Charge stabilization via electron exchange: excited charge separation in symmetric,central triphenylamine derived,dimethylaminophenyl–tetracyanobutadiene donor–acceptor conjugates

Photoinduced charge separation in donor–acceptor conjugates plays a pivotal role in technology breakthroughs, especially in the areas of efficient conversion of solar energy into electrical energy and fuels. Extending the lifetime of the charge separated species is a necessity for their practical utilization, and this is often achieved by following the mechanism of natural photosynthesis where the process of electron/hole migration occurs distantly separating the radical ion pairs. Here, we hypothesize and demonstrate a new mechanism to stabilize the charge separated states via the process of electron exchange among the different acceptor entities in multimodular donor–acceptor conjugates. For this, star-shaped, central triphenylamine derived, dimethylamine–tetracyanobutadiene conjugates have been newly designed and characterized. Electron exchange was witnessed upon electroreduction in conjugates having multiple numbers of electron acceptors. Using ultrafast spectroscopy, the occurrence of excited state charge separation, and the effect of electron exchange in prolonging the lifetime of charge separated states in the conjugates having multiple acceptors have been successfully demonstrated. This work constitutes the first example of stabilizing charge-separated states via the process of electron exchange.

The significance of electron exchange in stabilizing the charge-separated state is revealed in multi-modular donor–acceptor conjugates.     

Visible-light-induced intramolecular charge transfer in the radical spirocyclisation of indole-tethered ynones

Indole-tethered ynones form an intramolecular electron donor–acceptor complex that can undergo visible-light-induced charge transfer to promote thiyl radical generation from thiols. This initiates a novel radical chain sequence, based on dearomatising spirocyclisation with concomitant C–S bond formation. Sulfur-containing spirocycles are formed in high yields using this simple and mild synthetic protocol, in which neither transition metal catalysts nor photocatalysts are required. The proposed mechanism is supported by various mechanistic studies, and the unusual radical initiation mode represents only the second report of the use of an intramolecular electron donor–acceptor complex in synthesis.

Indole-tethered ynones form an intramolecular electron donor–acceptor complex that can undergo visible-light-induced charge transfer to promote thiyl radical generation from thiols.     

Photoactive electron donor–acceptor complex platform for Ni-mediated C(sp3)–C(sp2) bond formation

A dual photochemical/nickel-mediated decarboxylative strategy for the assembly of C(sp³)–C(sp²) linkages is disclosed. Under light irradiation at 390 nm, commercially available and inexpensive Hantzsch ester (HE) functions as a potent organic photoreductant to deliver catalytically active Ni(0) species through single-electron transfer (SET) manifolds. As part of its dual role, the Hantzsch ester effects a decarboxylative-based radical generation through electron donor–acceptor (EDA) complex activation. This homogeneous, net-reductive platform bypasses the need for exogenous photocatalysts, stoichiometric metal reductants, and additives. Under this cross-electrophile paradigm, the coupling of diverse C(sp³)-centered radical architectures (including primary, secondary, stabilized benzylic, α-oxy, and α-amino systems) with (hetero)aryl bromides has been accomplished. The protocol proceeds under mild reaction conditions in the presence of sensitive functional groups and pharmaceutically relevant cores.

This works demonstrates the implementation of an electron donor–acceptor (EDA) complex platform toward Ni-catalyzed C(sp³)–C(sp²) bond formation, circumventing the need for exogenous photocatalysts, additives, and stoichiometric metal reductants.     

Activating intramolecular singlet exciton fission by altering π-bridge flexibility in perylene diimide trimers for organic solar cells

In this study, two analogous perylene diimide (PDI) trimers, whose structures show rotatable single bond π-bridge connection (twisted) vs. rigid/fused π-bridge connection (planar), were synthesized and investigated. We show via time resolved spectroscopic measurements how the π-bridge connections in A–π–D–π–A–π–D–π–A multichromophoric PDI systems strongly affect the triplet yield and triplet formation rate. In the planar compound, with stronger intramolecular charge transfer (ICT) character, triplet formation occurs via conventional intersystem crossing. However, clear evidence of efficient and fast intramolecular singlet exciton fission (iSEF) is observed in the twisted trimer compound with weaker ICT character. Multiexciton triplet generation and separation occur in the twisted (flexible-bridged) PDI trimer, where weak coupling among the units is observed as a result of the degenerate double triplet and quintet states, obtained by quantum chemical calculations. The high triplet yield and fast iSEF observed in the twisted compound are due not only to enthalpic viability but also to the significant entropic gain allowed by its trimeric structure. Our results represent a significant step forward in structure–property understanding, and may direct the design of new efficient iSEF materials.

