Circular Photoinduced Electron Transfer in a Donor‐Acceptor‐Acceptor Triad

An electron‐donor‐acceptor‐acceptor (D‐A₁‐A₂) triad has been developed that provides the first proof‐of‐concept for a photoinitiated molecular circuit. After photoexcitation into an optical charge‐transfer transition between D and A₁, subsequent thermal electron‐transfer from A₁^.? to A₂ is followed by geometric rearrangement in the D^.+‐A₁‐A₂^.? charge‐separated state to form an ion‐pair contact. This facilitates “forward” charge recombination between A₂^.? and D^.+ to complete the molecular circuit with an estimated quantum efficiency of 4 % in toluene at 298 K.     

Photoinduced Electron Transfer in an Amine–Corrole–Perylene Bisimide Assembly: Charge Separation over Terminal Components Favoured by Solvent Polarity

An assembly has been synthesised that consists of four units: a meso‐substituted corrole (C3), perylene bisimide (PI), and two electron‐rich triphenylamine (DPA) units. PI is connected through a 1,4‐phenylene bridge to C3, whereas the two DPA units are linked to C3 through a diphenyl ether linkage, which is used for the first time to connect the various moieties. Various synthetic strategies were elaborated, and the chosen one afforded the final system in six steps in an overall yield of 6 %. The resulting assembly, made of three different units, was named a “triad”. Excitation of the corrole (C3) or perylene bisimide (PI) units led to the charge‐separated state DPA‐C3⁺‐PI^? with a rate k>10¹¹ s^?1 in benzonitrile and dichloromethane (CH₂Cl₂) or with k of the order of 10¹⁰ s^?1 in toluene. The latter charge‐separated state decayed to the ground state with a rate k=1.8×10⁹ s^?1 in toluene. In the polar solvents benzonitrile and dichloromethane, recombination to the ground state competes with a charge shift to form the distal charge‐separated state, DPA⁺‐C3‐PI^?, the formation of which occurs with a yield of 50 %. Recombination to the ground state of DPA⁺‐C3‐PI^? occurs with a rate k=5×10⁷ s^?1 in CH₂Cl₂ and k=2×10⁷ s^?1 in benzonitrile.     

Ultrafast Photoinduced Energy and Electron Transfer in Multi‐Modular Donor–Acceptor Conjugates

New multi‐modular donor–acceptor conjugates featuring zinc porphyrin (ZnP), catechol‐chelated boron dipyrrin (BDP), triphenylamine (TPA) and fullerene (C₆₀), or naphthalenediimide (NDI) have been newly designed and synthesized as photosynthetic antenna and reaction‐center mimics. The X‐ray structure of triphenylamine‐BDP is also reported. The wide‐band capturing polyad revealed ultrafast energy‐transfer (k_ENT=1.0×10¹² s^?1) from the singlet excited BDP to the covalently linked ZnP owing to close proximity and favorable orientation of the entities. Introducing either fullerene or naphthalenediimide electron acceptors to the TPA‐BDP‐ZnP triad through metal–ligand axial coordination resulted in electron donor–acceptor polyads whose structures were revealed by spectroscopic, electrochemical and computational studies. Excitation of the electron donor, zinc porphyrin resulted in rapid electron‐transfer to coordinated fullerene or naphthalenediimide yielding charge separated ion‐pair species. The measured electron transfer rate constants from femtosecond transient spectral technique in non‐polar toluene were in the range of 5.0×10⁹–3.5×10¹⁰ s^?1. Stabilization of the charge‐separated state in these multi‐modular donor–acceptor polyads is also observed to certain level.     

