Vibronic effects accelerate the intersystem crossing processes of the through-space charge transfer states in the triptycene bridged acridine–triazine donor–acceptor molecule TpAT-tFFO

Quantum chemical studies employing combined density functional and multireference configuration interaction methods suggest five excited electronic states to be involved in the prompt and delayed fluorescence emission of TpAT-tFFO. Three of them, a pair of singlet and triplet charge transfer (CT) states (S₁ and T₁) and a locally excited (LE) triplet state (T₃), can be associated with the (Me → N) conformer, the other two CT-type states (S₂ and T₂) form the lowest excited singlet and triplet states of the (Me → Ph) conformer. The two conformers, which differ in essence by the shearing angle of the face-to-face aligned donor and acceptor moieties, are easily interconverted in the electronic ground state whereas the reorganization energy is substantial in the excited singlet state, thus explaining the two experimentally observed time constants of prompt fluorescence emission. Forward and reverse intersystem crossing between the singlet and triplet CT states is mediated by vibronic spin–orbit interactions involving the LE T₃ state. Low-frequency vibrational modes altering the distance and alignment of the donor and acceptor π-systems tune the S₁ and T₃ states (likewise S₂ and T₃) into and out of resonance. The enhancement of intersystem crossing due to the interplay of vibronic and spin–orbit coupling is considered a general feature of organic through-space charge-transfer thermally activated delayed fluorescence emitters.

DFT/MRCI quantum chemical studies suggest five excited electronic states to be involved in the prompt and delayed fluorescence emission of TpAT-tFFO.     

Heterogeneous electron transfer reorganization energy at the inner Helmholtz plane in a polybromide redox-active ionic liquid

In ionic liquids (ILs), the electric double layer (EDL) is where heterogeneous electron transfer (ET) occurs. Nevertheless, the relationship between the EDL structure and its kinetics has been rarely studied, especially for ET taking place in the inner Helmholtz plane (IHP). This is largely because of the lack of an appropriate model system for experiments. In this work, we determined the reorganization energy (λ) of Br₂ reduction in a redox-active IL 1-ethyl-1-methylpyrrolidinium polybromide (MEPBr_2n+1) based on the Marcus–Hush–Chidsey model. Exceptionally fast mass transport of Br₂ in MEPBr_2n+1 allows voltammograms to be obtained in which the current plateau is regulated by electron-transfer kinetics. This enables investigation of the microscopic environment in the IHP of the IL affecting electrocatalytic reactions through reorganization energy. As a demonstration, TiO₂-modified Pt was employed to show pH-dependent reorganization energy, which suggests the switch of major ions at the IHP as a function of surface charges of electrodes.

Ultrafast transport of Br₂ in a polybromide redox-active ionic liquid allows electron transfer-limited voltammograms of Br₂ reduction. The reorganization energy at the inner-Helmholtz plane can be determined based on the Marcus–Hush–Chidsey model.     

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.     

The effect of deuterium on the photophysical properties of DNA-stabilized silver nanoclusters

We investigated the effect of using D₂O versus H₂O as solvent on the spectroscopic properties of two NIR emissive DNA-stabilized silver nanoclusters (DNA–AgNCs). The two DNA–AgNCs were chosen because they emit in the same energy range as the third overtone of the O–H stretch. Opposite effects on the ns-lived decay were observed for the two DNA–AgNCs. Surprisingly, for one DNA–AgNC, D₂O shortened the ns decay time and enhanced the amount of µs-lived emission. We hypothesize that the observed effects originate from the differences in the hydrogen bonding strength and vibrational frequencies in the two diverse solvents. For the other DNA–AgNC, D₂O lengthened the ns decay time and made the fluorescence quantum yield approach unity at 5 °C.

We investigated the effect of using D₂O versus H₂O as solvent on the spectroscopic properties of two NIR emissive DNA-stabilized silver nanoclusters (DNA–AgNCs).     

