Donor-acceptor Complexes Research Articles

Conformational dynamics modulating electron transfer.

Diffusional dynamics of the donor-acceptor distance are responsible for the appearance of a new time scale of diffusion over the distance of electronic tunneling in electron-transfer reactions. The distance dynamics compete with the medium polarization dynamics in the dynamics-controlled electron-transfer kinetics. The pre-exponential factor of the electron-transfer rate constant switches, at the crossover distance, between a distance-independent, dynamics-controlled plateau and exponential distance decay. The crossover between two regimes is controlled by an effective relaxation time slowed down by a factor exponentially depending on the variance of the donor-acceptor displacement. Flexible donor-acceptor complexes must show a greater tendency for dynamics-controlled electron transfer. Energy chains based on electron transport are best designed by placing the redox cofactors near the crossover distance.

Charge transfer materials fabricated by supramolecular strategy with a broad emission spectrum for realizing information encryption

Novel charge transfer (CT) materials with a broad emission spectrum have been successfully developed in aqueous phase based on supramolecular self-assembly between different electron donors and electron acceptors. For electron donor BrAc (dimethylacridine-based derivative) with excellent self-aggregation property, it can co-aggregate with various electron acceptors to form nanoaggregates in water, leading to the multicolor CT emission with long luminescence lifetime. The emission colors cover from deep blue (425 nm) to orange (550 nm) region with lifetimes in the range of 61.2 ns–605.1 ns. As for the analogous donor (QaAc), which self-aggregation ability was poor, water-soluble pillar[5]arene (WP5) can be introduced to promote the aggregation to induce the similar CT emission. Moreover, reversible control of the CT emission and lifetime of BrAc-3TPYMB can be easily achieved via alternating addition of trifluoroacetic acid and triethylamine. Meanwhile, the donor–acceptor complex with white light emission can be conveniently constructed by incorporating three different acceptor molecules (3TMB, 3TPYMB, and TRZF2) with appropriate ratios. In addition, benefiting from the strong CT emission when donor and acceptor are close enough, thermal writing of quick response code and further information decryption has been successfully realized.

Crystallographic Characterisation of Organolithium and Organomagnesium Intermediates in Reactions of Aldehydes and Ketones

AbstractWe report reactions of LiNacNac and NacNacMg(TMP) with common organic substrates (TMP=2,2,6,6‐tetramethylpiperidide). Using bulky β‐diketiminate compound NacNac (Me, Dipp), we have trapped metalated intermediates amenable to X‐ray crystallographic study. LiNacNac and acetone produced the NacNac‐free hexameric diacetone alkoxide [{LiO(MeC(=O)CH2C(Me)2}6]; whereas pinacolone gave the simple monomeric donor–acceptor complex [Li{(MeCN‐2,6‐iPr2C6H3)2CH}{O=C(Me)tBu}]. Benzaldehyde produced dimeric [Li{(MeCN‐2,6‐iPr2C6H3)2CC(=O)Ph}{O=C(Ph)OCH2Ph}]2, where one benzaldehyde molecule has inserted in to the γ‐carbon position of the NacNac ligand, with a molecule of benzyl benzoate derived from a Tishchenko reaction of the aldehyde acting as a terminal donor to lithium. Tetranuclear, mixed dimer [{LiO(MeCN‐2,6‐iPr2C6H3)2CH‐CH(Ph)}2{LiO(PhC(=O)}2] containing the same modified NacNac ligand was the fortuitous product from repeating the reaction of LiNacNac and benzaldehyde in a solution presumably contaminated with benzoic acid. Combining NacNacMg(TMP) with pinacolone affords monomeric heteroleptic [Mg{(MeCN‐2,6‐iPr2C6H3)2CH}{OC(tBu)(Me)CH2C(=O)tBu}] with an aldolate constituting the second anion. Completing the set is dimeric [Mg{(MeCN‐2,6‐iPr2C6H3)2CH}{O(C=CH2)Ph}2], where the enolate derived from acetophenone bridges the magnesium centres.

