Electron Donor Acceptor Molecules Research Articles

Direct observation of chirality-induced spin selectivity in electron donor-acceptor molecules.

The role of chirality in determining the spin dynamics of photoinduced electron transfer in donor-acceptor molecules remains an open question. Although chirality-induced spin selectivity (CISS) has been demonstrated in molecules bound to substrates, experimental information about whether this process influences spin dynamics in the molecules themselves is lacking. Here we used time-resolved electron paramagnetic resonance spectroscopy to show that CISS strongly influences the spin dynamics of isolated covalent donor-chiral bridge-acceptor (D-Bχ-A) molecules in which selective photoexcitation of D is followed by two rapid, sequential electron-transfer events to yield D•+-Bχ-A•-. Exploiting this phenomenon affords the possibility of using chiral molecular building blocks to control electron spin states in quantum information applications.

Naphthalimide-phenothiazine dyads: effect of conformational flexibility and matching of the energy of the charge-transfer state and the localized triplet excited state on the thermally activated delayed fluorescence.

In order to investigate the joint influence of the conformation flexibility and the matching of the energies of the charge-transfer (CT) and the localized triplet excited (3LE) states on the thermally activated delayed fluorescence (TADF) in electron donor–acceptor molecules, a series of compact electron donor–acceptor dyads and a triad were prepared, with naphthalimide (NI) as electron acceptor and phenothiazine (PTZ) as electron donor. The NI and PTZ moieties are either directly connected at the 3-position of NI and the N-position of the PTZ moiety via a C–N single bond, or they are linked through a phenyl group. The tuning of the energy order of the CT and LE states is achieved by oxidation of the PTZ unit into the corresponding sulfoxide, whereas conformation restriction is imposed by introducing ortho-methyl substituents on the phenyl linker, so that the coupling magnitude between the CT and the 3LE states can be controlled. The singlet oxygen quantum yield (ΦΔ) of NI-PTZ is moderate in n-hexane (HEX, ΦΔ = 19%). TADF was observed for the dyads, the biexponential luminescence lifetime are 16.0 ns (99.9%)/14.4 μs (0.1%) for the dyad and 7.2 ns (99.6%)/2.0 μs (0.4%) for the triad. Triplet state was observed in the nanosecond transient absorption spectra with lifetimes in the 4–48 μs range. Computational investigations show that the orthogonal electron donor–acceptor molecular structure is beneficial for TADF. These calculations indicate small energetic difference between the 3LE and 3CT states, which are helpful for interpreting the ns-TA spectra and the origins of TADF in NI-PTZ, which is ultimately due to the small energetic difference between the 3LE and 3CT states. Conversely, NI-PTZ-O, which has a higher CT state and bears a much more stabilized 3LE state, does not show TADF.

Charge transfer of ZnTPP/C60 cocrystal-hybridized bioimplants satisfies osteosarcoma eradication with antitumoral, antibacterial and osteogenic performances

Inferior bone-tissue regeneration, rapid tumor recurrence, and severe bacterial infection are the dominating challenges of osteosarcoma resection, which result in the failure of surgical intervention, and even amputation in serious circumstances. Herein, the multifunctional scaffolds (termed as ZCBS) are elaborately designed by in-situ integration of two-dimensional (2D) cocrystals with bioactive-glass scaffolds (BS) for significant osteosarcoma ablation, bacterial sterilization, and neo-bone regeneration. The efficient charge transfer between electron donor (zinc (II) tetraphenylporphyrin, ZnTPP) and acceptor (fullerene, C60) molecules of 2D cocrystals facilitates ZCBS with prominent photothermal-conversion performance for osteosarcoma elimination and bacterial eradication. Meanwhile, the gradual release of C60 and Zn2+ is beneficial to the reinforced antibacterial capability of ZCBS. Furthermore, the macropore structures and progressive release of Zn2+, Ca2+, and PO43- endow ZCBS with excellent osteogenic performance in promoting bone-tissue regeneration. Collectively, the engineered ZCBS bioscaffolds feature intrinsically multifunctional properties including antitumor, antibacterial, and osteogenic bioactivities, which support ZCBS for efficient osteosarcoma eradication, antibacterial treatment, and bone-tissue regeneration both in vitro and in vivo. Therefore, the developed “cocrystal engineering” strategy towards ZCBS with multifunctional bioactivities offer a competitive approach for osteosarcoma- and bacterial infection-induced bone regeneration.