Catalytic electron drives host–guest recognition

Electron injection is demonstrated to trigger electrocatalytic chain reactions capable of releasing a solvent molecule and forming a redox active guest molecule. One-electron reduction of a hydroxy anthrone derivative (AQH–CH₂CN) results in the formation of an anthraquinone radical anion (AQ˙⁻) and acetonitrile (CH₃CN). The resulting fragment of AQ˙⁻ exhibits high stability under mild reducing conditions, and it has enough reducing power to reduce the reactant of AQH–CH₂CN. Hence, subsequent electron transfer from AQ˙⁻ to AQH–CH₂CN yields the secondary AQ˙⁻ and CH₃CN, while the initial AQ˙⁻ is subsequently oxidized to AQ. Overall, the reactants of AQH–CH₂CN are completely converted into AQ and CH₃CN in sustainable electrocatalytic chain reactions. These electrocatalytic chain reactions are mild and sustainable, successfully achieving catalytic electron-triggered charge-transfer (CT) complex formation. Reactant AQH–CH₂CN is non-planar, making it unsuitable for CT interaction with an electron donor host compound (U_HAnt₂) bearing parallel anthracene tweezers. However, conversion of AQH–CH₂CN to planar electron acceptor AQ by the electrocatalytic chain reactions turns on CT interaction, generating a host CT complex with U_HAnt₂ (AQ ⊂ U_HAnt₂). Therefore, sustainable electrocatalytic chain reactions can control CT interactions using only a catalytic amount of electrons, ultimately affording a one-electron switch associated with catalytic electron-triggered turn-on molecular recognition.

The reactants of AQH–CH₂CN are converted into AQ and CH₃CN in sustainable electrocatalytic chain reactions, successfully achieving catalytic electron-triggered charge-transfer (CT) complex formation.     

Hot-exciton harvesting via through-space single-molecule based white-light emission and optical waveguides

Through-space donor–alkyl bridge–acceptor (D–σ–A) luminogens are developed as new organic single-molecule white light emitters (OSMWLEs) involving multiple higher lying singlet (S_n) and triplet (T_m) states (hot-excitons). Experimental and theoretical results confirm the origin of white light emission due to the co-existence of prompt fluorescence from locally excited states, thermally activated delayed fluorescence (TADF), and fast/slow dual phosphorescence color mixing simultaneously. Notably, the fast phosphorescence was observed due to trace amounts of isomeric impurities from commercial carbazole, while H-/J-aggregation resulted in slow phosphorescence. Crystal structure-packing-property analysis revealed that the alkyl chain length induced supramolecular self-assembly greatly influenced the solid-state optical properties. Remarkably, the 1D-microrod crystals of OSMWLEs demonstrated the first examples of triplet harvesting waveguides by self-guiding the generated phosphorescence through light propagation along their longitudinal axis. This work thus highlights an uncommon design strategy to achieve multi-functional OSMWLEs with in-depth mechanistic insights and optical waveguiding applications making them a potentially new class of white emissive materials.

Through-space donor–alkyl bridge–acceptor multifunctional organic single molecules that simultaneously displayed white light emission, thermally activated delayed fluorescence, room temperature dual phosphorescence and optical wave-guiding properties.     

A novel type of donor–acceptor cyclopropane with fluorine as the donor: (3 + 2)-cycloadditions with carbonyls

gem-Difluorocyclopropane diester is disclosed as a new type of donor–acceptor cyclopropane, which smoothly participates in (3 + 2)-cycloadditions with various aldehydes and ketones. This work represents the first application of gem-difluorine substituents as an unconventional donor group for activating cyclopropane substrates in catalytic cycloaddition reactions. With this method, a wide variety of densely functionalized gem-difluorotetrahydrofuran skeletons, which are otherwise difficult to prepare, could be readily assembled in high yields under mild reaction conditions. Computational studies show that the cleavage of the C–C bond between the difluorine and diester moieties occurs upon a S_N2-type attack of the carbonyl oxygen.

A new type of donor–acceptor cyclopropane with gem-difluorine as an unconventional donor group undergoes (3 + 2)-cycloadditions with various aldehydes/ketones, affording densely functionalized gem-difluorotetrahydrofurans.     