Cyclo[18]carbon‐A new class of electron acceptor for organic solar cells applications

The all-carboatomic ring, cyclo[18]carbon (C18), has the potential to act as an electron acceptor due to promising electronic and optical properties. In this study, we first illustrated the geometrical, electronic, and excited-state properties of C18 using various hybrid and long-range corrected density functional theory (DFT) methods. Further, we studied the nature of intermolecular interactions between dimers of C18 to gain insights into packing configurations of cyclo[18] in dimer and trimer configurations. Also, using the state-of-the-art DFT methods, we have reported the thorough characterization of the lowest excited-state (i.e. charge-transfer state) in various donor-acceptor model complexes based on pentacene and C18. We established an interplay between the molecular packing of C18 and pentacene molecules on the energy of charge transfer state. All these results could help in the designing of more efficient organic solar cells.

Visible-Light-Induced [4+1] Cyclization-Aromatization of Acylsilanes and α,β-Unsaturated Ketones

Visible-Light-Induced [4+1] Cyclization-Aromatization of Acylsilanes and α,β-Unsaturated Ketones

Recent Advances in Employing Catalytic Donors and Acceptors in Electron Donor–Acceptor Complex Photochemistry

Electron donor-acceptor (EDA) complexes provide a means to initiate radical reactions under visible light irradiation using substrates that do not absorb visible light individually. Catalytic approaches to complex formation are vital for advancing this synthetic strategy as it decouples the complexation and photogeneration of radicals from substrate functionalization, a limitation inherent to stoichiometric approaches that restricts structural diversity. This Synopsis highlights recent developments in EDA complex photochemistry in which either the donor or acceptor are employed catalytically.

Exchange Spin Coupling in Optically Excited States.

In optically excited states in molecules and materials, coupling between local electron spins plays an important role for their photoemission properties and is interesting for potential applications in quantum information processing. Recently, it was experimentally demonstrated that the photogenerated local spins in donor-acceptor metal complexes can interact with the spin of an attached radical, resulting in a spin-coupling-dependent mixing of excited doublet states, which controls the local spin density distributions on donor, acceptor, and radical subunits in optically excited states. In this work, we propose an energy-difference scheme to evaluate spin coupling in optically excited states, using unrestricted and spin-flip simplified time-dependent density functional theory. We apply it to three platinum complexes which have been studied experimentally to validate our methodology. We find that all computed coupling constants are in excellent agreement with the experimental data. In addition, we show that the spin coupling between donor and acceptor in the optically excited state can be fine-tuned by replacing platinum with palladium and zinc in the structure. Besides the two previously discussed excited doublet states (one bright and one dark), our calculations reveal a third, bright excited doublet state which was not considered previously. This third state possesses the inverse spin polarization on donor and acceptor with respect to the previously studied bright doublet state and is by an order of magnitude brighter, which might be interesting for optically controlling local spin polarizations with potential applications in spin-only information transfer and manipulation of connected qubits.

Iodine Uptake by Zr-/Hf-Based UiO-66 Materials: The Influence of Metal Substitution on Iodine Evolution.