Caging and photo-triggered uncaging of singlet oxygen by excited state engineering of electron donor–acceptor-linked molecular sensors

Singlet oxygen (1O2), one of the most sought-after species in oxidative chemical reactions and photodynamic cancer therapy, is activated and neutralized in the atmosphere and living cells. It is essential to see "when" and "where" 1O2 is produced and delivered to understand and utilize it. There is an increasing demand for molecular sensor tools to capture, store, and supply 1O2, controlled by light and engineered singlet and triplet states, indicating the 1O2-capturing-releasing state. Here, we demonstrate the outstanding potential of an aminocoumarin-methylanthracene-based electron donor–acceptor molecule (1). Spectroscopic measurements confirm the formation of an endoperoxide (1-O2) which is not strongly fluorescent and remarkably different from previously reported 1O2 sensor molecules. Moreover, the photoexcitation on the dye in 1-O2 triggers fluorescence enhancement by the oxidative rearrangement and a competing 1O2 release. The unique ability of 1 will pave the way for the spatially and temporally controlled utilization of 1O2 in various areas such as chemical reactions and phototherapies.

Theoretical exploration of 1,3-Indanedione as electron acceptor-cum-anchoring group for designing sensitizers towards DSSC applications

The present work highlights the DFT and TD-DFT calculations of a few organic sensitizers designed based on a new electron-acceptor, 1,3-indanedione, which is a well-known electron-acceptor for designing new electron donor–acceptor molecules. Nine organic sensitizers (GR1-9) have been designed based on a modified 1,3-indanedione electron-acceptor and conventional electron-donor moieties. Optimization studies reveal that all dyes have twisted configurations, and therefore, the aggregation on the TiO2 semiconductor is expected to be less. GR2 dye shows the smallest energy gap, 2.43 eV, as compared to others which indicates an effective electronic excitation and injection. The dyes’ energy levels are compatible with the conduction band of TiO2 and redox potentials of the redox couple. Thermodynamic parameters indicate that the GR1, GR2, and GR5 dyes regenerate at a faster rate as compared to the other dyes. Further, NBO calculations demonstrate the dipolar nature of the designed molecules. Electronic spectra of dyes were red-shifted by 18–29 nm in acetonitrile solvent, which shifts further towards red-region upon adsorbing on to titania. The absorption spectrum of the GR1@TiO2 system shows a remarkable shift, 92 nm, and extends to the NIR region. The electron density of LUMO and LUMO + 1 is majorly confined to TiO2 moiety upon binding, which indicates complete electron donation from dye to the TiO2. Overall, our studies reveal that the 1,3-indanedione skeleton has the potential to serve as an electron-acceptor in designing new organic sensitizers for DSSCs. Therefore by conjugating conventional electron-donors with the 1,3-indanedione electron-acceptor, a new class of organic sensitizers can perhaps be synthesized for DSSC applications.

New near-infrared absorbing conjugated electron donor–acceptor molecules with a fused tetrathiafulvalene–naphthalene diimide framework

New semiconducting D–A molecules with a fused tetrathiafulvalene–naphthalene diimide framework show near-infrared absorptions and emissions with maxima up to 1062 nm and quantum yields up to 1.64%.

Excited-State Symmetry Breaking and the Laporte Rule.

Excited-state symmetry breaking (ES-SB) is common to a large number of multibranched electron donor-acceptor (DA) molecules in polar environments. During this process, the electronic excitation, originally evenly distributed over the molecule, localizes, at least partially, on one branch. Due to the absence of an unambiguous spectroscopic signature in the UV-vis region, electronic transient absorption (TA) has not been the method of choice for real-time observation of this phenomenon. Herein, we demonstrate that the Laporte rule, which states that one-photon transitions conserving parity are forbidden in centrosymmetric molecules, provides such clear signature of ES-SB in electronic TA spectroscopy. Using a dicyanoanthracene-based D-A-D dye, we show that transitions from the S1 state of this molecule, which are initially Laporte forbidden, become allowed upon ES-SB. This leads to the rise of new TA bands, whose intensity provides a direct measure of the extent of asymmetry in the excited state.