Engaging Copper(III) Corrole as an Electron Acceptor: Photoinduced Charge Separation in Zinc Porphyrin–Copper Corrole Donor–Acceptor Conjugates

An electron‐deficient copper(III) corrole was utilized for the construction of donor–acceptor conjugates with zinc(II) porphyrin (ZnP) as a singlet excited state electron donor, and the occurrence of photoinduced charge separation was demonstrated by using transient pump–probe spectroscopic techniques. In these conjugates, the number of copper corrole units was varied from 1 to 2 or 4 units while maintaining a single ZnP entity to observe the effect of corrole multiplicity in facilitating the charge‐separation process. The conjugates and control compounds were electrochemically and spectroelectrochemically characterized. Computational studies revealed ground state geometries of the compounds and the electron‐deficient nature of the copper(III) corrole. An energy level diagram was established to predict the photochemical events by using optical, emission, electrochemical, and computational data. The occurrence of charge separation from singlet excited zinc porphyrin and charge recombination to yield directly the ground state species were evident from the diagram. Femtosecond transient absorption spectroscopy studies provided spectral evidence of charge separation in the form of the zinc porphyrin radical cation and copper(II) corrole species as products. Rates of charge separation in the conjugates were found to be of the order of 10¹⁰ s^?1 and increased with increasing multiplicity of copper(III) corrole entities. The present study demonstrates the importance of copper(III) corrole as an electron acceptor in building model photosynthetic systems.     

Ultrafast Photoinduced Electron Transfer and Charge Stabilization in Donor–Acceptor Dyads Capable of Harvesting Near‐Infrared Light

To harvest energy from the near‐infrared (near‐IR) and infrared (IR) regions of the electromagnetic spectrum, which constitutes nearly 70 % of the solar radiation, there is a great demand for near‐IR and IR light‐absorbing sensitizers that are capable of undergoing ultrafast photoinduced electron transfer when connected to a suitable electron acceptor. Towards achieving this goal, in the present study, we report multistep syntheses of dyads derived from structurally modified BF₂‐chelated azadipyrromethene (ADP; to extend absorption and emission into the near‐IR region) and fullerene as electron‐donor and electron‐acceptor entities, respectively. The newly synthesized dyads were fully characterized based on optical absorbance, fluorescence, geometry optimization, and electrochemical studies. The established energy level diagram revealed the possibility of electron transfer either from the singlet excited near‐IR sensitizer or singlet excited fullerene. Femtosecond and nanosecond transient absorption studies were performed to gather evidence of excited state electron transfer and to evaluate the kinetics of charge separation and charge recombination processes. These studies revealed the occurrence of ultrafast photoinduced electron transfer leading to charge stabilization in the dyads, and populating the triplet states of ADP, benzanulated‐ADP and benzanulated thiophene‐ADP in the respective dyads, and triplet state of C₆₀ in the case of BF₂‐chelated dipyrromethene derived dyad during charge recombination. The present findings reveal that these sensitizers are suitable for harvesting light energy from the near‐IR region of the solar spectrum and for building fast‐responding optoelectronic devices operating under near‐IR radiation input.     

Photoinduced Charge Separation in a Donor–Spacer–Acceptor Dyad with N‐Annulated Perylene Donor and Methylviologen Acceptor

The first donor–acceptor species in which a strongly emissive N‐annulated perylene dye is connected to a methylviologen electron acceptor unit via its macrocyclic nitrogen atom, is prepared by a stepwise, modular procedure. The absorption spectra, redox behavior, spectroelectrochemistry and photophysical properties of this dyad and of its model species are investigated, also by pump–probe fs transient absorption spectroscopy. Photoinduced oxidative electron transfer from the excited state of the dyad, centered on the N‐annulated perylene subunit, to the appended methyviologen electron acceptor takes place in a few ps. The charge‐separated species recombines in 19 ps. Our results indicate that N‐annulated perylene can be connected to functional units by taking advantage of the macrocyclic nitrogen, an option never used until now, without losing their properties, so opening the way to new designing approaches.     

