Charge Transfer Character Research Articles

Performance of Density Functionals for Excited-State Properties of Isolated Chromophores and Exciplexes: Emission Spectra, Solvatochromic Shifts, and Charge-Transfer Character.

This study assesses the performance of various meta-generalized gradient approximation (meta-GGA), global hybrid, and range-separated hybrid (RSH) density functionals in capturing the excited-state properties of organic chromophores and their excited-state complexes (exciplexes). Motivated by their uses in solar energy harvesting and photoredox CO2 reduction, we use oligo-(p-phenylenes) and their excited-state complexes with triethylamine as model systems. We focus on the fluorescence properties of these systems, specifically emission energies. We also consider solvatochromic shifts and wave function characteristics. The latter is described by using reduced quantities such as natural transition orbitals (NTOs) and exciton descriptors. The functionals are benchmarked against the experimental fluorescence spectra and the equation-of-motion coupled-cluster method with single and double excitations. Both in isolated chromophores and in exciplexes, meta-GGA functionals drastically underestimate the emission energies and exhibit significant exciton delocalization and anticorrelation between electron and hole motion. The performance of global hybrid functionals is strongly dependent on the percentage of exact exchange. Our study identifies RSH GGAs as the best-performing functionals, with ωPBE demonstrating the best agreement with experimental results. RSH meta-GGAs often overestimate emission energies in exciplexes and yield larger hole NTOs. Their performance can be improved by optimally tuning the range-separation parameter.

Hexylation Stabilises Twisted Backbone Configurations in the Prototypical Low-Bandgap Copolymer PCDTBT.

Conjugated donor-acceptor copolymers hold great potential as materials for high-performance organic photovoltaics, organic transistors and organic thermoelectric devices. Their low optical bandgap is achieved by alternation of donor and acceptor moieties along the polymer chain, leading to a pronounced charge-transfer character of electronic excitations. However, the influence of appended side chains and of chemical defects of the backbone on their photophysical and conformational properties remains largely unexplored on the level of individual chains. Here, we employ room temperature single-molecule photoluminescence spectroscopy on four compounds based on the prototypical copolymer PCDTBT with systematically changed chemical structure. Our results show that an increasing density of statistically added hexyl chains to the TBT comonomer distorts the molecular conformation, likely through the increase of average dihedral angles along the backbone. We find that, although the conformation becomes more twisted with high hexyl density, the side chains appear to stabilize the backbone in this twisted conformation. In addition, we demonstrate that homocoupling defects along the backbone barely influence the PL spectra of single chains, and thus intra-chain electronic properties.

Aggregation/Crystallization-Induced Emission in Naphthyridine-Based Carbazolyl-Modified Donor-Acceptor Boron Dyes Tunable by Fluorine Atoms.

Four donor-acceptor boron difluoride complexes based on the carbazole electron donor and the [1,3,5,2]oxadiazaborinino[3,4-a][1,8]naphthyridine acceptor were designed, synthesized, and systematically spectroscopically investigated in solutions, in dye-doped polymer films, and in the solid states. The dyes exhibit an intense blue to red solid-state emission with photoluminescence quantum yields of up to 59 % in pure dye samples and 86 % in poly(methyl methacrylate) films. All boron complexes show aggregation-induced emission and reversible mechanofluorochromism. The optical properties of these dyes and their solid state luminescence can be tuned by substitution pattern, i. e., the substituents at the naphthyridine unit. Exchange of CH3 - for CF3 -groups does not only increase the intramolecular charge transfer character, but also provides a crystallization-induced emission enhancement.

Disentangling the multiorbital contributions of excitons by photoemission exciton tomography

Excitons are realizations of a correlated many-particle wave function, specifically consisting of electrons and holes in an entangled state. Excitons occur widely in semiconductors and are dominant excitations in semiconducting organic and low-dimensional quantum materials. To efficiently harness the strong optical response and high tuneability of excitons in optoelectronics and in energy-transformation processes, access to the full wavefunction of the entangled state is critical, but has so far not been feasible. Here, we show how time-resolved photoemission momentum microscopy can be used to gain access to the entangled wavefunction and to unravel the exciton’s multiorbital electron and hole contributions. For the prototypical organic semiconductor buckminsterfullerene (C60), we exemplify the capabilities of exciton tomography and achieve unprecedented access to key properties of the entangled exciton state including localization, charge-transfer character, and ultrafast exciton formation and relaxation dynamics.

Sulfone-Functionalized Chichibabin's Hydrocarbons: Stable Diradicaloids with Symmetry Breaking Charge Transfer Contributing to NIR Emission beyond 900 nm.