We show via time resolved spectroscopy that triplet formation proceeds via intersystem crossing in a rigid-bridged perylene diimide trimer and via efficient and fast intramolecular singlet exciton fission in the analogous flexible-bridged trimer.     

Donor–acceptor–acceptor-type near-infrared fluorophores that contain dithienophosphole oxide and boryl groups: effect of the boryl group on the nonradiative decay

The use of donor–π–acceptor (D–π–A) skeletons is an effective strategy for the design of fluorophores with red-shifted emission. In particular, the use of amino and boryl moieties as the electron-donating and -accepting groups, respectively, can produce dyes that exhibit high fluorescence and solvatochromism. Herein, we introduce a dithienophosphole P-oxide scaffold as an acceptor–spacer to produce a boryl- and amino-substituted donor–acceptor–acceptor (D–A–A) π-system. The thus obtained fluorophores exhibit emission in the near-infrared (NIR) region, while maintaining high fluorescence quantum yields even in polar solvents (e.g. λ_em = 704 nm and Φ_F = 0.69 in CH₃CN). A comparison of these compounds with their formyl- or cyano-substituted counterparts demonstrated the importance of the boryl group for generating intense emission. The differences among these electron-accepting substituents were examined in detail using theoretical calculations, which revealed the crucial role of the boryl group in lowering the nonradiative decay rate constant by decreasing the non-adiabatic coupling in the internal conversion process. The D–A–A framework was further fine-tuned to improve the photostability. One of these D–A–A dyes was successfully used in bioimaging to visualize the blood vessels of Japanese medaka larvae and mouse brain.

Combination of electron-accepting diarylboryl terminal groups and dithienophosphole oxide spacers with electron-donating triarylamine moieties produces donor–acceptor–acceptor type π-systems, which exhibit emissions in the near-infrared region.     

Electron spin polarization generated by transport of singlet and quintet multiexcitons to spin-correlated triplet pairs during singlet fissions

Singlet fission (SF) is expected to exceed the Shockley–Queisser theoretical limit of efficiency of organic solar cells. Transport of spin-entanglement in the triplet–triplet pair state via one singlet exciton is a promising phenomenon for several energy conversion applications including quantum information science. However, direct observation of electron spin polarization by transport of entangled spin-states has not been presented. In this study, time-resolved electron paramagnetic resonance has been utilized to observe the transportation of singlet and quintet characters generating correlated triplet–triplet (T + T) exciton-pair states by probing the electron spin polarization (ESP) generated in thin films of 6,13-bis(triisopropylsilylethynyl)pentacene. We have clearly demonstrated that the ESP detected at the resonance field positions of individual triplet excitons is dependent on the morphology and on the detection delay time after laser flash to cause SF. ESP was clearly explained by quantum superposition of singlet–triplet–quintet wavefunctions via picosecond triplet-exciton dissociation as the electron spin polarization transfer from strongly exchange-coupled singlet and quintet TT states to weakly-coupled spin-correlated triplet pair states. Although the coherent superposition of spin eigenstates was not directly detected, the present interpretation of the spin correlation of the separated T + T exciton pair may pave new avenues not only for elucidating the vibronic role in the de-coupling between two excitons but also for scalable quantum information processing using quick T + T dissociation via one-photon excitation.

Singlet fission (SF) is expected to exceed the Shockley–Queisser theoretical limit of efficiency of organic solar cells.     

Catalytic (3 + 2) annulation of donor–acceptor aminocyclopropane monoesters and indoles

The efficient catalytic activation of donor–acceptor aminocyclopropanes lacking the commonly used diester acceptor is reported here in a (3 + 2) dearomative annulation with indoles. Bench-stable tosyl-protected aminocyclopropyl esters were converted into cycloadducts in 46–95% yields and up to 95 : 5 diastereomeric ratio using catalytic amounts of triethylsilyl triflimide. Tricyclic indoline frameworks containing four stereogenic centers including all-carbon quaternary centers were obtained.