Tuning Optical and Electron Donor Properties by Peripheral Thio–Aryl Substitution of Subphthalocyanine: A New Series of Donor–Acceptor Hybrids for Photoinduced Charge Separation

Subphthalocyanine (SubPc), a unique ring‐reduced member of the common phthalocyanines family, although known for its higher absorptivity, reveals narrow absorption with peak maxima around 570 nm thus limiting its utility in light‐energy‐harvesting applications. In the present study, by peripheral thio–aryl substitution of SubPc macrocycle, the spectral properties have been modulated to extend the absorption and emission well into the visible/near‐IR region. Additionally, for α‐ring‐substituted derivatives, facile oxidation of SubPc was witnessed, thus making these derivatives better electron donors. Next, the preparation of donor–acceptor dyads containing the well‐known electron acceptor C₆₀ connected to the central boron atom of SubPc was accomplished by making use of the 1,3‐dipolar cycloaddition reaction. Control experiments and free‐energy calculations using the redox and spectral data suggested that the observed fluorescence quenching of SubPc in these dyads is due to electron transfer. Accordingly, transient spectral studies performed both in polar and nonpolar solvents conclusively proved electron transfer to be the quenching mechanism in these dyads. The measured rate constants by fitting kinetic data revealed efficient charge separation and charge recombination processes, suggesting that these dyads could be useful materials for the construction of light‐to‐electricity or light‐to‐fuel production devices.     

Biomimetic Donor–Acceptor Motifs in Conjugated Polymers for Promoting Exciton Splitting and Charge Separation

Natural photosynthesis serves as a model for energy and chemical conversions, and motivates the search of artificial systems that mimic nature′s energy‐ and electron‐transfer chains. However, bioinspired systems often suffer from the partial or even large loss of the charge separation state, and show moderate activity owing to the fundamentally different features of the multiple compounds. Herein, a selenium and cyanamide‐functionalized heptazine‐based melon (DA‐HM) is designed as a unique bioinspired donor–acceptor (D‐A) light harvester. The combination of the photosystem and electron shuttle in a single species, with both n‐ and p‐type conductivities, and extended spectral absorption, endows DA‐HM with a high efficiency in the transfer and separation of photoexcited charge carriers, resulting in photochemical activity. This work presents a unique conjugated polymeric system that shows great potential for solar‐to‐chemical conversion by artificial photosynthesis.     

Light‐Driven Charge Separation in Isoxazolidine–Perylene Bisimide Dyads

A series of arrays for light‐driven charge separation is presented, in which perylene tetracarboxylic bisimide is the light‐absorbing chromophore and electron acceptor, whereas isoxazolidines are colourless electron donors, the electron‐releasing properties of which are increased with respect to the amino group by means of the α‐effect. Charge separation (CS) in toluene over a distance ranging from ≈10 to ≈16 Å, with efficiencies of ≈95 to ≈50 % and CS lifetimes from 300 ps to 15 ns, are demonstrated. In dichloromethane the charge recombination reaction is faster than charge separation, preventing accumulation of the CS state. The effects of solvent polarity and molecular structure are discussed in the frame of current theories.     

Photoinduced Electron Transfer within a Zinc Porphyrin–Cyclobis(paraquat‐p‐phenylene) Donor–Acceptor Dyad

Understanding the mechanism of efficient photoinduced electron‐transfer processes is essential for developing molecular systems for artificial photosynthesis. Towards this goal, we describe the synthesis of a donor–acceptor dyad comprising a zinc porphyrin donor and a tetracationic cyclobis(paraquat‐p‐phenylene) (CBPQT⁴⁺) acceptor. The X‐ray crystal structure of the dyad reveals the formation of a dimeric motif through the intermolecular coordination between the triazole nitrogen and the central Zn metal of two adjacent units of the dyad. Photoinduced electron transfer within the dyad in MeCN was investigated by femtosecond and nanosecond transient absorption spectroscopy, as well as by transient EPR spectroscopy. Photoexcitation of the dyad produced a weakly coupled ZnP^+.–CBPQT^3+. spin‐correlated radical‐ion pair having a τ=146 ns lifetime and a spin–spin exchange interaction of only 0.23 mT. The long radical‐ion‐pair lifetime results from weak donor–acceptor electronic coupling as a consequence of having nine bonds between the donor and the acceptor, and the reduction in reorganization energy for electron transfer caused by charge dispersal over both paraquat units within CBPQT^3+..     