While monoradical emitters have emerged as a new route toward efficient organic light-emitting diodes, the luminescence property of organic diradicaloids is still scarcely explored. Herein, by devising a novel radical-radical coupling-based synthetic approach, we report a new class of sulfone-functionalized Chichibabin's hydrocarbon derivatives, SD-1-3, featuring varied substituent patterns and moderate to high diradical characters of 0.44-0.70, as highly stable diradicaloids with rarely seen NIR emission beyond 900 nm. Via comprehensive experimental and theoretical investigations, we reveal that the optoelectronic and magnetic properties of these materials are significantly tuned by the variations of substitutions (H/CF3/OMe) on the molecular skeletons. More importantly, quantum chemical computations indicate that the embedding of sulfone groups has contributed to a breaking of their quasi-C2 symmetry of these diradicaloid molecules and results in an excited-state charge transfer character. Therefore, a remarkably deep NIR emissive wavelength of up to 998 nm, together with a large Stokes shift (∼386 nm), is achieved for the CF3-based SD-2 molecule in tetrahydrofuran. To the best of our knowledge, such a luminescent wavelength of SD-2 has represented the longest wavelengths among the currently reported organic fluorescent radicals. Overall, our work not only establishes a new synthetic approach toward stable Chichibabin's hydrocarbons but also paves the way for designing NIR emissive open-shell materials with both fundamental understanding and feasible control of their luminescent properties.

Elucidation of the role of metals in the adsorption and photodegradation of herbicides by metal-organic frameworks

Here, four MOFs, namely Sc-TBAPy, Al-TBAPy, Y-TBAPy, and Fe-TBAPy (TBAPy: 1,3,6,8-tetrakis(p-benzoic acid)pyrene), were characterized and evaluated for their ability to remediate glyphosate (GP) from water. Among these materials, Sc-TBAPy demonstrates superior performance in both the adsorption and degradation of GP. Upon light irradiation for 5 min, Sc-TBAPy completely degrades 100% of GP in a 1.5 mM aqueous solution. Femtosecond transient absorption spectroscopy reveals that Sc-TBAPy exhibits enhanced charge transfer character compared to the other MOFs, as well as suppressed formation of emissive excimers that could impede photocatalysis. This finding was further supported by hydrogen evolution half-reaction (HER) experiments, which demonstrated Sc-TBAPy’s superior catalytic activity for water splitting. In addition to its faster adsorption and more efficient photodegradation of GP, Sc-TBAPy also followed a selective pathway towards the oxidation of GP, avoiding the formation of toxic aminomethylphosphonic acid observed with the other M3+-TBAPy MOFs. To investigate the selectivity observed with Sc-TBAPy, electron spin resonance, depleted oxygen conditions, and solvent exchange with D2O were employed to elucidate the role of different reactive oxygen species on GP photodegradation. The findings indicate that singlet oxygen (1O2) plays a critical role in the selective photodegradation pathway achieved by Sc-TBAPy.

Ultralong organic room-temperature phosphorescence modulated by balancing intramolecular charge transfer and localized excitation character of excited states

Long emission lifetime is the defining character of organic room-temperature phosphorescence (RTP) and afterglow materials. In the absence of heavy atom effect, organic localized excitation (LE) systems show small phosphorescence rates and exhibit potential to form long-lived phosphorescence materials. However, such LE systems usually have limited population of T1 states because of large singlet-triplet splitting energy (ΔEST, around 1 eV). Here we report ultralong RTP by balancing intramolecular charge transfer and localized excitation character of excited states. Aromatic functional groups of moderate electron-donating strength are selected to build difluoroboron β-diketonate (BF2bdk) systems with moderate intramolecular charge transfer (ICT) character in their S1 states. Such molecular design gives rise to ΔEST around 0.5 eV and is enough to populate BF2bdk's T1 states. Significantly, the resultant BF2bdk's T1 states exhibit 85–90% 3LE character and display long phosphorescence lifetimes up to 1.38 s upon doping under ambient conditions. This study shows that simple design of organic system can also lead to high-performance RTP materials and provide an insight into the fundamental photophysics of organic triplet system.