A catalytic dearomatization of indoles with D–A aminocyclopropane monoesters for the synthesis of highly substituted indolines.     

Exploiting radical-pair intersystem crossing for maximizing singlet oxygen quantum yields in pure organic fluorescent photosensitizers

Fluorescent photosensitizers (PSs) often encounter low singlet oxygen (¹O₂) quantum yields and fluorescence quenching in the aggregated state, mainly involving the intersystem crossing process. Herein, we successfully realize maximizing ¹O₂ quantum yields of fluorescent PSs through promoting radical-pair intersystem crossing (RP-ISC), which serves as a molecular symmetry-controlling strategy of donor–acceptor (D–A) motifs. The symmetric quadrupolar A–D–A molecule PTP exhibits an excellent ¹O₂ quantum yield of 97.0% with bright near-infrared fluorescence in the aggregated state. Theoretical and ultrafast spectroscopic studies suggested that the RP-ISC mechanism dominated the formation of the triplet for PTP, where effective charge separation and an ultralow singlet–triplet energy gap (0.01 eV) enhanced the ISC process to maximize ¹O₂ generation. Furthermore, in vitro and in vivo experiments demonstrated the dual function of PTP as a fluorescent imaging agent and an anti-cancer therapeutic, with promising potential applications in both diagnosis and theranostics.

Maximizing singlet oxygen quantum yields of a fluorescent photosensitizer for realizing approximately 100% utilization of excitons by precisely controlling the molecular symmetry.     

Insight into the drastically different triplet lifetimes of BODIPY obtained by optical/magnetic spectroscopy and theoretical computations

The triplet state lifetimes of organic chromophores are crucial for fundamental photochemistry studies as well as applications as photosensitizers in photocatalysis, photovoltaics, photodynamic therapy and photon upconversion. It is noteworthy that the triplet state lifetime of a chromophore can vary significantly for its analogues, while the exact reason was rarely studied. Herein with a few exemplars of typical BODIPY derivatives, which show triplet lifetimes varying up to 110-fold (1.4–160 μs), we found that for these derivatives with short triplet state lifetimes (ca. 1–3 μs), the electron spin polarization (ESP) pattern of the time-resolved electron paramagnetic resonance (TREPR) spectra of the triplet state is inverted at a longer delay time after laser pulse excitation, as a consequence of a strong anisotropy in the decay rates of the zero-field state sublevel of the triplet state. For the derivatives showing longer triplet state lifetimes (>50 μs), no such ESP inversion was observed. The observed fast decay of one sublevel is responsible for the short triplet state lifetime; theoretical computations indicate that it is due to a strong coupling between the T_z sublevel and the ground state mediated by the spin–orbit interaction. Another finding is that the heavy atom effect on the shortening of the triplet state lifetime is more significant for the T₁ states with lower energy. To the best of our knowledge, this is the first systematic study to rationalize the short triplet state lifetime of visible-light-harvesting organic chromophores. Our results are useful for fundamental photochemistry and the design of photosensitizers showing long-lived triplet states.

The electron spin polarization inversion and anisotropic decay of triplet substates explain the short triplet state lifetime of BODIPY derivatives.     

Exploiting single-electron transfer in Lewis pairs for catalytic bond-forming reactions

A single-electron transfer (SET) between tris(pentafluorophenyl)borane (B(C₆F₅)₃) and N,N-dialkylanilines is reported, which is operative via the formation of an electron donor–acceptor (EDA) complex involving π-orbital interactions as a key intermediate under dark conditions or visible-light irradiation depending on the structure of the aniline derivatives. This inherent SET in the Lewis pairs initiates the generation of the corresponding α-aminoalkyl radicals and their additions to electron-deficient olefins, revealing the ability of B(C₆F₅)₃ to act as an effective one-electron redox catalyst.

Radical–ion pair generation from common Lewis pairs and its application to catalytic carbon–carbon bond formation.     