Synthesis and Electronic Properties of Directly Linked Dihydrodiazatetracene Dimers.

5,12-Dihydro-5,12-diazatetracene (DHDAT) dimers with different substitution patterns are synthesized: a symmetric one with a C-C bond between the monomer units (1) and two asymmetric ones with a C-N bond between the monomer units (2 and 3). The DHDAT units are planar in the C-C linked dimer 1 but perpendicularly oriented in the C-N linked dimers 2 and 3 (from X-ray analysis). The electronic ground-state interaction between the two units is large in 1 and small in 2 and 3. The emission behavior of 3 is different from that of other dimers and its monomer; it displays positive solvatochromism, characteristic for electron donor-acceptor molecules, despite its donor-donor type structure. Compound 3 exhibits a unique multi-step thermochromic emission behavior. The emission behavior is attributed to the asymmetric distribution of the HOMO and LUMO of DHDAT.

Selective and rapid detection of nerve agent simulants by polymer fibers with a fluorescent chemosensor in gas phase

Nerve agents (NAs) are the most feared and unpredictable chemical warfare agents (CWAs) on the battlefield and in the hands of terrorists. To cope with chemical terrorism or chemical warfare, it is urgent to establish a rapid and reliable detection method for NAs. In this work, we have developed two 6-aminoquinolin-2-yl-methanols (AQmol-1 and AQmol-2), which can selectively detect two nerve agent simulants, diisopropylfluorophosphate (DFP) and diethylchlorophosphate (DCP), over other organophosphate compunds. In this sensing reaction, the hydroxy group of two sensors is phosphorylated by DFP/DCP and simulanutaus protonation of nitrigen of the quinoline to form a stronger electron donor-acceptor (DA) molecule over the sensor molecule, giving corresponding fluorescence response. Therein, AQmol-2 diplays ratiometirc fluorescence response towards DFP/DCP with a lower limit of detection (LOD) 0.18 μM or 0.16 μM, respectively. Furthermore, two AQmol-2 embedded solid polymers, membrane and fibers (the diameter <1 μm), were fabricated for detection of DFP/DCP vapor. Both AQmol-2-embedded solid-state polymers can detect DFP/DCP vapor more rapidly over those (about 30 min) in solutions. The polymer fibers from an electrospaning technology give more rapid response toward DCP (within 20 s) over that (3 min) of the membrane. Therefore, AQmol-2-embedded polymer nanofibrosis is promissing way for selective and rapid detection of nerve agents in gas phase.

Effect of Electron-Nuclear Hyperfine Interactions on Multiple-Quantum Coherences in Photogenerated Covalent Radical (Qubit) Pairs.

Ultrafast photodriven electron transfer reactions starting from an excited singlet state in an organic donor-acceptor molecule can generate a spin-correlated radical pair (RP) with an initially entangled spin state that may prove useful as a two-qubit pair in quantum information protocols. Here we investigate the effects of modulating electron-nuclear hyperfine coupling by rapidly transferring an electron between two equivalent sites comprising the reduced acceptor of the RP. A covalent electron donor-acceptor molecule including a tetrathiafulvalene (TTF) donor, a 4-aminonaphthalene-1,8-imide (ANI) chromophoric primary acceptor, and an m-xylene bridged cyclophane having two equivalent pyromellitimides (PI2), TTF-ANI-PI2, as a secondary acceptor was synthesized along with an analogous molecule having one pyromellitimide (PI) acceptor, TTF-ANI-PI. Photoexcitation of ANI within each molecule results in sub-nanosecond formation of TTF+•-ANI-PI-• and TTF+•-ANI-PI2-•. The effect of reducing electron-nuclear hyperfine interactions in TTF+•-ANI-PI2-• relative to TTF+•-ANI-PI-• on decoherence of multiple-quantum coherences has been measured by pulse-EPR spectroscopy. This contribution is especially relevant in the absence of modulation of exchange or dipolar interactions, as with the RP at a fixed distance in the molecules in this work. The theoretical prediction of the contribution from an ensemble of hyperfine interactions to decoherence in these RPs is shown to be less than the full width at half-maximum of the quantum beat frequencies measured experimentally. Pulse bandwidth and off-resonant excitation by square microwave pulses are proposed as larger contributors to decoherence in these molecules than the hyperfine interactions, and specific pulse shapes relevant to arbitrary waveform generation are introduced.