Many works reported the encapsulation of iodine in metal-organic frameworks as well as the I2 → I3- chemical conversion. This transformation has been examined by adsorbing gaseous iodine on a series of UiO-66 materials and the different Hf/Zr metal ratios (0-100% Hf) were evaluated during the evolution of I2 into I3-. The influence of the hafnium content on the UiO-66 structure was highlighted by PXRD, SEM images, and gas sorption tests. The UiO-66(Hf) presented smaller lattice parameter (a = 20.7232 Å), higher crystallite size (0.18 ≤ Φ ≤ 3.33 μm), and smaller SSABET (818 m2·g-1) when compared to its parent UiO-66(Zr) ─ a = 20.7696 Å, 100 ≤ Φ ≤ 250 nm, and SSABET = 1262 m2·g-1. The effect of replacing Zr atoms by Hf in the physical properties of the UiO-66 was deeply evaluated by a spectroscopic study using UV-vis, FTIR, and Raman characterizations. In this case, the Hf presence reduced the band gap of the UiO-66, from 4.07 eV in UiO-66(Zr) to 3.98 eV in UiO-66(Hf). Furthermore, the UiO-66(Hf) showed a blue shift for several FTIR and Raman bands, indicating a stiffening on the implied interatomic bonds when comparing to UiO-66(Zr) spectra. Hafnium was found to clearly favor the capture of iodine [285 g·mol-1, against 230 g·mol-1 for UiO-66(Zr)] and the kinetic evolution of I2 into I3- after 16 h of I2 filtration. Three iodine species were typically identified by Raman spectroscopy and chemometric analysis. These species are as follows: "free" I2 (206 cm-1), "perturbed" I2 (173 cm-1), and I3- (115 and 141 cm-1). It was also verified, by FTIR spectroscopy, that the oxo and hydroxyl groups of the inorganic [M6O4(OH)4] (M = Zr, Hf) cluster were perturbed after the adsorption of I2 into UiO-66(Hf), which was ascribed to the higher acid character of Hf. Finally, with that in mind and considering that the EPR results discard the possibility of a redox phenomenon involving the tetravalent cations (Hf4+ or Zr4+), a mechanism was proposed for the conversion of I2 into I3- in UiO-66─based on an electron donor-acceptor complex between the aromatic ring of the BDC linker and the I2 molecule.

Alkyl/Glycosyl Sulfoxides as Radical Precursors and Their Use in the Synthesis of Pyridine Derivatives.

We report here the use of simple and readily available alkyl sulfoxides as precursors to radicals and their application in the preparation of pyridine derivatives. We show that alkyl sulfoxides, N-methoxy pyridinium salts and fluoride anions form electron donor-acceptor (EDA) complexes in solution, which, upon visible light irradiation, undergo a radical chain process to afford various pyridine derivatives smoothly. This reaction displays broad scope with respect to both sulfoxides and N-methoxy pyridiniums. The synthetic versatility of sulfoxides as a handle in chemistry adds to their power as radical precursors. Glycosyl sulfoxides are converted to the corresponding pyridyl C-glycosides with high stereoselectivities. Computational and experimental studies provide insights into the reaction mechanism.

Visible-Light-Promoted Cross-Coupling of O-Aryl Oximes and Nitrostyrenes to Access Cyanoalkylated Alkenes.

A photoinduced, photocatalyst-free cyanoalkylation of nitrostyenes was explored, affording a series of cyanoalkylated alkenes in moderate to good yields. Mechanistic studies reveal that an electron donor-acceptor complex formed between O-aryl oximes and DIPEA is presumably involved in this process. The excellent functional group compatibility of this newly designed synthetic protocol allows for cyanoalkylation of structurally varied substrates, which offers an eco-friendly pathway for the assembly of cyanoalkylated alkenes.

Donor Acceptor Complexes between the Chalcogen Fluorides SF2, SeF2, SeF4and TeF4and an N‐Heterocyclic Carbene

The majority of binary chalcogen fluorides are fiercely reactive and extremely difficult to handle. Here, we show that access to crystalline donor‐acceptor complexes between chalcogen difluorides (sulfur, selenium) and tetrafluorides (selenium, tellurium) with the N‐heterocyclic carbene (NHC) 1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene (IPr) is possible conveniently and safely without the need to generate the highly unstable EF2 (E=S, Se) or the very toxic and corrosive SeF4.

Visible-Light-Driven Thioesterification of Aryl Halides with Potassium Thiocarboxylates: Transition-Metal Catalyst-Free Incorporation of Sulfur Functionalities into an Aromatic Ring.

Reactions of acceptor-substituted aryl iodides and bromides with potassium thiocarboxylates under white light irradiation allow for the preparation of S-aryl thioesters including synthetically versatile S-aryl thioacetates. This transition-metal and external photocatalyst-free method features extremely mild reaction conditions compared with those used in transition-metal-catalyzed protocols. Reactions proceed via the initial formation of an electron donor-acceptor (EDA) complex in the ground state, which was supported by UV-vis spectra. Electron paramagnetic resonance (EPR) spin-trapping experiments using phenyl-N-tert-butylnitrone (PBN) have revealed the radical nature of the reaction.

