Intermediate Charge Transfer State Research Articles

Unlocking amplified magneto-photocurrent using multi-field manipulation in nonfullerene organic bulk heterojunction systems.

An effective manipulation of polaron pairs (PPs) for realizing amplified magneto-photocurrent (AMPC) is of critical importance toward the development of low power consumption and high-performance organic spin-optoelectronic devices, for instance magneto-photo-volatile memories. By far, it is challenging and there is a lack of method to reach AMPC. The typical magneto-photocurrent due to the light-matter interanion is primarily for unveiling the spin-dependent electron-hole dissociation in organic solar cells. Herein, we achieved an AMPC of ∼140% in nonfullerene organic bulk heterojunction systems at room temperature. We found that the amplification can be effectively triggered by a multi-field to a large number of photogenerated PPs at intermediate charge transfer states. We further postulate that, at steady state, they may experience a cyclic photophysical process due to the triplet-exciton polaron interaction. This study paves the way for the realization of AMPC in the organic spin-optoelectronic system.

Excited-State Charge Transfer in Push-Pull Platinum(II) π-Extended Porphyrins Fused with Pentacenequinone.

Platinum(II) π-extended porphyrins fused with pentacenequinone and dihydropentacene have been successfully synthesized. These porphyrins were investigated using various techniques including absorption, steady-state, and time-resolved phosphorescence spectroscopy and differential pulse voltammetry. UV-vis absorption spectra of pentacenequinone-fused porphyrins (SW-Pt1 and SW-Pt2) showed unusually broad and nontypical absorption patterns. Phosphorescence spectra of SW-Pt1, SW-Pt2, and SW-Pt3 displayed similar emissions in the 704-706 nm region indicating electronic transitions of similar origin; however, the triplet lifetimes were found to be quenched in the case of both SW-Pt1 and SW-Pt2, suggesting the occurrence of excited-state events. Facile reductions were obtained for both the pentacene-quinone-fused monomer (SW-Pt2) and dimer (SW-Pt1) and were identified to be located at the pentacenequinone components. The observed orbital segregations for SW-Pt2 and SW-Pt1 from DFT calculations supported the possibility of charge transfer in these push-pull systems. Interestingly, the established energy level diagram revealed that the charge transfer from the triplet excited Pt porphyrin is thermodynamically an uphill process. Systematic studies involving both femtosecond and nanosecond transient absorption techniques revealed that the singlet excited Pt porphyrins undergo an intermediate charge transfer state prior to populating the triplet state, providing a plausible explanation for phosphorescence quenching. The lifetime of the intermediate charge transfer states was found to be 25.9 and 5.68 ps, respectively, for SW-Pt1 and SW-Pt2.

Cover Feature: Symmetrically Functionalized Copper and Silver Corrole‐Bis‐Tetracyanobutadiene Push‐Pull Conjugates: Efficient Population of Triplet States via Charge Transfer (Chem. Eur. J. 41/2023)

Chemistry–art–culture combo: Rangoli, an ancient art from the Indian subcontinent, creates designs on the floor by using dry powders. A rangoli of the structure of the investigated compound is depicted here to link chemistry to art to culture. An efficient population of triplet excited states via the intermediate charge-transfer state formed as a function of excitation wavelength is demonstrated by using ultrafast pump–probe spectroscopy in these symmetrically functionalized push–pull systems. More information can be found in the Research Article by M. Sankar, F. D'Souza, and co-workers (DOI: 10.1002/chem.202301341). Artists: I. Yadav, N. Rana, R. Jangra and S. Rathi.

Charge transfer as a mechanism for chlorophyll fluorescence concentration quenching

