge mobility, reduced amorphous intermixing domain size and long-lived charge transfer state compared to the alkyl chain counterpart, which are beneficial to achieve higher short-circuit current density (Jsc ) and fill factor (FF), simultaneously. Thereinto, the PM6 : BZ-E31 based device achieves a higher power conversion efficiency (PCE) of 18.33 %, which is the highest PCE among the OSCs based on the SMAs with BZ-core. Our work demonstrated the strategy of ester substituted side chain is a feasible and effective approach to develop more efficient SMAs for OSCs.

Endonuclease mimetic activity of laccase with sequence preference following redox potential and interaction of bases

Degradation of lignin, a natural macromolecule, by laccase via substrate radicals has been intensively studied. However, the interactions between laccase and DNA have not been thoroughly elucidated to date. In this report, we demonstrate that laccase has the endonuclease-mimetic activity with the sequence preference. The decay of plasmid and cDNA was observed with atomic force microscopy (AFM), electron paramagnetic resonance (EPR) and DNA sequencing. Concomitantly, ▪ appeared, which produced the DNA lesion. The sequencing results showed that A and AA were the preferred nucleotides flanking the cleaved sites. The hydrogen bonds between complementary base pairs and the base redox potential were responsible for the long-lived charge transfer state within the A-repetitive sequence governing the sequence preference. This discovery implies alternative strategies of surviving the phosphorus stress and resistance to alien DNA in certain species, in which laccase is abundant. These results enrich our understanding of the mechanisms of DNA damage and are important for the interpretation of disease treatment.

Nanosecond Metal-to-Ligand Charge-Transfer State in an Fe(II) Chromophore: Lifetime Enhancement via Nested Potentials.

Examples of Fe complexes with long-lived (≥1 ns) charge-transfer states are limited to pseudo-octahedral geometries with strong σ-donor chelates. Alternative strategies based on varying both coordination motifs and ligand donicity are highly desirable. Reported herein is an air-stable, tetragonal FeII complex, Fe(HMTI)(CN)2 (HMTI = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene), with a 1.25 ns metal-to-ligand charge-transfer (MLCT) lifetime. The structure has been determined, and the photophysical properties have been examined in a variety of solvents. The HMTI ligand is highly π-acidic due to low-lying π*(C═N), which enhances ΔFe via stabilizing t2g orbitals. The inflexible geometry of the macrocycle results in short Fe-N bonds, and density functional theory calculations show that this rigidity results in an unusual set of nested potential energy surfaces. Moreover, the lifetime and energy of the MLCT state depends strongly on the solvent environment. This dependence is caused by modulation of the axial ligand-field strength by Lewis acid-base interactions between the solvent and the cyano ligands. This work represents the first example of a long-lived charge transfer state in an FeII macrocyclic species.

Ferrous and ferric complexes with cyclometalating N-heterocyclic carbene ligands: a case of dual emission revisited.

Iron N-heterocyclic carbene (FeNHC) complexes with long-lived charge transfer states are emerging as a promising class of photoactive materials. We have synthesized [FeII(ImP)2] (ImP = bis(2,6-bis(3-methylimidazol-2-ylidene-1-yl)phenylene)) that combines carbene ligands with cyclometalation for additionally improved ligand field strength. The 9 ps lifetime of its 3MLCT (metal-to-ligand charge transfer) state however reveals no benefit from cyclometalation compared to Fe(ii) complexes with NHC/pyridine or pure NHC ligand sets. In acetonitrile solution, the Fe(ii) complex forms a photoproduct that features emission characteristics (450 nm, 5.1 ns) that were previously attributed to a higher (2MLCT) state of its Fe(iii) analogue [FeIII(ImP)2]+, which led to a claim of dual (MLCT and LMCT) emission. Revisiting the photophysics of [FeIII(ImP)2]+, we confirmed however that higher (2MLCT) states of [FeIII(ImP)2]+ are short-lived (<10 ps) and therefore, in contrast to the previous interpretation, cannot give rise to emission on the nanosecond timescale. Accordingly, pristine [FeIII(ImP)2]+ prepared by us only shows red emission from its lower 2LMCT state (740 nm, 240 ps). The long-lived, higher energy emission previously reported for [FeIII(ImP)2]+ is instead attributed to an impurity, most probably a photoproduct of the Fe(ii) precursor. The previously reported emission quenching on the nanosecond time scale hence does not support any excited state reactivity of [FeIII(ImP)2]+ itself.