Influential effect of C^N ligands containing O, S, and Se heteroatoms in the color tuning of four phosphorescent Ir(III) complexes

AbstractA group of new iridium(III) complexes were rationally designed and synthesized with 2‐phenylbenzo[d]oxazole (bo), 2‐phenylbenzo[d]thiazole (bt), 2‐(thiophen‐2‐yl)benzo[d]thiazole (thbt), and 2‐(selenophen‐2‐yl)benzo[d]thiazole (sebt) as C^N ligands and bis(diphenylthiophosphoryl)amide (S‐tpip) as ancillary ligand. They are phosphorescent in a wide region of green to red with short lifetimes around 0.31–0.98 μs and quantum yields up to 64.7%. The detailed photophysical properties were investigated by experiment and further supported by density functional theory (DFT) calculation. These research results show that the spectroscopic properties are tuned by the replacement between oxygen, sulfur, and selenium or the change in aromatic ring. It has been demonstrated that the lowest energy‐level absorption and emission are dominated apparently by C^N ligands, and are ascribed to metal‐to‐ligand charge transfer (MLCT) and intra‐ligand charge transfer (ILCT) characters.

Tailoring the Dynamics of Excited‐State Charge Transfer through Conformational Engineering to Improve Second Near‐Infrared Fluorescence for High‐Resolution Osteosarcoma Imaging

The dynamics of excited‐state charge transfer (CT) in second near‐infrared (NIR‐II) fluorophore proceeds with conformational change that govern fluorescence. Unveiling the relationship between CT dynamics and conformational change in excited state is of great fundamental significance in optimizing NIR‐II fluorescence but remains less explored. This study unveils the pivotal role of large conformational change in promoting the evolution of emissive CT state into nonemissive CT state in NIR‐II fluorophore (CA‐BBT). Spectroscopic and computational results reveal that large conformational rotation/twisting leads to a pronounced increase in the CT character in excited state. This heightened CT character in CA‐BBT enables a rapid evolution of emissive CT state into a nonemissive CT state within 1.4 ps, as observed by ultrafast spectroscopy. Subsequently, this nonemissive state dominates nonradiative decay, resulting in very low NIR‐II fluorescence. Preventing such detrimental evolution by constraining the conformational dynamics of CA‐BBT results in a 10‐fold enhancement of NIR‐II fluorescence, enabling high‐resolution dynamic visualization of vasculature within osteosarcoma. This study offers a profound understanding of the relationship between CT dynamics and conformational changes in NIR‐II fluorescence, presenting innovative perspectives to develop bright NIR‐II fluorophores.

Twisted Phosphors that Violate Kasha's Exciton Model in Organic Systems

Comprehensive SummaryKasha's exciton model proposes that T1 energy levels of organic compounds are insensitive to molecular aggregation and microenvironment change because of negligible small transition dipole moments of T1 states. This model holds true in most organic systems till now. Here we report the fabrication of twisted organic phosphors with intramolecular charge transfer characters and flexible molecular structures. When doped into different organic matrices, the twisted phosphor adopts different conformation, exhibits distinct phosphorescence colors and T1 energy levels, which violates Kasha's exciton model in organic system. Given that the change of phosphorescence colors and maxima can be readily distinguished by human eyes and conventional instrument, the twisted phosphors would be exploited as a new type of molecular probe, which would exhibit potential application in optical sensing and stimuli‐responsive systems.

Probing Charge Transfer Character in Modern Donor/Acceptor Materials via Electroabsorption Spectroscopy.

We use electroabsorption (EA) spectroscopy to probe the charge transfer (CT) character in neat films and blends of donors and acceptors of interest for organic electronic applications. In particular, we compare the CT character in two polymer donor and non-fullerene acceptor blends, including 3,9-bis(2-methylene-((3-(1,1-dicyanomethylene)-6,7-difluoro)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (IT-4F) and 2,2'-((2Z,2'Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″:4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (Y6). Like classic polymer/fullerene blends, the blend based on IT-4F exhibits primarily first derivative-like EA features, suggesting localized exciton formation upon photoexcitation. However, the Y6-based blend has an EA spectrum that is dominated by second derivative-like features, consistent with CT character. We show that this signal originates primarily from Y6. We find that Y6 exhibits the highest dipole moment change (7.5 ± 2.5 D) of the molecules that comprise this study, consistent with a high degree of the CT character, and a relatively large polarization volume of 361 ± 70 Å3, consistent with strong electron delocalization. These results point to the origins of exceptional performance of organic photovoltaics (OPVs) based on Y6.

Intramolecular charge transfer character of D-π-A chromophores with modulating the subunits sequence of π-bridge

Two D-B-A compounds (TRD and TTRD) were designed with the different bridges (B1 and B2) consisting of T and TT moieties. They were synthesized and investigated by UV–Vis spectra, steady state emission spectra, X-ray diffraction, electrochemical measurement, the photovoltaic performances and theoretical calculation. The large Stokes shift suggested the formation of an intramolecular charge transfer (ICT) state in the excited state. TTRD based device showed high short-circuit current density (JSC) and fill factor (FF). It was essential to understanding the underlying mechanism caused by the subtle structural difference of the two spacers. The results showed that the B2 bridge extending the electron increment region has shown a significant improvement for excitation delocalization, which played a crucial role in improving effective dissociation of the ICT excitons, leading to the increase of photogenerated charge carriers.