Highly concentrated solutions of chlorophyll display rapid fluorescence quenching. The same devastating energy loss is not seen in photosynthetic light-harvesting antenna complexes, despite the need for chromophores to be in close proximity to facilitate energy transfer. A promising, though unconfirmed mechanism for the observed quenching is energy transfer from an excited chlorophyll monomer to a closely associated chlorophyll pair that subsequently undergoes rapid nonradiative decay to the ground state via a short-lived intermediate charge-transfer state. In this work, we make use of newly emerging fast methods in quantum chemistry to assess the feasibility of this proposed mechanism. We calculate rate constants for the initial charge separation, based on Marcus free-energy surfaces extracted from molecular dynamics simulations of solvated chlorophyll pairs, demonstrating that this pathway will compete with fluorescence (i.e., drive quenching) at experimentally measured quenching concentrations. We show that the rate of charge separation is highly sensitive to interchlorophyll distance and the relative orientations of chromophores within a quenching pair. We discuss possible solvent effects on the rate of charge separation (and consequently the degree of quenching), using the light-harvesting complex II (LH2) protein from rps. acidophila as a specific example of how this process might be controlled in a protein environment. Crucially, we reveal that the LH2 antenna protein prevents quenching, even at the high chlorophyll concentrations required for efficient energy transfer, by restricting the range of orientations that neighboring chlorophyll pairs can adopt.

On the Cooperative Origin of Solvent-Enhanced Symmetry-Breaking Charge Transfer in a Covalently Bound Tetracene Dimer Leading to Singlet Fission.

Singlet fission in covalently bound acene dimers in solution is driven by the interplay of excitonic and singlet correlated triplet 1(TT) states with intermediate charge-transfer states, a process which depends sensitively on the solvent environment. We use high-level electronic structure methods to explore this singlet fission process in a linked tetracene dimer, with emphasis on the symmetry-breaking mechanism for the charge-transfer (CT) states induced by low-frequency antisymmetric vibrations and polar/polarizable solvents. A combination of the second-order algebraic diagrammatic construction (ADC(2)) and density functional theory/multireference configuration interaction (DFT/MRCI) methods are employed, along with a state-specific conductor-like screening model (COSMO) solvation model in the former case. This work quantifies, for the first time, an earlier mechanistic proposal [Alvertis et al., J. Am. Chem. Soc. 2019, 141, 17558] according to which solvent-induced symmetry breaking leads to a high-energy CT state which interacts with the correlated triplet state, resulting in singlet fission. An approximate assessment of the nonadiabatic interactions between the different electronic states underscores that the CT states are essential in facilitating the transition from the bright excitonic state to the 1(TT) state leading to singlet fission. We show that several types of symmetry-breaking inter- and intra-fragment vibrations play a crucial role in a concerted mechanism with the solvent environment and with the symmetric inter-fragment torsion, which tunes the admixture of excitonic and CT states. This offers a new perspective on how solvent-induced symmetry-breaking CT can be understood and how it cooperates with intramolecular mechanisms in singlet fission.

Origin of Chirality Induced Spin Selectivity in Photoinduced Electron Transfer.

Here we propose a mechanism by which spin-polarization can be generated dynamically in chiral molecular systems undergoing photoinduced electron transfer. The proposed mechanism explains how spin-polarization emerges in systems where charge transport is dominated by incoherent hopping, mediated by spin-orbit and electronic exchange couplings through an intermediate charge transfer state. We derive a simple expression for the spin-polarization that predicts a nonmonotonic temperature dependence, consistent with recent experiments, and a maximum spin-polarization that is independent of the magnitude of the spin-orbit coupling. We validate this theory using approximate quantum master equations and the numerically exact hierarchical equations of motion. The proposed mechanism of chirality induced spin selectivity should apply to many chiral systems, and the ideas presented here have implications for the study of spin transport at temperatures relevant to biology and provide simple principles for the molecular control of spins in fluctuating environments.

A computational exploration of aggregation-induced excitonic quenching mechanisms for perylene diimide chromophores.

Perylene diimide (PDI) derivatives are widely used materials for luminescent solar concentrator (LSC) applications due to their attractive optical and electronic properties. In this work, we study aggregation-induced exciton quenching pathways in four PDI derivatives with increasing steric bulk, which were previously synthesized. We combine molecular dynamics and quantum chemical methods to simulate the aggregation behavior of chromophores at low concentration and compute their excited state properties. We found that PDIs with small steric bulk are prone to aggregate in a solid state matrix, while those with large steric volume displayed greater tendencies to isolate themselves. We find that for the aggregation class of PDI dimers, the optically accessible excitations are in close energetic proximity to triplet charge transfer (CT) states, thus facilitating inter-system crossing and reducing overall LSC performance. While direct singlet fission pathways appear endothermic, evidence is found for the facilitation of a singlet fission pathway via intermediate CT states. Conversely, the insulation class of PDI does not suffer from aggregation-induced photoluminescence quenching at the concentrations studied here and therefore display high photon output. These findings should aid in the choice of PDI derivatives for various solar applications and suggest further avenues for functionalization and study.