Green-/NIR-light-controlled rapid photochromism featuring reversible thermally activated delayed fluorescence and photoelectronic switching

Fluorescent dithienylethene-based photochromic materials have been attracting considerable attention owing to their wide applications in biological and materials sciences. However, the limitations of detrimental UV irradiation for photocyclization, short emission lifetime, and inefficient photoresponsive speed still need to be addressed. Herein, a novel dithienylethene photochromic molecule, BFBDTE, has been prepared by the incorporation of a difluoroboron β-diketonate (BF₂bdk) unit. The strong electron acceptor BF₂bdk not only reduces the energy gap of the open isomer, ensuring visible light-controlled fluorescence switching, but also promotes intersystem crossing for the generation of thermally activated delayed fluorescence (TADF). Upon alternating irradiation with green and NIR light, BFBDTE presents a rare example of photochromism, fluorescence and TADF switching in various polar solvents and a poly(methyl methacrylate) (PMMA) film. Meanwhile, it shows rapid and well repeatable cyclization (12 s) and cycloreversion reactions (20 s) in PMMA, accompanied by fast TADF switching within 11 s. Furthermore, photo-electrochemical measurements reveal a remarkable on-off photoelectronic response (photocurrent density ratio: I_light/I_dark = 684) between the open- and closed-form of BFBDTE. These remarkable merits make BFBDTE promising for photoswitchable molecular devices, optical memory storage systems, NIR detectors, and photoelectric switching.

Controlled by the alternating irradiation of green and NIR light, difluoroboron modifed dithienylethene shows rapid photochromism and photoelectronic switching.     

Circumventing the scaling relationship on bimetallic monolayer electrocatalysts for selective CO2 reduction

Electrochemical conversion of CO₂ into value-added chemicals continues to draw interest in renewable energy applications. Although many metal catalysts are active in the CO₂ reduction reaction (CO₂RR), their reactivity and selectivity are nonetheless hindered by the competing hydrogen evolution reaction (HER). The competition of the HER and CO₂RR stems from the energy scaling relationship between their reaction intermediates. Herein, we predict that bimetallic monolayer electrocatalysts (BMEs) – a monolayer of transition metals on top of extended metal substrates – could produce dual-functional active sites that circumvent the scaling relationship between the adsorption energies of HER and CO₂RR intermediates. The antibonding interaction between the adsorbed H and the metal substrate is revealed to be responsible for circumventing the scaling relationship. Based on extensive density functional theory (DFT) calculations, we identify 11 BMEs which are highly active and selective toward the formation of formic acid with a much suppressed HER. The H–substrate antibonding interaction also leads to superior CO₂RR performance on monolayer-coated penta-twinned nanowires.

Dual-functional active sites are designed to circumvent the scaling relationship between the HER and CO₂RR on bimetallic monolayer electrocatalysts.     

A practical and sustainable two-component Minisci alkylation via photo-induced EDA-complex activation

An operationally simple, open-air, and efficient light-mediated Minisci C–H alkylation method is described, based on the formation of an electron donor–acceptor (EDA) complex between nitrogen-containing heterocycles and redox-active esters. In contrast to previously reported protocols, this method does not require a photocatalyst, an external single electron transfer agent, or an oxidant additive. Achieved under mildly acidic and open-air conditions, the reaction incorporates primary-, secondary-, and tertiary radicals, including bicyclo[1.1.1]pentyl (BCP) radicals, along with various heterocycles to generate Minisci alkylation products in moderate to good yields. Additionally, the method is exploited to generate a stereo-enriched, hetereoaryl-substituted carbohydrate.

An operationally simple, open-air, and efficient light-mediated Minisci C–H alkylation method is described, based on the formation of an electron donor–acceptor (EDA) complex between nitrogen-containing heterocycles and redox-active esters.     