Ab initio investigation of excited state charge transfer pathways in differently capped bithiophene cages.

The electronic excitations of conformationally constrained bithiophene cage systems as previously investigated by Lewis et al. (J. Am. Chem. Soc. 143, 18548 (2021)) are revisited, employing the correlated ab initio Scaled Opposite-Spin Algebraic Diagrammatic Construction Second Order electronic structure method. Quantitative descriptors are determined to assess the extent of charge transfer between the bithiophene moieties and the capping domains, represented by either phenyl or triazine groups. The investigation substantiates intrinsic differences in the photophysical behavior of these two structural variants and reveals the presence of lower-energy excited states characterized by noteworthy charge transfer contributions in the triazine cage system. The manifestation of this charge transfer character is discernible even at the Franck-Condon geometry, persisting throughout the relaxation of the excited state. By examining isolated monomer building blocks, we confirm the existence of analogous charge transfer contributions in their excitations. Employing this methodological approach facilitates the prospective identification of potential wall/cap chromophore pairs, wherein charge transfer pathways can be accessed within the energetically favorable regime.

Delocalisation enables efficient charge generation in organic photovoltaics, even with little to no energetic offset.

Organic photovoltaics (OPVs) are promising candidates for solar-energy conversion, with device efficiencies continuing to increase. However, the precise mechanism of how charges separate in OPVs is not well understood because low dielectric constants produce a strong attraction between the charges, which they must overcome to separate. Separation has been thought to require energetic offsets at donor-acceptor interfaces, but recent materials have enabled efficient charge generation with small offsets, or with none at all in neat materials. Here, we extend delocalised kinetic Monte Carlo (dKMC) to develop a three-dimensional model of charge generation that includes disorder, delocalisation, and polaron formation in every step from photoexcitation to charge separation. Our simulations show that delocalisation dramatically increases charge-generation efficiency, partly by enabling excitons to dissociate in the bulk. Therefore, charge generation can be efficient even in devices with little to no energetic offset, including neat materials. Our findings demonstrate that the underlying quantum-mechanical effect that improves the charge-separation kinetics is faster and longer-distance hops between delocalised states, mediated by hybridised states of exciton and charge-transfer character.

Single-molecule detection of a terrylenediimide-based near-infrared emitter.

Environment-sensitive fluorescent agents with near-infrared (NIR) emission are in great demand owing to their applications in biomedical and quantum technologies. We report a novel NIR absorbing (λ Abs max = 734 nm) and emitting (λ Fl max = 814 nm) terrylenediimide (TDI) based donor-acceptor chromophore (TDI-TPA4), exhibiting polarity-sensitive single-photon emission. By virtue of the charge transfer (CT) character, ensemble level measurements revealed solvatochromism and NIR emission (ϕ Fl = 26.2%), overcoming the energy gap law. The CT nature of the excited states is further validated by state-of-the-art fragment-based excited state theoretical analysis. To mimic the polarity conditions at the single-molecule level, TDI-TPA4 was immobilized in polystyrene (PS; low polar) and poly(vinyl alcohol) (PVA; high polar) matrices, which enables tuning of the energy levels of the locally excited state and charge-separated (CS) state. Minimal blinking and prolonged survival time of the TDI-TPA4 molecule in the PS matrix, in contrast to the PVA matrix, possibly confirms the implication of the energy gap law and polarity sensitivity of TDI-TPA4. The existence of the CT state in nonpolar and CS state in polar solvents was confirmed by transient absorption measurements in the femtosecond regime. The current work sheds light on the design principle for NIR single-photon emitting organic chromophores for deep tissue imaging and probing the nanoscale heterogeneity.

Evaluation of a same-metal PCB-based three-electrode system via impedance studies using potassium ferricyanide.