Covalent Radical Pairs as Spin Qubits: Influence of Rapid Electron Motion between Two Equivalent Sites on Spin Coherence.

Ultrafast photodriven electron transfer reactions starting from an excited singlet state in an organic donor-acceptor molecule generate a radical pair (RP) in which the two spins are initially entangled and, in principle, can serve as coupled spin qubits in quantum information science (QIS) applications, provided that spin coherence lifetimes in these RPs are long. Here we investigate the effects of electron transfer between two equivalent sites comprising the reduced acceptor of the RP. A covalent electron donor-acceptor molecule (D-C-A24+) including a p-methoxyaniline donor (D), a 4-aminonaphthalene-1,8-imide chromophoric primary acceptor (C), and a m-xylene bridged cyclophane having two equivalent phenyl-extended viologens (A24+) as a secondary acceptor was synthesized along with the analogous molecule having one phenyl-extended viologen acceptor and a second, more difficult to reduce 2,5-dimethoxyphenyl-extended viologen in a very similar cyclophane structure (D-C-A4+). Photoexcitation of C within each molecule results in subnanosecond formation of D+•-C-A23+• and D+•-C-A3+•. The spin dynamics of these RPs were characterized by time-resolved EPR spectroscopy and magnetic field effects on the RP yield in both CH3CN and CD3CN. The data show that rapid electron hopping within A23+• promotes spin decoherence in D+•-C-A23+• relative to D+•-C-A3+• having a monomeric acceptor, while the interaction of the RP electron spins with the nuclear spins of the solvent have little or no effect on the spin dynamics. These observations provide important information for designing and understanding novel molecular assemblies of spin qubits with long coherence times for QIS applications.

Nitrile Vibration Reports Induced Electric Field and Delocalization of Electron in the Charge-Transfer State of Aryl Nitriles.

An electric field is created upon photoinduced charge separation in electron donor-acceptor (D-A) molecules. The photophysics of a prototypical D-A molecule, 4-(dimethylamino)-benzonitrile (DMABN), has been under extensive investigation for decades. Here, by using the framework of the vibrational Stark effect (VSE), we show that the nitrile vibration quantifies a significant induced electric field in the intramolecular charge-transfer state of DMABN. We further demonstrate that such a phenomenon can be observed in a structurally similar aryl nitrile and that the VSE depends on solvent polarity due to dielectric screening. Our current work shows how the superb sensitivity of the nitrile vibration can be used to identify the nature of electron delocalization and quantify the induced electric field in photoinduced charge transfer processes.

Understanding the Charge Transfer at the Interface of Electron Donors and Acceptors: TTF-TCNQ as an Example.

Charge transfer between an electron donor and an electron acceptor is widely accepted as being independent of their relative configurations if the interaction between them is weak; however, the limit of this concept for an interacting system has not yet been well established. Our study of prototypical electron donor-acceptor molecules, tetrathiafulvalene-tetracyanoquinodimethane, using density functional theory based on an advanced functional, clearly demonstrates that for interacting molecules, their configurational arrangement is as important as their individual electronic properties in the asymptotic limit to determine the charge transfer direction. For the first time, we demonstrate that by changing their relative orientation, one can reverse the charge transfer direction of the pair, causing the molecules to exchange roles as donor and acceptor. Our theory has important implications for understanding the interfacial charge-transfer mechanism of hybrid systems and related phenomena.

Donor-Acceptor Properties of a Single-Molecule Altered by On-Surface Complex Formation.