Visible-Light-Promoted Desulfurative Alkylation of Alkyl Thianthrenium Salts with Activated Olefins.

Reactions involving an alkyl radical generated from a primary alcohol by photochemistry are rare and challenging. Herein, we present a photocatalyst- and metal-free approach that enables the generation of an alkyl radical from the corresponding alcohol and the subsequent C(sp3)-C(sp3) bond formation with activated olefin, via an alkyl thianthrenium salt/Hantzsch ester electron donor-acceptor complex. This protocol for the conversion of a C-OH bond to a C-C bond is highly functionality tolerant and can successfully be used in late-stage functionalization of pharmaceuticals.

Polyimide Copolymers and Nanocomposites: A Review of the Synergistic Effects of the Constituents on the Fire-Retardancy Behavior

Carbon-based polymer can catch fire when used as cathode material in batteries and supercapacitors, due to short circuiting. Polyimide is known to exhibit flame retardancy by forming char layer in condensed phase. The high char yield of polyimide is attributed to its aromatic nature and the existence of a donor–acceptor complex in its backbone. Fabrication of hybrid polyimide material can provide better protection against fire based on multiple fire-retardancy mechanisms. Nanocomposites generally show a significant enhancement in mechanical, electrical, and thermal properties. Nanoparticles, such as graphene and carbon nanotubes, can enhance flame retardancy in condensed phase by forming a dense char layer. Silicone-based materials can also provide fire retardancy in condensed phase by a similar mechanism as polyimide. However, some inorganic fire retardants, such as phosphazene, can enhance flame retardancy in gaseous phase by releasing flame inhibiting radicals. The flame inhibiting radicals generated by phosphazene are released into the gaseous phase during combustion. A hybrid system constituted of polyimide, silicone-based additives, and phosphazene would provide significant improvement in flame retardancy in both the condensed phase and gas phase. In this review, several flame-retardant polyimide-based systems are described. This review which focuses on the various combinations of polyimide and other candidate fire-retardant materials would shed light on the nature of an effective multifunctional flame-retardant hybrid materials.

Unraveling the formation mechanism of hybrid Zr conversion coating on advanced high strength stainless steels

This research unravels the formation mechanism of a hybrid conversion treatment including the well-established Zr conversion coating with a silane-based organic additive and Cu-based inorganic additive. The deposition mechanism of this coating was investigated on the thermal oxide film of Advanced High Strength Stainless Steels (AHSSS). This coating has been characterized using advanced surface analytical techniques such as XPS, FEG-AES, GDOES, and ToF-SIMS. The results showed that the simultaneous presence of these two additives results in the formation of a donor-acceptor complex between amine groups and Cu ions. The final coating contains Cu oxide together with a Cu-aminosilane complex, Zr oxide deposited mainly around Cu oxide and the aminosilane layer on the outer surface.

Nickel-Catalyzed Three-Component Alkylacylation of Alkenes Enabled by a Photoactive Electron Donor-Acceptor Complex.

An electron donor-acceptor complex-enabled, nickel-catalyzed three-component net-reductive 1,2-alkylacylation of alkenes is developed. This conjunctive reductive acyl cross-coupling process obviates the use of an exogenous photocatalyst and a stoichiometric metal-based reductant, affording various synthetically useful 1,3-dicarbonyl compounds in good yields with a broad substrate scope and excellent functional group tolerance. Both alkyl and acyl electrophiles are derived from the highly abundant and readily accessible carboxylic acids, making the catalytic 1,2-dicarbofunctionalization more synthetically general and sustainable.

Tetrachlorophthalimides as Organocatalytic Acceptors for Electron Donor-Acceptor Complex Photoactivation.

Excitation of photoactive electron donor-acceptor (EDA) complexes is an effective way to generate radicals. Applications in a catalytic regime typically use catalytic donors. Herein, we report that readily available electron-poor tetrachlorophthalimides can act as effective organocatalytic acceptors to trigger the formation of EDA complexes with a variety of radical precursors not amenable to previous catalytic methods. Excitation with visible light generates carbon radicals under mild conditions. The versatility of this EDA complex catalytic platform allowed us to develop mechanistically distinct radical reactions, including in combination with a cobalt-based catalytic system. Quantum yield measurements established that a closed catalytic cycle is operational, which hints at the ability of tetrachlorophthalimides to readily turn over and govern each catalytic cycle.