We report for the first time the successful acquisition of electrochemical impedance spectroscopy data using an unconventional same-metal PCB-based three-electrode system. Conventional three-electrode systems primarily require expensive and bulky electrodes, and a high volume of analytes to conduct electrochemical impedance spectroscopy studies. The miniaturized PCB-based three-electrode system used in this work requires only trace amounts of analytes in the order of 10-20 μL owing to the design of the electrode sensor. Prominent standard redox probe potassium ferricyanide was used for impedance spectroscopic characterization studies. The results obtained were in congruence with existing literature; additionally the PCB-based three-electrode system demonstrated significantly higher repeatability, reproducibility, and consistency across different models of electrochemical instrumentations. Interestingly, the electrochemical impedance spectroscopy data of the PCB-3T sensor exhibited a consistent semi-circular impedance curve on a Nyquist plot and two distinct phase change regions on a Bode plot indicative of a simplified Randles cell model with an excellent circuit fit. Additionally this model provides an accurate impedance model for analysing trace analytes of potassium ferricyanide. Based on the circuit fitting model, potassium ferricyanide samples of varying concentrations at 1 mM, 5 mM, 10 mM, 15 mM and 20 mM demonstrated characteristic EIS charge transfer resistance corresponding to 435, 300, 233, 72 and 55 kΩ, respectively, and solution resistance of 260, 254, 218, 169 and 157 Ω, respectively. Therefore, the proposed novel same-metal three-electrode sensor can be employed in effective analysis and detection of samples with high accuracy and high sensitivity for trace amounts of analytes.

Ligand-to-metal charge transfer facilitates photocatalytic oxygen atom transfer (OAT) with cis-dioxo molybdenum(vi)-Schiff base complexes.

Systems incorporating the cis-Mo(O)2 motif catalyse a range of important thermal homogeneous and heterogeneous oxygen atom transfer (OAT) reactions spanning biological oxidations to platform chemical synthesis. Analogous light-driven processes could offer a more sustainable approach. The cis-Mo(O)2 complexes reported here photocatalyse OAT under visible light irradiation, and operate via a non-emissive excited state with substantial ligand-to-metal charge-transfer (LMCT) character, in which a Mo[double bond, length as m-dash]O π*-orbital is populated via transfer of electron density from a chromophoric salicylidene-aminophenol (SAP) ligand. SAP ligands can be prepared from affordable commercially-available precursors. The respective cis-Mo(O)2-SAP catalysts are air stable, function in the presence of water, and do not require additional photosensitisers or redox mediators. Benchmark OAT between phosphines and sulfoxides shows that electron withdrawing groups (e.g. C(O)OMe, CF3) are necessary for photocatalytic activity. The photocatalytic system described here is mechanistically distinct from both thermally catalysed OAT by the cis-Mo(O)2 motif, as well as typical photoredox systems that operate by outer sphere electron transfer mediated by long-lived emissive states. Both photoactivated and thermally activated OAT steps are coupled to establish a catalytic cycle, offering new opportunities for the development of photocatalytic atom transfer based on readily-available, high-valent metals, such as molybdenum.

Azaborahelicene fluorophores derived from four-coordinate N,C-boron chelates: synthesis, photophysical and chiroptical properties.

A series of six azaborahelicenes with varying electron-donor substitution at the 4-position of the aryl residue (i.e., naphthyl) or with variable π-extension of the aryl residue (thianthrenyl, anthryl, pyrenyl) was prepared with an efficient and flexible synthetic protocol. These different types of functionalization afforded notably pronounced intramolecular charge-transfer (ICT) character for the dyes with the strongest electron donor substitution (NMe2) or easiest to oxidize aryl residues, as evidenced by photophysical investigations. These effects also impact the corresponding chiroptical properties of the separated M- and P-enantiomers, which notably display circularly polarized luminescence (CPL) with dissymmetry factors in the order of magnitude of 10-4 to 10-3. Theoretical calculations confirm the optical spectroscopy data and are in agreement with the proposed involvement of ICT processes.

Modeling of pressure-induced charge transfer character in piezoluminescent pyridylvinylanthracene crystals

External pressure alters the nature of the emissive state of piezoluminescent pyridylvinylanthracene crystals.

Effect of the protein environment on the excited state phenomena in a bacteriophytochrome.

The excited state processes of a bacteriophytochrome are studied using high-level multireference methods. The various non-radiative channels of deactivation are identified for the chromophore. The effects of the protein environment and substituents are elucidated for these excited state processes. It is observed that while the excited states are completely delocalized in the Franck-Condon (FC) region, they acquire significant charge transfer character near the conical intersections. Earlier studies have emphasized the delocalized nature of the excited states in the FC region, which leads to absorption spectra with minimal Stokes shift [Rumyantsev et al., Sci. Rep., 2015, 5, 18348]. The effect of the protein environment on the vertical excitation energies was minimal, while that on the conical intersection (CI) energetics was significant. This may lead one to believe that it is charge transfer driven. However, energy decomposition analysis shows that it is the effect of the dispersion of nearby residues and the steric effect on the rings and substituents that lead to the large effect of proteins on the energetics of the CIs.