Improving the Photoinduced Charge Separation Parameters in Corrole–Perylene Carboximide Dyads by Tuning the Redox and Spectroscopic Properties of the Components

A couple of corrole–perylene carboximide dyads ( C2‐PIa and C2‐PIx ) have been synthesized and their photoreactivity has been evaluated. We aimed at obtaining better performances for photoinduced charge separation, both in terms of efficiency and in terms of lifetime, with respect to formerly studied systems. The energy level of the charge‐separated state was tuned by selecting perylene and corrole components with diverse redox and spectroscopic properties. High spectroscopic energy levels of the perylene carboximide derivatives (PIs) allow a fast charge separation to be maintained in competition with an energy‐transfer process from the PI to the corrole unit. Yields and lifetimes of charge separation in toluene are, respectively, 75 % and 2.5 μs for C2‐PIa and 65 % and 24 ns for C2‐PIx . The results and the effect of solvent polarity are discussed in the framework of current energy‐ and electron‐transfer theories.     

Ultrafast Electron Transfer from Photoexcited CdSe Quantum Dots to Methylviologen

The ultrafast charge separation at the quantum dot (QD)/molecular acceptor interface was investigated in terms of acceptor concentration and the size of the QD. Time‐resolved experiments revealed that the electron transfer (ET) from the photoexcited QD to the molecular acceptor methylviologen (MV²⁺) occurs on the fs time scale for large acceptor concentrations and that the ET rate is strongly reduced for low concentrations. The increase in the acceptor concentration is accompanied with a growth in the overlap of donor and acceptor wavefunctions, resulting in a faster reaction until the MV²⁺ concentration reaches a saturation limit of 0.3–0.4 MV²⁺ nm^?2. Moreover, we found significant QD size dependence of the ET reaction, which is explained by a change of the free energy (ΔG).     

Efficient Intramolecular Charge Transfer in Oligoyne‐Linked Donor–π–Acceptor Molecules

Studies are reported on a series of triphenylamine–(C?C)_n–2,5‐diphenyl‐1,3,4‐oxadiazole dyad molecules (n=1–4, 1 , 2 , 3 and 4 , respectively) and the related triphenylamine‐C₆H₄–(C?C)₃–oxadiazole dyad 5 . The oligoyne‐linked D–π–A (D=electron donor, A=electron acceptor) dyad systems have been synthesised by palladium‐catalysed cross‐coupling of terminal alkynyl and butadiynyl synthons with the corresponding bromoalkynyl moieties. Cyclic voltammetric studies reveal a reduction in the HOMO–LUMO gap in the series of compounds 1 – 4 as the oligoyne chain length increases, which is consistent with extended conjugation through the elongated bridges. Photophysical studies provide new insights into conjugative effects in oligoyne molecular wires. In non‐polar solvents the emission from these dyad systems has two different origins: a locally excited (LE) state, which is responsible for a π*→π fluorescence, and an intramolecular charge transfer (ICT) state, which produces charge‐transfer emission. In polar solvents the LE state emission vanishes and only ICT emission is observed. This emission displays strong solvatochromism and analysis according to the Lippert–Mataga–Oshika formalism shows significant ICT for all the luminescent compounds with high efficiency even for the longer more conjugated systems. The excited‐state properties of the dyads in non‐polar solvents vary with the extent of conjugation. For more conjugated systems a fast non‐radiative route dominates the excited‐state decay and follows the Engelman–Jortner energy gap law. The data suggest that the non‐radiative decay is driven by the weak coupling limit.     

Suppression of Charge Recombination by Auxiliary Atoms in Photoinduced Charge Separation Dynamics with Mn Oxides: A Theoretical Study