Modular synthesis,host–guest complexation and solvation-controlled relaxation of nanohoops with donor–acceptor structures

Carbon nanohoops with donor–acceptor (D–A) structures are attractive electronic materials and biological fluorophores, but their synthesis is usually challenging. Moreover, the preparation of D–A nanohoop fluorophores exhibiting high fluorescence quantum yields beyond 500 nm remains a key challenge. This study presents a modular synthetic approach based on an efficient metal-free cyclocondensation reaction that readily produced nine congeners with D–A or donor–acceptor–donor′ (D–A–D′) structures, one of which is water-soluble. The tailored molecular design of nanohoops enabled a systematic and detailed study of their host–guest complexation with fullerene, optical properties, and charge transfer (CT) dynamics using X-ray crystallography, fluorescence titration, steady and ultrafast transient absorption spectroscopy, and theoretical calculations. The findings revealed intriguing physical properties associated with D–A motifs, such as tight binding with fullerene, moderate fluorescence quantum yields (37–67%) beyond 540 nm, and unique solvation-controlled CT relaxation of D–A–D′ nanohoops, where two CT states (D–A and A–D′) can be effectively tuned by solvation, resulting in dramatically changed relaxation pathways in different solvents.

A modular synthetic approach based on cyclocondensation reaction is introduced to produce nine nanohoops with tunable donor–acceptor structures.     

A site-differentiated [4Fe–4S] cluster controls electron transfer reactivity of Clostridium acetobutylicum [FeFe]-hydrogenase I

One of the many functions of reduction–oxidation (redox) cofactors is to mediate electron transfer in biological enzymes catalyzing redox-based chemical transformation reactions. There are numerous examples of enzymes that utilize redox cofactors to form electron transfer relays to connect catalytic sites to external electron donors and acceptors. The compositions of relays are diverse and tune transfer thermodynamics and kinetics towards the chemical reactivity of the enzyme. Diversity in relay design is exemplified among different members of hydrogenases, enzymes which catalyze reversible H₂ activation, which also couple to diverse types of donor and acceptor molecules. The [FeFe]-hydrogenase I from Clostridium acetobutylicum (CaI) is a member of a large family of structurally related enzymes where interfacial electron transfer is mediated by a terminal, non-canonical, His-coordinated, [4Fe–4S] cluster. The function of His coordination was examined by comparing the biophysical properties and reactivity to a Cys substituted variant of CaI. This demonstrated that His coordination strongly affected the distal [4Fe–4S] cluster spin state, spin pairing, and spatial orientations of molecular orbitals, with a minor effect on reduction potential. The deviations in these properties by substituting His for Cys in CaI, correlated with pronounced changes in electron transfer and reactivity with the native electron donor–acceptor ferredoxin. The results demonstrate that differential coordination of the surface localized [4Fe–4S]His cluster in CaI is utilized to control intermolecular and intramolecular electron transfer where His coordination creates a physical and electronic environment that enables facile electron exchange between electron carrier molecules and the iron–sulfur cluster relay for coupling to reversible H₂ activation at the catalytic site.

Histidine coordination of the distal [4Fe–4S] cluster in [FeFe]-hydrogenase was demonstrated to tune the cluster spin-states, spin-pairing and surrounding molecular orbitals to enable more facile electron transfer compared to cysteine coordination.     

Highly efficient Förster resonance energy transfer between an emissive tetraphenylethylene-based metal–organic cage and the encapsulated dye guest

The host–guest strategy presents an ideal way to achieve efficient Förster resonance energy transfer (FRET) by forcing close proximity between an energy donor and acceptor. Herein, by encapsulating the negatively charged acceptor dyes eosin Y (EY) or sulforhodamine 101 (SR101) in the cationic tetraphenylethene-based emissive cage-like host donor Zn-1, host–guest complexes were formed that exhibit highly efficient FRET. The energy transfer efficiency of Zn-1⊃EY reached 82.4%. To better verify the occurrence of the FRET process and make full use of the harvested energy, Zn-1⊃EY was successfully used as a photochemical catalyst for the dehalogenation of α-bromoacetophenone. Furthermore, the emission color of the host–guest system Zn-1⊃SR101 could be adjusted to exhibit bright white-light emission with the CIE coordinates (0.32, 0.33). This work details a promising approach to enhance the efficiency of the FRET process by the creation of a host–guest system between the cage-like host and dye acceptor, thus serving as a versatile platform for mimicking natural light-harvesting systems.