Delocalization effects in singlet fission: Comparing models with two and three interacting molecules.

We present surface hopping simulations of singlet fission in 2,5-bis(fluorene-9-ylidene)-2,5-dihydrothiophene (ThBF). In particular, we performed simulations based on quantum mechanics/molecular mechanics (QM/MM) schemes in which either two or three ThBF molecules are inserted in the QM region and embedded in their MM crystal environment. Our aim was to investigate the changes in the photodynamics that are brought about by extending the delocalization of the excited states beyond the minimal model of a dimer. In the simulations based on the trimer model, compared to the dimer-based ones, we observed a faster time evolution of the state populations, with the largest differences associated with both the rise and decay times for the intermediate charge transfer states. Moreover, for the trimer, we predicted a singlet fission quantum yield of ∼204%, which is larger than both the one extracted for the dimer (∼179%) and the theoretical upper limit of 200% for the dimer-based model of singlet fission. Although our study cannot account for the effects of extending the delocalization beyond three molecules, our findings clearly indicate how and why the singlet fission dynamics can be affected.

Rapid Excited-State Deactivation of BODIPY Derivatives by a Boron-Bound Catechol.

The excited-state dynamics and energetics of a series of BODIPY-derived chromophores bound to a catechol at the boron position were investigated with a combination of static and time-resolved spectroscopy, electrochemistry, and density functional theory calculations. Compared with the difluoro-BODIPY-derived parent compounds, the addition of the catechol at the boron reduced the excited-state lifetime by three orders of magnitude. Deactivation of the excited state proceeded through an intermediate charge-transfer state accessed from the initial optically excited π* state in <1 ps. Despite differences in the structures of the BODIPY derivatives and absorption maxima that spanned the visible portion of the spectrum, all compounds exhibited the same, rapid, excited-state deactivation mechanism, suggesting the generality of the observed dynamics within this class of compounds.

Combination of Charge Delocalization and Disorder Enables Efficient Charge Separation at Photoexcited Organic Bilayers

We study incoherent charge separation in a lattice model of an all-organic bilayer. Charge delocalization is taken into account by working in the basis of electron–hole pair eigenstates, and the separation is described as a series of incoherent hops between these states. We find that relatively weak energetic disorder, in combination with good charge delocalization, can account for efficient and weakly field- and temperature-dependent separation of the strongly bound charge transfer (CT) state. The separation efficiency is determined by the competition between the recombination from the initial CT state and the escape toward intermediate CT states, from which free-charge states can be reached with certainty. The separation of donor excitons also exhibits quite high yields, less bound excitons separating more efficiently. Overall, our results support the notion that efficient charge separation can be achieved even out of strongly bound pair states without invoking coherent effects.

Charge Generation in Organic Solar Cells: Interplay of Quantum Dynamics, Decoherence, and Recombination

The dynamics of photoinduced charge generation is studied for donor–acceptor (D–A) organic interfaces, with focus on the interplay of quantum dynamics, decoherence effects, and recombination. A coarse-grained molecular envelope function model is developed to enable the investigation of large scale D–A heterojunctions, taking into account morphology and molecular orientation as well as the underlying quantum nature of the system. Simulations show that, upon photoexcitation, Frenkel excitons delocalize over several molecules in <300 fs. At the interface, they dissociate without dwelling in intermediate charge transfer states, evincing that exciton motion and dissociation cannot be describe by point particle models. Moreover, as decoherence suppresses the excitonic quantum coherence length, it also decreases the geminate recombination rate. Although ultrafast coherent charge separation is more efficient at early times and, particularly, for excitons created at the interface, diffusion becomes important for e...