Porphyrin-based donor–acceptor COFs as efficient and reusable photocatalysts for PET-RAFT polymerization under broad spectrum excitation

Covalent organic frameworks (COFs) are crystalline and porous organic materials attractive for photocatalysis applications due to their structural versatility and tunable optical and electronic properties. The use of photocatalysts (PCs) for polymerizations enables the preparation of well-defined polymeric materials under mild reaction conditions. Herein, we report two porphyrin-based donor–acceptor COFs that are effective heterogeneous PCs for photoinduced electron transfer-reversible addition–fragmentation chain transfer (PET-RAFT). Using density functional theory (DFT) calculations, we designed porphyrin COFs with strong donor–acceptor characteristics and delocalized conduction bands. The COFs were effective PCs for PET-RAFT, successfully polymerizing a variety of monomers in both organic and aqueous media using visible light (λ_max from 460 to 635 nm) to produce polymers with tunable molecular weights (MWs), low molecular weight dispersity, and good chain-end fidelity. The heterogeneous COF PCs could also be reused for PET-RAFT polymerization at least 5 times without losing photocatalytic performance. This work demonstrates porphyrin-based COFs that are effective catalysts for photo-RDRP and establishes design principles for the development of highly active COF PCs for a variety of applications.

Porphyrin-based donor–acceptor COFs are effective heterogeneous photocatalysts for photoinduced electron transfer-reversible addition–fragmentation chain transfer (PET-RAFT), including for aqueous polymerizations and under red-light excitation.     

Charge-transfer biexciton annihilation in a donor–acceptor co-crystal yields high-energy long-lived charge carriers

Organic donor–acceptor (D–A) co-crystals have attracted much interest due to their important optical and electronic properties. Co-crystals having ⋯DADA⋯ π-stacked morphologies are especially interesting because photoexcitation produces a charge-transfer (CT) exciton, D˙⁺–A˙⁻, between adjacent D–A molecules. Although several studies have reported on the steady-state optical properties of this type of CT exciton, very few have measured the dynamics of its formation and decay in a single D–A co-crystal. We have co-crystallized a peri-xanthenoxanthene (PXX) donor with a N,N-bis(3-pentyl)-2,5,8,11-tetraphenylperylene-3,4:9,10-bis(dicarboximide) (Ph4PDI) acceptor to give an orthorhombic PXX–Ph4PDI ⋯DADA⋯ π-stacked co-crystal with a CT transition dipole moment that is perpendicular to the transition moments for S_n ← S₀ excitation of PXX and Ph4PDI. Using polarized, broadband, femtosecond pump–probe microscopy, we have determined that selective photoexcitation of Ph4PDI in the single co-crystal results in CT exciton formation within the 300 fs instrument response time. At early times (0.3 ≤ t ≤ 500 ps), the CT excitons decay with a t^−1/2 dependence, which is attributed to CT biexciton annihilation within the one-dimensional ⋯DADA⋯ π-stacks producing high-energy, long-lived (>8 ns) electron–hole pairs in the crystal. These energetic charge carriers may prove useful in applications ranging from photovoltaics and opto-electronics to photocatalysis.

Femtosecond transient absorption microscopy of donor–acceptor single co-crystals shows that photogenerated charge transfer excitons in one-dimensional donor–acceptor π stacks annihilate to produce high-energy, long-lived electrons and holes.     

Intrinsic photogeneration of long-lived charges in a donor-orthogonal acceptor conjugated polymer