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.

Long-Lived Charge-Transfer State in Spiro Compact Electron Donor-Acceptor Dyads Based on Pyromellitimide-Derived Rhodamine: Charge Transfer Dynamics and Electron Spin Polarization.

We observed a long‐lived charge transfer (CT) state in a novel orthogonal compact electron donor–acceptor dyads, with closed form of rhodamine (Rho) as electron donor and pyromellitimide (PI),or thionated PI, as electron acceptor. The two parts in the dyads are connected via a spiro quaternary carbon atom, thus the torsion between the donor and acceptor is completely inhibited, which is beneficial to reduce the reorganization energy and to exploit the Marcus inverted region effect to prolong the CT state lifetime. Femtosecond transient absorption spectra show that the charge separation is rather fast, while nanosecond transient absorption spectra confirmed the formation of long‐lived CT state (2.6 μs). Time‐resolved electron paramagnetic resonance (TREPR) spectra determined the spin multiplicity of the long living state and assigned it to a 3CT state. Replacement of an oxygen atom in the PI part with a sulfur atom favoring classical intersystem crossing processes, causes a consistently shortening of the lifetime of the 3CT state (0.29 μs).

Electron spin-controlled charge transfer and the resulting long-lived charge transfer state: from transition metal complexes to organic compounds.

The generation of long-lived charge transfer (CT) states in electron donor/acceptor dyads upon photoexcitation is crucial for artificial photosynthesis, photocatalysis and photovoltaics. Electron spin control is a novel strategy to prolong the CT state lifetime via generation of the 3CT triplet state, instead of the traditional short-lived 1CT state. This method involves a local triplet excited state (3LE) as the precursor of charge separation (CS), and the electron forbidden feature of the charge recombination (CR) of 3CT → S0vs. the electron spin allowed 1CT → S0 prolongs the CT state lifetime. In this article, we summarized the recent developments and challenges in this emerging fascinating area.

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%.

Long-Lived Charge-Transfer State from B-N Frustrated Lewis Pairs Enchained in Supramolecular Copolymers.

The field of supramolecular polymers is rapidly expanding; however, the exploitation of these systems as functional materials is still elusive. To become competitive, supramolecular polymers must display microstructural order and the emergence of new properties upon copolymerization. To tackle this, a greater understanding of the relationship between monomers’ design and polymer microstructure is required as well as a set of functional monomers that efficiently interact with one another to synergistically generate new properties upon copolymerization. Here, we present the first implementation of frustrated Lewis pairs into supramolecular copolymers. Two supramolecular copolymers based on π-conjugated O-bridged triphenylborane and two different triphenylamines display the formation of B–N pairs within the supramolecular chain. The remarkably long lifetime and the circularly polarized nature of the resulting photoluminescence emission highlight the possibility to obtain an intermolecular B–N charge transfer. These results are proposed to be the consequences of the enchainment of B–N frustrated Lewis pairs within 1D supramolecular aggregates. Although it is challenging to obtain a precise molecular picture of the copolymer microstructure, the formation of random blocklike copolymers could be deduced from a combination of optical spectroscopic techniques and theoretical simulation.

Excimer Intermediates en Route to Long-Lived Charge-Transfer States in Single-Stranded Adenine DNA as Revealed by Nonadiabatic Dynamics.

The ultrafast time evolution of a single-stranded adenine DNA is studied using a hybrid multiscale quantum mechanics/molecular mechanics (QM/MM) scheme coupled to nonadiabatic surface hopping dynamics. As a model, we use (dA)20 where a stacked adenine tetramer is treated quantum chemically. The dynamical simulations combined with on-the-fly quantitative wave function analysis evidence the nature of the long-lived electronically excited states formed upon absorption of UV light. After a rapid decrease of the initially excited excitons, relaxation to monomer-like states and excimers occurs within 100 fs. The former monomeric states then relax into additional excimer states en route to forming stabilized charge-transfer states on a longer timescale of hundreds of femtoseconds. The different electronic-state characters is reflected on the spatial separation between the adenines: excimers and charge-transfer states show a much smaller spatial separation than the monomer-like states and the initially formed excitons.

Long-Lived Charge-Transfer State Induced by Spin-Orbit Charge Transfer Intersystem Crossing (SOCT-ISC) in a Compact Spiro Electron Donor/Acceptor Dyad.