Magnetic field enhancement of organic photovoltaic cells performance

Charge separation is a critical process for achieving high efficiencies in organic photovoltaic cells. The initial tightly bound excitonic electron-hole pair has to dissociate fast enough in order to avoid photocurrent generation and thus power conversion efficiency loss via geminate recombination. Such process takes place assisted by transitional states that lie between the initial exciton and the free charge state. Due to spin conservation rules these intermediate charge transfer states typically have singlet character. Here we propose a donor-acceptor model for a generic organic photovoltaic cell in which the process of charge separation is modulated by a magnetic field which tunes the energy levels. The impact of a magnetic field is to intensify the generation of charge transfer states with triplet character via inter-system crossing. As the ground state of the system has singlet character, triplet states are recombination-protected, thus leading to a higher probability of successful charge separation. Using the open quantum systems formalism we demonstrate that the population of triplet charge transfer states grows in the presence of a magnetic field, and discuss the impact on carrier population and hence photocurrent, highlighting its potential as a tool for research on charge transfer kinetics in this complex systems.

Ultrafast Electronic Energy Transfer in an Orthogonal Molecular Dyad.

Understanding electronic energy transfer (EET) is an important ingredient in the development of artificial photosynthetic systems and photovoltaic technologies. Although EET is at the heart of these applications and crucially influences their light-harvesting efficiency, the nature of EET over short distances for covalently bound donor and acceptor units is often not well understood. Here we investigate EET in an orthogonal molecular dyad (BODT4), in which simple models fail to explain the very origin of EET. On the basis of nonadiabatic ab initio molecular dynamics calculations and ultrafast fluorescence experiments, we gain detailed microscopic insights into the ultrafast electrovibrational dynamics following photoexcitation. Our analysis offers molecular-level insights into these processes and reveals that it takes place on time scales ≲100 fs and occurs through an intermediate charge-transfer state.

Magnetic field dependence of singlet fission in solutions of diphenyl tetracene.

Magnetic field effects provide a convenient and specific probe of singlet exciton fission within optoelectronic devices. Here, we demonstrate that this tool may also be applied to screen potential fission material candidates in solution. We characterize the phenomenon in diphenyl tetracene (DPT), which shows strong fluorescence modulation and the expected field dependence in its transient decay as a function of concentration. Solution measurements may also be used to test for the presence of an intermediate charge transfer state, but we observe no changes to the field dependence of DPT singlet exciton fission in toluene relative to chloroform.

An Efficient Indirect Mechanism for the Ultrafast Intersystem Crossing in Copper Porphyrins

The ultrafast dynamics of copper tetraphenylporphyrin (CuTPP), copper octaethylporphyrin (CuOEP), and of the free base tetraphenylporphyrin (H2TPP), excited in the S2 state have been investigated in the gas phase by femtosecond pump/probe experiments. The porphyrins were excited in the Soret band at 400 nm. Strikingly, the S2-S1 internal conversion in H2TPP is very rapid (110 fs), as compared to that of ZnTPP (600 fs), previously observed. In turn, CuTPP and CuOEP, excited in S2, follow an efficient and different relaxation pathway from that of other open-shell metalloporphyrins. These two molecules exhibit a sequential four-step decay ending on a slow evolution in the nanosecond range (2)S2 → (2)CT → (2)T → (2)Ground State. This latter evolution is linked to the formation of the (2)T, tripdoublet state in CuTPP, observed in the condensed phase. It is shown that an intermediate charge transfer state plays a crucial role in linking the porphyrin centered (1)ππ* and (3)ππ* configurations. A simple model is presented that allows a rapid evolution between these two configurations, via coupling of the porphyrin π system with the free d electron on the copper. The mechanism obviates the need for the spin orbit coupling within the porphyrin. The result is that these copper porphyrins can exhibit an ultrafast apparent intersystem crossing, unprecedented for organic molecules.

Electron Transfer in Quantum-Dot-Sensitized ZnO Nanowires: Ultrafast Time-Resolved Absorption and Terahertz Study

Photoinduced electron injection dynamics from CdSe quantum dots to ZnO nanowires is studied by transient absorption and time-resolved terahertz spectroscopy measurements. Ultrafast electron transfer from the CdSe quantum dots to ZnO is proven to be efficient already on a picoseconds time scale (τ = 3-12 ps). The measured kinetics was found to have a two-component character, whose origin is discussed in detail. The obtained results suggest that electrons are injected into ZnO via an intermediate charge transfer state.