Efficient charge photogeneration in conjugated polymers typically requires the presence of a second component to act as electron acceptor. Here, we report a novel low band-gap conjugated polymer with a donor/orthogonal acceptor motif: poly-2,6-(4,4-dihexadecyl-4H-cyclopenta [2,1-b:3,4-b′]dithiophene)-alt-2,6-spiro [cyclopenta[2,1-b:3,4-b′]dithiophene-4,9′-fluorene]-2′,7′-dicarbonitrile, referred to as PCPDT-sFCN. The role of the orthogonal acceptor is to spatially isolate the LUMO from the HOMO, allowing for negligible exchange energy between electrons in these orbitals and minimising the energy gap between singlet and triplet charge transfer states. We employ ultrafast and microsecond transient absorption spectroscopy to demonstrate that, even in the absence of a separate electron acceptor, PCPDT-sFCN shows efficient charge photogeneration in both pristine solution and film. This efficient charge generation is a result of an isoenergetic singlet/triplet charge transfer state equilibrium acting as a reservoir for charge carrier formation. Furthermore, clear evidence of enhanced triplet populations, which form in less than 1 ps, is observed. Using group theory, we show that this ultrafast triplet formation is due to highly efficient, quantum mechanically allowed intersystem crossing between the bright, initially photoexcited local singlet state and the triplet charge transfer state. Remarkably, the free charges that form via the charge transfer state are extraordinarily long-lived with millisecond lifetimes, possibly due to the stabilisation imparted by the spatial separation of PCPDT-sFCN''s donor and orthogonal acceptor motifs. The efficient generation of long-lived charge carriers in a pristine polymer paves the way for single-material applications such as organic photovoltaics and photodetectors.

The spatial separation of PCPDT-sFCN''s donor and orthogonal acceptor motifs allows efficient photogeneration of extraordinarily long-lived charge carriers in the pristine polymer, providing an important step towards single-material optoelectronics.     

High-efficiency dynamic sensing of biothiols in cancer cells with a fluorescent β-cyclodextrin supramolecular assembly

A unique fluorescent supramolecular assembly was constructed using coumarin-modified β-cyclodextrin as a reversible ratiometric probe and an adamantane-modified cyclic arginine–glycine–aspartate peptide as a cancer-targeting agent via host–guest inclusion complexation. Importantly, the coumarin-modified β-cyclodextrin not only showed higher sensitivity than the parent coumarin derivatives owing to the presence of numerous hydroxyl groups on the cyclodextrin but also provided a hydrophobic cavity for encapsulation of a cancer-targeting agent. The assembly showed a reversible and fast response to biothiols with a micromolar dissociation constant, as well as outstanding cancer cell permeability, which can be used for high-efficiency real-time monitoring of biothiols in cancer cells. This supramolecular assembly strategy endows the fluorescent probe with superior performance for dynamic sensing of biothiols.

A unique fluorescent supramolecular assembly was constructed from coumarin-modified β-cyclodextrin and an adamantane-modified cyclic arginine–glycine–aspartate peptide for high-efficiency real-time monitoring of biothiols in cancer cells.     

Polariton-assisted manipulation of energy relaxation pathways: donor–acceptor role reversal in a tuneable microcavity

Resonant interaction between excitonic transitions of molecules and localized electromagnetic field allows the formation of hybrid light–matter polaritonic states. This hybridization of the light and the matter states has been shown to significantly alter the intrinsic properties of molecular ensembles placed inside the optical cavity. Here, we have observed strong coupling of excitonic transition in a pair of closely located organic dye molecules demonstrating an efficient donor-to-acceptor resonance energy transfer with the mode of a tuneable open-access cavity. Analysing the dependence of the relaxation pathways between energy states in this system on the cavity detuning, we have demonstrated that predominant strong coupling of the cavity photon to the exciton transition in the donor dye molecule can lead not only to an increase in the donor–acceptor energy transfer, but also to an energy shift large enough to cause inversion between the energy states of the acceptor and the mainly donor lower polariton energy state. Furthermore, we have shown that the polariton-assisted donor–acceptor chromophores'' role reversal or “carnival effect” not only changes the relative energy levels of the donor–acceptor pair, but also makes it possible to manipulate the energy flow in the systems with resonant dipole–dipole interaction and direct energy transfer from the acceptor to the mainly donor lower polariton state. Our experimental data are the first confirmation of the theoretically predicted possibility of polariton-assisted energy transfer reversal in FRET systems, thus paving the way to new avenues in FRET-imaging, remote-controlled chemistry, and all-optical switching.

Polariton-assisted donor–acceptor role reversal in resonant energy transfer between organic dyes tagged with the terminus of the closed oligonucleotide-based molecular beacon strongly coupled to electromagnetic modes of a tuneable microcavity.     