Electron donor-acceptor molecules are of outstanding interest in molecular electronics and organic solar cells for their intramolecular charge transfer controlled via electrical or optical excitation. The preservation of their electronic character in the ground state upon adsorption on a surface is cardinal for their implementation in such single-molecule devices. Here, we investigate by atomic force microscopy and scanning tunneling microscopy a prototypical system consisting of a π-conjugated tetrathiafulvalene-fused dipyridophenazine molecule adsorbed on thin NaCl films on Cu(111). Depending on the adsorption site, the molecule is found either in a nearly undisturbed free state or in a bound state. In the latter case, the molecule adopts a specific adsorption site, leading to the formation of a chelate complex with a single Na+ alkali cation pulled out from the insulating film. Although expected to be electronically decoupled, the charge distribution of the complex is drastically modified, leading to the loss of the intrinsic donor-acceptor character. The chelate complex formation is reversible with respect to lateral manipulations, enabling tunable donor-acceptor molecular switches activated by on-surface coordination.

Substitution Effects on the Photoinduced Charge-Transfer Properties of Novel Perylene-3,4,9,10-tetracarboxylic Acid Derivatives.

We report here the synthesis and photophysical study of a series of electron donor–acceptor molecules, in which electron-donating 4-methoxyphenoxy groups are attached to the 1,7-bay positions of four different perylene tetracarboxylic acid derivatives, namely, perylene tetraesters 1, perylene monoimide diesters 2, perylene bisimides 3, and perylene monobenzimidazole monoimides 4. These perylene derivatives are used because of their increasing order of electron-accepting capability upon moving from 1 to 4. Two additional donor–acceptor molecules are synthesized by linking electron-donating 4-methoxyphenyl groups to the imide position of perylene monoimide diester 2 and perylene bisimide 3. The motivation for this study is to achieve a good control over the photoinduced charge-transfer (CT) process in perylene-based systems by altering the position of electron donors and tuning the electron deficiency of perylene core. A comprehensive study of the photophysical properties of these molecules has shown a highly systematic trend in the magnitude of CT as a function of increased electron deficiency of the perylene core and solvent polarity. Importantly, just by changing the attachment of electron-donating group from “bay” to “imide” position, we are able to block the CT process. This implies that the positioning of the electron donor at the perylene core strongly influences the kinetics of the photoinduced CT process. In these compounds, the CT process is characterized by the quenching of fluorescence and singlet excited-state lifetimes as compared to model compounds bearing non-electron-donating 4-tert-butylphenoxy groups. Transient absorption spectroscopy did not reveal spectra of CT states. This most likely implies that the CT state is not accumulated, because of the faster charge recombination.

Spin Polarization Transfer from a Photogenerated Radical Ion Pair to a Stable Radical Controlled by Charge Recombination

Photoexcitation of electron donor-acceptor molecules frequently produces radical ion pairs with well-defined initial spin-polarized states that have attracted significant interest for spintronics. Transfer of this initial spin polarization to a stable radical is predicted to depend on the rates of the radical ion pair recombination reactions, but this prediction has not been tested experimentally. In this study, a stable radical/electron donor/chromophore/electron acceptor molecule, BDPA•-mPD-ANI-NDI, where BDPA• is α,γ-bisdiphenylene-β-phenylallyl, mPD is m-phenylenediamine, ANI is 4-aminonaphthalene-1,8-dicarboximide, and NDI is naphthalene-1,4:5,8-bis(dicarboximide), was synthesized. Photoexcitation of ANI produces the triradical BDPA•-mPD+•-ANI-NDI-• in which the mPD+•-ANI-NDI-• radical ion pair is spin coupled to the BDPA• stable radical. BDPA•-mPD+•-ANI-NDI-• and its counterpart lacking the stable radical are found to exhibit spin-selective charge recombination in which the triplet radical ion pair 3(mPD+•-ANI-NDI-•) is in equilibrium with the 3*NDI charge recombination product. Time-resolved EPR measurements show that this process is associated with an inversion of the sign of the polarization transferred to BDPA• over time. The polarization transfer rates are found to be strongly solvent dependent, as shifts in this equilibrium affect the spin dynamics. These results demonstrate that even small changes in electron transfer dynamics can have a large effect on the spin dynamics of photogenerated multispin systems.