Direct and charge transfer state mediated photogeneration in polymer–fullerene bulk heterojunction solar cells

We investigated photogeneration yield and recombination dynamics in blends of poly(3-hexyl thiophene) (P3HT) and poly[2-methoxy-5 -(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) with [6,6]-phenyl-C61butyric acid methyl ester (PC61BM) by means of temperature dependent time delayed collection field measurements. In MDMO-PPV:PC61BM, we find a strongly field dependent polaron pair dissociation which can be attributed to geminate recombination in the device. Our findings are in good agreement with field dependent photoluminescence measurements published before, supporting a scenario of polaron pair dissociation via an intermediate charge transfer state. In contrast, polaron pair dissociation in P3HT:PC61BM shows only a very weak field dependence, indicating an almost field independent polaron pair dissociation or a direct photogeneration. Furthermore, we found Langevin recombination for MDMO-PPV:PC61BM and strongly reduced Langevin recombination for P3HT:PC61BM.

Luminescence Characteristics of Ba&lt;sub&gt;0.5&lt;/sub&gt;Sr&lt;sub&gt;0.5&lt;/sub&gt;TiO&lt;sub&gt;3&lt;/sub&gt;:Pr&lt;sub&gt;x,&lt;/sub&gt; Al&lt;sub&gt;y&lt;/sub&gt; Powders Synthesized by Citrate-Nitride Combustion Process

Ba0.5Sr0.5TiO3:Pr powders co-doped with and without Al were synthesized by citrate-nitride combustion process. To investigate the effect and mechanism of Al dopant, samples with various Al3+ and Pr3+ content were prepared. The excitation and emission spectra were detected. Enhanced red emission around 613 nm was obtained by Al addition. Moreover, an emission at 491 nm was observed. Substitute situation of Pr3+ ions in the lattice was discussed. And the mechanism of energy transition was explained by the model of an intermediate charge transfer state.

Electron-Exchange-Assisted Photon Energy Up-Conversion in Thin Films of π-Conjugated Polymeric Composites

The mechanism of triplet–triplet annihilation (TTA)-induced up-converted (UC) delayed luminescence is studied in two different binary organic systems consisting of platinum(II) octaethyl porphyrin (PtOEP) mixed with either poly(fluorene) (PF26) or ladder-type pentaphenylene (L5Ph). Cyclic voltammetry and differential pulse voltammetry are employed for estimating the ionization potentials of PtOEP and L5Ph. Delayed luminescence spectroscopy sets the energy of the lowest excited triplet state of L5Ph 0.20 eV higher than the triplet state of PtOEP (1.90 eV). The different phosphorescence PtOEP lifetime indicates differences in PtOEP aggregation in the polymer matrices. The presented results propose that the difference in the relative intensities of the delayed UC luminescence is determined by the difference between the ionization potentials of PtOEP and the polymer matrix. In the solid state, the electric-field-induced quenching of the delayed L5Ph UC luminescence suggests the formation of an intermediate charge-transfer state after the TTA within the PtOEP domains.

Energy Transfer by Way of an Exciplex Intermediate in Flexible Boron Dipyrromethene-Based Allosteric Architectures

We have designed and synthesized a series of modular, dual-color dyes comprising a conventional boron dipyrromethene (Bodipy) dye, as a yellow emitter, and a Bodipy dye possessing extended conjugation that functions as a red emitter. A flexible tether of variable length, built from ethylene glycol residues, connects the terminal dyes. A critical design element of this type of dyad relates to a secondary amine linkage interposed between the conventional Bodipy and the tether. Cyclic voltammetry shows both Bodipy dyes to be electroactive and indicates that the secondary amine is quite easily oxidized. The ensuing fluorescence quenching is best explained in terms of the rapid formation of an intermediate charge-transfer state. In fact, exciplex-type emission is observed in weakly polar solvents and over a critical temperature range. In the dual-color dyes, direct excitation of the yellow emitter results in the appearance of red fluorescence, indicating that the exciplex is likely involved in the energy-transfer event, and provides for a virtual Stokes shift of 5000 cm(-1). Replacing the red emitter with a higher energy absorber (namely, pyrene) facilitates the collection of near-UV light and extends the virtual Stokes shift to 8000 cm(-1). Modulation of the efficacy of intramolecular energy transfer is achieved by preorganization of the connector in the presence of certain cations. This latter behavior, which is fully reversible, corresponds to an artificial allosteric effect.