Resolving electron injection from singlet fission-borne triplets into mesoporous transparent conducting oxides

Photoinduced electron transfer into mesoporous oxide substrates is well-known to occur efficiently for both singlet and triplet excited states in conventional metal-to-ligand charge transfer (MLCT) dyes. However, in all-organic dyes that have the potential for producing two triplet states from one absorbed photon, called singlet fission dyes, the dynamics of electron injection from singlet vs. triplet excited states has not been elucidated. Using applied bias transient absorption spectroscopy with an anthradithiophene-based chromophore (ADT-COOH) adsorbed to mesoporous indium tin oxide (nanoITO), we modulate the driving force and observe changes in electron injection dynamics. ADT-COOH is known to undergo fast triplet pair formation in solid-state films. We find that the electronic coupling at the interface is roughly one order of magnitude weaker for triplet vs. singlet electron injection, which is potentially related to the highly localized nature of triplets without significant charge-transfer character. Through the use of applied bias on nanoITO:ADT-COOH films, we map the electron injection rate constant dependence on driving force, finding negligible injection from triplets at zero bias due to competing recombination channels. However, at driving forces greater than −0.6 eV, electron injection from the triplet accelerates and clearly produces a trend with increased applied bias that matches predictions from Marcus theory with a metallic acceptor.

The rate of photoinduced electron transfer from triplet excited states after singlet fission in molecules adsorbed to mesoporous oxide substrates is shown through transient absorption studies to depend systematically on applied bias.     

Design of BODIPY dyes as triplet photosensitizers: electronic properties tailored for solar energy conversion,photoredox catalysis and photodynamic therapy

BODIPYs are renowned fluorescent dyes with strong and tunable absorption in the visible region, high thermal and photo-stability and exceptional fluorescence quantum yields. Transition metal complexes are the most commonly used triplet photosensitisers, but, recently, the use of organic dyes has emerged as a viable and more sustainable alternative. By proper design, BODIPY dyes have been turned from highly fluorescent labels into efficient triplet photosensitizers with strong absorption in the visible region (from green to orange). In this perspective, we report three design strategies: (i) halogenation of the dye skeleton, (ii) donor–acceptor dyads and (iii) BODIPY dimers. We compare pros and cons of these approaches in terms of optical and electrochemical properties and synthetic viability. The potential applications of these systems span from energy conversion to medicine and key examples are presented.

BODIPYs offer a versatile platform to build organic triplet photosensitisers for PDT, TTA upconversion and photocatalysis. Tuning their properties provides the opportunity of replacing heavy-metal complexes and can lead to improved sustainability.     

Chromophore-radical excited state antiferromagnetic exchange controls the sign of photoinduced ground state spin polarization

A change in the sign of the ground-state electron spin polarization (ESP) is reported in complexes where an organic radical (nitronylnitroxide, NN) is covalently attached to a donor–acceptor chromophore via two different meta-phenylene bridges in (bpy)Pt(CAT-m-Ph-NN) (mPh-Pt) and (bpy)Pt(CAT-6-Me-m-Ph-NN) (6-Me-mPh-Pt) (bpy = 5,5′-di-tert-butyl-2,2′-bipyridine, CAT = 3-tert-butylcatecholate, m-Ph = meta-phenylene). These molecules represent a new class of chromophores that can be photoexcited with visible light to produce an initial exchange-coupled, 3-spin (bpy˙⁻, CAT⁺˙ = semiquinone (SQ), and NN), charge-separated doublet ²S₁ (S = chromophore excited spin singlet configuration) excited state. Following excitation, the ²S₁ state rapidly decays to the ground state by magnetic exchange-mediated enhanced internal conversion via the ²T₁ (T = chromophore excited spin triplet configuration) state. This process generates emissive ground state ESP in 6-Me-mPh-Pt while for mPh-Pt the ESP is absorptive. It is proposed that the emissive polarization in 6-Me-mPh-Pt results from zero-field splitting induced transitions between the chromophoric ²T₁ and ⁴T₁ states, whereas predominant spin–orbit induced transitions between ²T₁ and low-energy NN-based states give rise to the absorptive polarization observed for mPh-Pt. The difference in the sign of the ESP for these molecules is consistent with a smaller excited state ²T₁ – ⁴T₁ gap for 6-Me-mPh-Pt that derives from steric interactions with the 6-methyl group. These steric interactions reduce the excited state pairwise SQ-NN exchange coupling compared to that in mPh-Pt.