Charge separation is one of the most crucial processes in photochemical dynamics of energy conversion, widely observed ranging from water splitting in photosystem II (PSII) of plants to photoinduced oxidation reduction processes. Several basic principles, with respect to charge separation, are known, each of which suffers inherent charge recombination channels that suppress the separation efficiency. We found a charge separation mechanism in the photoinduced excited-state proton transfer dynamics from Mn oxides to organic acceptors. This mechanism is referred to as coupled proton and electron wave-packet transfer (CPEWT), which is essentially a synchronous transfer of electron wave-packets and protons through mutually different spatial channels to separated destinations passing through nonadiabatic regions, such as conical intersections, and avoided crossings. CPEWT also applies to collision-induced ground-state water splitting dynamics catalyzed by Mn₄CaO₅ cluster. For the present photoinduced charge separation dynamics by Mn oxides, we identified a dynamical mechanism of charge recombination. It takes place by passing across nonadiabatic regions, which are different from those for charge separations and lead to the excited states of the initial state before photoabsorption. This article is an overview of our work on photoinduced charge separation and associated charge recombination with an additional study. After reviewing the basic mechanisms of charge separation and recombination, we herein studied substituent effects on the suppression of such charge recombination by doping auxiliary atoms. Our illustrative systems are X–Mn(OH)₂ tied to N-methylformamidine, with X=OH, Be(OH)₃, Mg(OH)₃, Ca(OH)₃, Sr(OH)₃ along with Al(OH)₄ and Zn(OH)₃. We found that the competence of suppression of charge recombination depends significantly on the substituents. The present study should serve as a useful guiding principle in designing the relevant photocatalysts.     

Charge Separation in Graphene‐Decorated Multimodular Tris(pyrene)–Subphthalocyanine–Fullerene Donor–Acceptor Hybrids

A new approach to probe the effect of graphene on photochemical charge separation in donor–acceptor conjugates is devised. For this, multimodular donor–acceptor conjugates, composed of three molecules of pyrene, a subphthalocyanine, and a fullerene C₆₀ ((Pyr)₃SubPc‐C₆₀), have been synthesized and characterized. These systems were hybridized on few‐layer graphene through π–π stacking interactions of the three pyrene moieties. The hybrids were characterized using Raman, HRTEM, and spectroscopic and electrochemical techniques. The energy levels of the donor–acceptor conjugates were fine‐tuned upon interaction with graphene and photoinduced charge separation in the absence and presence of graphene was studied by femtosecond transient absorption spectroscopy. Accelerated charge separation and recombination was detected in these graphene‐decorated conjugates suggesting that they could be used as materials for fast‐responding optoelectronic devices and in light energy harvesting applications.     

环双(百草枯对苯撑)-双2-萘甲酸三缩四乙二醇酯二元超分子给受体体系光诱导电子转移研究

本文利用核磁氢谱、吸收光谱和荧光光谱证明了环双(百草枯对苯撑)(CBPQT)与双2-萘甲酸三缩四乙二醇(N-P₄-N)在乙腈溶液中能够形成1:1的二元超分子给受体体系.瞬态吸收光谱的研究表明该超分子体系中光诱导电子转移的速率k_CS>1.0×10⁸s^-1,电子回传的速率k_CR=1.26×10³s^-1,光诱导电子转移所生成电荷分离态的寿命长达794μs.     

Systematic Investigation of Photoinduced Electron Transfer Controlled by Internal Charge Transfer and Its Consequences for Selective PdCl2 Coordination

Fluoroionophores of fluorophore–spacer–receptor format were prepared for detection of PdCl₂ by fluorescence enhancement. The fluorescent probes 1 – 13 consist of a fluorophore group, an alkyl spacer and a dithiomaleonitrile PdCl₂ receptor. First, varying the length of the alkylene spacer (compounds 1 – 3 ) revealed a dominant through‐space pathway for oxidative photoinduced electron transfer (PET) in CH₂‐bridged dithiomaleonitrile fluoroionophores. Second, fluorescent probes 4 – 9 containing two anthracene or pyrene fragments connected through CH₂ bridges to the dithiomaleonitrile unit were synthesized. Modulation of the oxidation potential (E_Ox) through electron‐withdrawing or ‐donating groups on the anthracene moiety regulates the thermodynamic driving force for oxidative PET (ΔG_PET) in bis(anthrylmethylthio)maleonitriles and therefore the fluorescence quantum yields (Φ_f), too. The new concept was confirmed and transferred to pyrenyl ligands, and fluorescence enhancements (FE) greater than 3.2 in the presence of PdCl₂ were achieved by 7 and 8 (FE=5.4 and 5.2). Finally, for comparison, monofluorophore ligands 10 – 13 were synthesized.