Highly efficient Förster resonance energy transfer was realized between an emissive metal–organic cage and encapsulated dyes through the close space distance forced by host–guest interaction.     

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.     

The simplest structure of a stable radical showing high fluorescence efficiency in solution: benzene donors with triarylmethyl radicals

Donor–radical acceptor systems have recently attracted much attention as efficient doublet emitters that offer significant advantages for applications such as OLEDs. We employed an alkylbenzene (mesityl group) as the simplest donor to date and added it to a diphenylpyridylmethyl radical acceptor. The (3,5-difluoro-4-pyridyl)bis[2,6-dichloro-4-(2,4,6-trimethylphenyl)phenyl]methyl radical (Mes₂F₂PyBTM) was prepared in only three steps from commercially available reagents. A stable radical composed of only one pyridine ring, four benzene rings, methyl groups, halogens, and hydrogens showed fluorescence of over 60% photoluminescence quantum yield (PLQY) in chloroform, dichloromethane, and PMMA. The key to high fluorescence efficiency was benzene rings perpendicular to the diphenylpyridylmethyl radical in the doublet ground (D₀) state. The relatively low energy of the β-HOMO and the electron-accepting character of the radical enabled the use of benzenes as electron donors. Furthermore, the structural relaxation of the doublet lowest excited (D₁) state was minimized by steric hindrance of the methyl groups. The reasons for this high efficiency include the relatively fast fluorescence transition and the slow internal conversion, both of which were explained by the overlap density between the D₁ and D₀ states.

By adding mesityl donors to a diphenylpyridyl radical acceptor, a highly luminescent stable radical was prepared in three steps from commercially available reagents. The photoluminescence quantum yield was as much as 69% in chloroform.     

An organophotocatalytic late-stage N–CH3 oxidation of trialkylamines to N-formamides with O2 in continuous flow

We report an organophotocatalytic, N–CH₃-selective oxidation of trialkylamines in continuous flow. Based on the 9,10-dicyanoanthracene (DCA) core, a new catalyst (DCAS) was designed with solubilizing groups for flow processing. This allowed O₂ to be harnessed as a sustainable oxidant for late-stage photocatalytic N–CH₃ oxidations of complex natural products and active pharmaceutical ingredients bearing functional groups not tolerated by previous methods. The organophotocatalytic gas–liquid flow process affords cleaner reactions than in batch mode, in short residence times of 13.5 min and productivities of up to 0.65 g per day. Spectroscopic and computational mechanistic studies showed that catalyst derivatization not only enhanced solubility of the new catalyst compared to poorly-soluble DCA, but profoundly diverted the photocatalytic mechanism from singlet electron transfer (SET) reductive quenching with amines toward energy transfer (E_nT) with O₂.

An N–CH₃-selective trialkylamine oxidation to N-formamides is reported in continuous flow using gaseous O₂. A novel, enhanced-solubility dicyanoanthracene organophotocatalyst switched the photochemical mechanism from electron to energy transfer.     

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.     

Buffering the local pH via single-atomic Mn–N auxiliary sites to boost CO2 electroreduction

Electrocatalytic CO₂ reduction driven by renewable energy has become a promising approach to rebalance the carbon cycle. Atomically dispersed transition metals anchored on N-doped carbon supports (M-N-C) have been considered as the most attractive catalysts to catalyze CO₂ to CO. However, the sluggish kinetics of M-N-C limits the large-scale application of this type of catalyst. Here, it is found that the introduction of single atomic Mn–N auxiliary sites could effectively buffer the locally generated OH⁻ on the catalytic interface of the single-atomic Ni–N–C sites, thus accelerating proton-coupled electron transfer (PCET) steps to enhance the CO₂ electroreduction to CO. The constructed diatomic Ni/Mn–N–C catalysts show a CO faradaic efficiency of 96.6% and partial CO current density of 13.3 mA cm⁻² at −0.76 V vs. RHE, outperforming that of monometallic single-atomic Ni–N–C or Mn–N–C counterparts. The results suggest that constructing synergistic catalytic sites to regulate the surface local microenvironment might be an attractive strategy for boosting CO₂ electroreduction to value-added products.