A change in the sign of the ground state electron spin polarization (ESP) is reported in complexes where an organic radical (nitronylnitroxide, NN) is covalently attached to a donor–acceptor chromophore via two different meta-phenylene bridges.     

On–off switch of charge-separated states of pyridine-vinylene-linked porphyrin–C60 conjugates detected by EPR

The design, synthesis, and electronic properties of a new series of D–π–A conjugates consisting of free base (H₂P) and zinc porphyrins (ZnP) as electron donors and a fullerene (C₆₀) as electron acceptor, in which the two electroactive entities are covalently linked through pyridine-vinylene spacers of different lengths, are described. Electronic interactions in the ground state were characterized by electrochemical and absorption measurements, which were further supported with theoretical calculations. Most importantly, charge-transfer bands were observed in the absorption spectra, indicating a strong push–pull behavior. In the excited states, electronic interactions were detected by selective photoexcitation under steady-state conditions, by time-resolved fluorescence investigations, and by pump probe experiments on the femto-, pico-, and nanosecond time scales. Porphyrin fluorescence is quenched for the different D–π–A conjugates, from which we conclude that the deactivation mechanisms of the excited singlet states are based on photoinduced energy- and/or electron transfer processes between H₂P/ZnP and C₆₀, mediated through the molecular spacers. The fluorescence intensity decreases and the fluorescence lifetimes shorten as the spacer length decreases and as the spacer substitution changes. With the help of transient absorption spectroscopy, the formation of charge-separated states involving oxidized H₂P/ZnP and reduced C₆₀ was confirmed. Lifetimes of the corresponding charge-separated states, which ranged from ∼400 picoseconds to 165 nanoseconds, depend on the spacer length, the spacer substitution, and the solvent polarity. Interestingly, D–π–A conjugates containing the longest linkers did not necessarily exhibit the longest charge-separated state lifetimes. The distances between the electron donors and the acceptors were calculated by molecular modelling. The longest charge-separated state lifetime corresponded to the D–π–A conjugate with the longest electron donor–acceptor distance. Likewise, EPR measurements in frozen media revealed charge separated states in all the D–π–A conjugates investigated. A sharp peak with g values ∼2.000 was assigned to reduced C₆₀, while a broader, less intense signal (g ∼ 2.003) was assigned to oxidized H₂P/ZnP. On–off switching of the formation and decay of the charge-separated states was detected by EPR at 77 K by repeatedly turning the irradiation source on and off.     

Method for accurate experimental determination of singlet and triplet exciton diffusion between thermally activated delayed fluorescence molecules

Understanding triplet exciton diffusion between organic thermally activated delayed fluorescence (TADF) molecules is a challenge due to the unique cycling between singlet and triplet states in these molecules. Although prompt emission quenching allows the singlet exciton diffusion properties to be determined, analogous analysis of the delayed emission quenching does not yield accurate estimations of the triplet diffusion length (because the diffusion of singlet excitons regenerated after reverse-intersystem crossing needs to be accounted for). Herein, we demonstrate how singlet and triplet diffusion lengths can be accurately determined from accessible experimental data, namely the integral prompt and delayed fluorescence. In the benchmark materials 4CzIPN and 4TCzBN, we show that the singlet diffusion lengths are (9.1 ± 0.2) and (12.8 ± 0.3) nm, whereas the triplet diffusion lengths are negligible, and certainly less than 1.0 and 1.2 nm, respectively. Theory confirms that the lack of overlap between the shielded lowest unoccupied molecular orbitals (LUMOs) hinders triplet motion between TADF chromophores in such molecular architectures. Although this cause for the suppression of triplet motion does not occur in molecular architectures that rely on electron resonance effects (e.g. DiKTa), we find that triplet diffusion is still negligible when such molecules are dispersed in a matrix material at a concentration sufficiently low to suppress aggregation. The novel and accurate method of understanding triplet diffusion in TADF molecules will allow accurate physical modeling of OLED emitter layers (especially those based on TADF donors and fluorescent acceptors).

A method for measuring triplet diffusion between TADF molecules is presented, and implications of limited triplet diffusion for OLEDs discussed.