We prepared conceptually novel, fully rigid, spiro compact electron donor (Rhodamine B, lactam form, RB)/acceptor (naphthalimide; NI) orthogonal dyad to attain the long‐lived triplet charge‐transfer (3CT) state, based on the electron spin control using spin‐orbit charge transfer intersystem crossing (SOCT‐ISC). Transient absorption (TA) spectra indicate the first charge separation (CS) takes place within 2.5 ps, subsequent SOCT‐ISC takes 8 ns to produce the 3NI* state. Then the slow secondary CS (125 ns) gives the long‐lived 3CT state (0.94 μs in deaerated n‐hexane) with high energy level (ca. 2.12 eV). The cascade photophysical processes of the dyad upon photoexcitation are summarized as 1NI*→1CT→3NI*→3CT. With time‐resolved electron paramagnetic resonance (TREPR) spectra, an EEEAAA electron‐spin polarization pattern was observed for the naphthalimide‐localized triplet state. Our spiro compact dyad structure and the electron spin‐control approach is different to previous methods for which invoking transition‐metal coordination or chromophores with intrinsic ISC ability is mandatory.

Charge separation, charge recombination, long-lived charge transfer state formation and intersystem crossing in organic electron donor/acceptor dyads

The recent developments in charge separation, long-lived charge transfer state formation and charge recombination-induced intersystem crossing are summarized.

Long-Lived Charge-Transfer States of Nickel(II) Aryl Halide Complexes Facilitate Bimolecular Photoinduced Electron Transfer.

Here we investigate the photophysics and photochemistry of Ni(II) aryl halide complexes common to cross-coupling and Ni/photoredox reactions. Computational and ultrafast spectroscopic studies reveal that these complexes feature long-lived 3MLCT excited states, implicating Ni as an underexplored alternative to precious metal photocatalysts. Moreover, we show that 3MLCT Ni(II) engages in bimolecular electron transfer with ground-state Ni(II), which enables access to Ni(III) in the absence of external oxidants or photoredox catalysts. As such, it is possible to facilitate Ni-catalyzed C-O bond formation solely by visible light irradiation, thus representing an alternative strategy for catalyst activation in Ni cross-coupling reactions.

Ultrafast Charge-Transfer Dynamics in the Iron-Sulfur Complex of Rhodobacter capsulatus Ferredoxin VI.

Iron-sulfur proteins play essential roles in various biological processes. Their electronic structure and vibrational dynamics are key to their rich chemistry but nontrivial to unravel. Here, the first ultrafast transient absorption and impulsive coherent vibrational spectroscopic (ICVS) studies on 2Fe-2S clusters in Rhodobacter capsulatus ferreodoxin VI are characterized. Photoexcitation initiated populations on multiple excited electronic states that evolve into each other in a long-lived charge-transfer state. This suggests a potential light-induced electron-transfer pathway as well as the possibility of using iron-sulfur proteins as photosensitizers for light-dependent enzymes. A tyrosine chain near the active site suggests potential hole-transfer pathways and affirms this electron-transfer pathway. The ICVS data revealed vibrational bands at 417 and 484 cm-1, with the latter attributed to an excited-state mode. The temperature dependence of the ICVS modes suggests that the temperature effect on protein structure or conformational heterogeneities needs to be considered during cryogenic temperature studies.

(Invited) Sensitizing Charge Carrier Generation in a Conjugated Polymer Using a C70-Encapsulated Covalent Organic Polyhedron

This presentation will report on the photophysics of a covalent organic polyhedron molecule (COP-5) that contains two porphyrin molecules in the cage structure and with an encapsulated C70 molecule bound in its core. The photo-induced electron transfer processes in this structure create anomalously long-lived charge-transfer states that also respond in an unconventional fashion to the dielectric constant of the solvent. Preliminary results on using this complex to sensitize the production of long-lived charge carriers in a conjugated polymer will also be reported, where the carrier yields and kinetics are tracked using time-resolved microwave conductivity. The purpose of this work is to gain a better understanding of the nature of charge transfer (CT) and charge-separated (CS) states in the production of carriers in conjugated polymers blended with fullerenes.

Nanoscale transport of charge-transfer states in organic donor-acceptor blends.