Zero Quantum Coherence in a Series of Covalent Spin-Correlated Radical Pairs

Photoinitiated subnanosecond electron transfer within covalently linked electron donor-acceptor molecules can result in the formation of a spin-correlated radical pair (SCRP) with a well-defined initial singlet spin configuration. Subsequent coherent mixing between the SCRP singlet and triplet ms = 0 spin states, the so-called zero quantum coherence (ZQC), is of potential interest in quantum information processing applications because the ZQC can be probed using pulse electron paramagnetic resonance (pulse-EPR) techniques. Here, pulse-EPR spectroscopy is utilized to examine the ZQC oscillation frequencies and ZQC dephasing in three structurally well-defined D-A systems. While transitions between the singlet and triplet ms = 0 spin states are formally forbidden (Δms = 0), they can be addressed using specific microwave pulse turning angles to map information from the ZQC onto observable single quantum coherences. In addition, by using structural variations to tune the singlet-triplet energy gap, the ZQC frequencies determined for this series of molecules indicate a stronger dependence on the electronic g-factor than on electron-nuclear hyperfine interactions.

Chemical Self-Doping of Organic Nanoribbons for High Conductivity and Potential Application as Chemiresistive Sensor.

Intrinsically low electrical conductivity of organic semiconductors hinders their further development into practical electronic devices. Herein, we report on an efficient chemical self-doping to increase the conductivity through one-dimensional stacking arrangement of electron donor-acceptor (D-A) molecules. The D-A molecule employed was a 1-methylpiperidine-substituted perylene tetracarboxylic diimide (MP-PTCDI), of which the methylpiperidine moiety is a strong electron donor, and can form a charge transfer complex with PTCDI (acting as the acceptor), generating anionic radical of PTCDI as evidenced in molecular solutions. Upon self-assembling into nanoribbons through columnar π-π stacking, the intermolecular charge transfer interaction between methylpiperidine and PTCDI would be enhanced, and the electrons generated are delocalized along the π-π stacking of PTCDIs, leading to enhancement in conductivity. The conductive fiber materials thus produced can potentially be used as chemiresistive sensor for vapor detection of electron deficient chemicals such as hydrogen peroxide, taking advantage of the large surface area of nanofibers. As a major component of improvised explosives, hydrogen peroxide remains a critical signature chemical for public safety screening and monitoring.

Photoinduced Electron Transfer within Supramolecular Donor-Acceptor Peptide Nanostructures under Aqueous Conditions.

We report the synthesis, self-assembly, and electron transfer capabilities of peptide-based electron donor-acceptor molecules and supramolecular nanostructures. These modified peptides contain π-conjugated oligothiophene electron donor cores that are peripherally substituted with naphthalene diimide electron acceptors installed via imidation of site-specific lysine residues. These molecules self-assemble into one-dimensional nanostructures in aqueous media, as shown through steady-state absorption, photoluminescence, and circular dichroism spectra, as well as transmission electron microscopy. Excitation of the oligothiophene donor moieties results in electron transfer to the acceptor units, ultimately creating polar, charge-separated states that persist for over a nanosecond as observed with transient absorption spectroscopy. This study demonstrates how transient electric fields can be engineered into aqueous nanomaterials of biomedical relevance through external, temporally controlled photonic inputs.

Organic Electron Donor–Acceptor Photoredox Catalysts: Enhanced Catalytic Efficiency toward Controlled Radical Polymerization

In this study, we designed and synthesized novel organic single electron donor-acceptor molecules containing a free base porphyrin and a thiocarbonylthio group. The porphyrin acts as a light-harvesting antenna and donates an excited electron upon light irradiation to the electron-accepting thiocarbonylthio group. The excited electronic state of the donor-acceptor generates a radical from the thiocarbonylthio compound to activate a living radical polymerization in the presence of monomers. Thus, these donor-acceptor systems play the roles of highly efficient photoredox catalysts and radical initiators. The presence of both donor and acceptor in a single molecule enhanced the electron transfer efficiency in comparison to the donor/acceptor mixture and consequently greatly increased polymerization rates of vinyl monomers under visible light irradiation. The polymerizations mediated by these electron donor-acceptor photoredox catalysts were investigated under green (λmax = 530 nm, 0.7 mW/cm2) and red (λmax = 635 nm, 0.7 mW/cm2) lights, which exhibited great control over molecular weights, molecular weight distributions, and end-group functionalities.