An effective strategy is developed to regulate the local microenvironment of single atomic Ni–N–C sites for accelerating CO₂ to CO conversion. The Ni/Mn–N–C catalysts shows a CO faradaic efficiency of 96.6% due to the accelerated reaction kinetics.     

A long-lived charge-separated state of spiro compact electron donor–acceptor dyads based on rhodamine and naphthalenediimide chromophores

Spiro rhodamine (Rho)-naphthalenediimide (NDI) electron donor–acceptor orthogonal dyads were prepared to generate a long-lived charge separation (CS) state based on the electron spin control approach, i.e. to form the ³CS state, not the ¹CS state, to prolong the CS state lifetime by the electron spin forbidden feature of the charge recombination process of ³CS → S₀. The electron donor Rho (lactam form) is attached via three σ bonds, including two C–C and one N–N bonds (Rho-NDI), or an intervening phenylene, to the electron acceptor NDI (Rho-Ph-NDI and Rho-PhMe-NDI). Transient absorption (TA) spectra show that fast intersystem crossing (ISC) (<120 fs) occurred to generate an upper triplet state localized on the NDI moiety (³NDI*), and then to form the CS state. For Rho-NDI in both non-polar and polar solvents, a long-lived ³CS state (lifetime τ = 0.13 μs) and charge separation quantum yield (Φ_CS) up to 25% were observed, whereas for Rho-Ph-NDI (τ_T = 1.1 μs) and Rho-PhMe-NDI (τ_T = 2.0 μs), a low-lying ³NDI* state was formed by charge recombination (CR) in n-hexane (HEX). In toluene (TOL), however, CS states were observed for Rho-Ph-NDI (0.37 μs) and Rho-PhMe-NDI (0.63 μs). With electron paramagnetic resonance (EPR) spectra, weak electronic coupling between the Rho and NDI moieties for Rho-NDI was proved. Time-resolved EPR (TREPR) spectra detected two transient species including NDI-localized triplets (formed via SOC-ISC) and a ³CS state. The CS state of Rho-NDI features the largest dipolar interaction (|D| = 184 MHz) compared to Rho-Ph-NDI (|D| = 39 MHz) and Rho-PhMe-NDI (|D| = 41 MHz) due to the smallest distance between Rho and NDI moieties. For Rho-NDI, the time-dependent e,a → a,e phase change of the CS state TREPR spectrum indicates that the long-lived CS state is based on the electron spin control effect.

Spiro compact rhodamine-naphthalenediimide electron donor–acceptor dyads show a long-lived charge separated state (lifetime: 0.72 μs) based on the electron spin control effect were reported.     

Charge transport through extended molecular wires with strongly correlated electrons

Electron–electron interactions are at the heart of chemistry and understanding how to control them is crucial for the development of molecular-scale electronic devices. Here, we investigate single-electron tunneling through a redox-active edge-fused porphyrin trimer and demonstrate that its transport behavior is well described by the Hubbard dimer model, providing insights into the role of electron–electron interactions in charge transport. In particular, we empirically determine the molecule''s on-site and inter-site electron–electron repulsion energies, which are in good agreement with density functional calculations, and establish the molecular electronic structure within various oxidation states. The gate-dependent rectification behavior confirms the selection rules and state degeneracies deduced from the Hubbard model. We demonstrate that current flow through the molecule is governed by a non-trivial set of vibrationally coupled electronic transitions between various many-body ground and excited states, and experimentally confirm the importance of electron–electron interactions in single-molecule devices.

Experimental studies of electron transport through an edge-fused porphyrin oligomer in a graphene junction are interpreted within a Hubbard dimer framework.