Charge-transfer (CT) states, bound combinations of an electron and a hole on separate molecules, play a crucial role in organic optoelectronic devices. We report direct nanoscale imaging of the transport of long-lived CT states in molecular organic donor-acceptor blends, which demonstrates that the bound electron-hole pairs that form the CT states move geminately over distances of 5-10 nm, driven by energetic disorder and diffusion to lower energy sites. Magnetic field dependence reveals a fluctuating exchange splitting, indicative of a variation in electron-hole spacing during diffusion. The results suggest that the electron-hole pair of the CT state undergoes a stretching transport mechanism analogous to an 'inchworm' motion, in contrast to conventional transport of Frenkel excitons. Given the short exciton lifetimes characteristic of bulk heterojunction organic solar cells, this work confirms the potential importance of CT state transport, suggesting that CT states are likely to diffuse farther than Frenkel excitons in many donor-acceptor blends.

Long-Lived LMCT in a d0 Vanadium(V) Complex by Internal Conversion to a State of 3dxy Character

The excited state dynamics of a d0 vanadium(V) oxido ligand-to-metal charge transfer (LMCT) complex, VOLF, were investigated via a combination of static optical and X-ray absorption (XAS) spectroscopy, transient optical absorption spectroscopy, and time-dependent density functional theory (TD-DFT). Upon excitation of the LMCT in the visible region, transient absorption data reveal that internal conversion traps the excited carrier population into a long-lived charge transfer state of 3dxy electron character, S1(dxy). The internal conversion is substantiated by an isosbestic point in the transient absorption data, two nearby charge transfer states that couple well by TD-DFT, multiple rates in the ground state recovery, and the decay kinetics of an excited state absorption with the energy of a d-d transition in O K-edge XAS spectra. The long lifetime (∼420 ps) of S1(dxy) can be ascribed to its poor optical and vibrational coupling to a distorted ground state (S0*) via a negligible electronic dipole transiti...

A heteroleptic push-pull substituted iron(II) bis(tridentate) complex with low-energy charge-transfer states.

A heteroleptic iron(II) complex [Fe(dcpp)(ddpd)](2+) with a strongly electron-withdrawing ligand (dcpp, 2,6-bis(2-carboxypyridyl)pyridine) and a strongly electron-donating tridentate tripyridine ligand (ddpd, N,N'-dimethyl-N,N'-dipyridine-2-yl-pyridine-2,6-diamine) is reported. Both ligands form six-membered chelate rings with the iron center, inducing a strong ligand field. This results in a high-energy, high-spin state ((5) T2 , (t2g )(4) (eg *)(2) ) and a low-spin ground state ((1) A1 , (t2g )(6) (eg *)(0) ). The intermediate triplet spin state ((3) T1 , (t2g )(5) (eg *)(1) ) is suggested to be between these states on the basis of the rapid dynamics after photoexcitation. The low-energy π(*) orbitals of dcpp allow low-energy MLCT absorption plus additional low-energy LL'CT absorptions from ddpd to dcpp. The directional charge-transfer character is probed by electrochemical and optical analyses, Mößbauer spectroscopy, and EPR spectroscopy of the adjacent redox states [Fe(dcpp)(ddpd)](3+) and [Fe(dcpp)(ddpd)](+) , augmented by density functional calculations. The combined effect of push-pull substitution and the strong ligand field paves the way for long-lived charge-transfer states in iron(II) complexes.

Measuring Electron and Hole Transfer in Core/Shell Nanoheterostructures

Using femtosecond transient absorption and time-resolved photoluminescence spectroscopy, we studied the electron versus hole dynamics in photoexcited quasi-type-II heterostructured nanocrystals with fixed CdTe core radii and varying CdSe shell coverage. By choosing the pump wavelength in resonance with the core or the shell states, respectively, we were able to measure the excited electron and hole dynamics selectively. Both, the core- and the shell-excited CdTe/CdSe nanocrystals showed the same spectral emission and photoluminescence lifetimes, indicating that ultrafast electron and hole transfer across the core/shell interface resulted in the identical long-lived charge transfer state. Both charge carriers have subpicosecond transfer rates through the interface, but the subsequent relaxation rates of the hole (τ(dec) ∼ 800 ps) and electron (τ(avg) ∼ 8 ps) are extremely different. On the basis of the presented transient absorption measurements and fitting of the steady-state spectra, we find that the electron transfer occurs in the Marcus inverted region and mixing between the CdTe exciton and charge transfer states takes place and therefore needs to be considered in the analysis.