Selectively Altering the Reactivity of Transient Organic Radical Ions via Their Solvation Environment.

Photoexcitation of the charge transfer band of electron donor-acceptor complexes composed of toluene and 1,2,4,5-tetracyanobenzene yields organic radical ion pairs whose ultrafast reactive dynamics are determined by equilibrium solvent properties. A comparative study of ultrafast reaction rates in a series of alkane alcohols identified their dependence on the local polarizability and hydrogen bond donating/accepting character of the solvent. Because of the rapid and efficient equilibration of these radical ion pairs into solvent-separated species, simple modifications to bulk conditions can be used as a means to selectively alter their decay rates. Selectively altering distinct stages in this photochemical cycle via cosolutes or additives is a valuable step toward understanding and controlling the reactivity of organic radical ions in complex environments.

High Quantum Yield Nitrogen-Doped Carbon Quantum Dot-Based Fluorescent Probes for Selective Sensing of 2,4,6-Trinitrotoluene

Fluorescent carbon quantum dots hold great promise for the determination of nitro-explosive 2,4,6-trinitrotoluene (TNT), a potential environmental pollutant. Here, a nitrogen-doped carbon quantum dot (N-CQD)-based fluorometric probe with high quantum yield (73.10%) was developed for the selective determination of TNT. N-CQDs were synthesized by the reflux method using citric acid (CA) as a carbon precursor and ethylenediamine (EDA) with diaminocyclohexane (DACH) as nitrogen precursors. N-CQDs, with excitation and emission wavelengths of 360 and 460 nm, respectively, were highly selective toward TNT among different types of explosives [i.e., tetryl, 2,4,6-trinitrophenol (TNP), 2,4-dinitrotoluene (DNT), 4-amino-2,6-dinitrotoluene (ADNT), HMX, 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), and pentaerythritol tetranitrate (PETN)]. As a result of the dominant FRET mechanism secondarily assisted by ground-state donor–acceptor complexation, the fluorescence of N-CQDs showed excellent quenching in the presence of TNT. The structure of N-CQDs was elucidated using X-ray photoelectron spectroscopy, X-ray diffraction, IR, Raman, high-resolution transmission electron microscopy, and dynamic light scattering techniques, and their interaction mechanism with TNT was resolved using the Gaussian (i.e., highest occupied molecular orbital–lowest unoccupied molecular orbital energy levels) program. The limit of detection and limit of quantification in aqueous media were 30.0 and 90.0 nM, respectively, while the Benesi–Hildebrand binding constant of N-CQDs was 2.22 × 103. In the presence of common soil ions, explosive mixtures, and camouflage materials, the N-CQDs could determine TNT with recoveries between 94.9 and 104.9%. In addition, sandy soil specimens were artificially contaminated with TNT as real samples, and the TNT extracted from these samples was determined by both N-CQDs and the reference liquid chromatography with tandem mass spectrometry method to validate the proposed fluorometric method. To design field detection techniques, two different support materials based on the thin layer chromatography-paper and hydrogel (N-CQD-gel) were developed, and TNT was determined visually at a μM level with both materials. The developed support materials make N-CQDs potentially useful in environmental sensor applications with their selective and sensitive sensing ability.

Sulfonylation enabled through the photoactivation of EDA complexes

In this issue of Chem Catalysis , Molander and co-workers report the visible-light photoactivation of electron donor-acceptor (EDA) complexes formed between thianthrenium and sodium sulfinate derivatives to generate sulfone-containing compounds in moderate to good yields. This approach can be used for late-stage functionalization and enables the retention of halide handles. In this issue of Chem Catalysis , Molander and co-workers report the visible-light photoactivation of electron donor-acceptor (EDA) complexes formed between thianthrenium and sodium sulfinate derivatives to generate sulfone-containing compounds in moderate to good yields. This approach can be used for late-stage functionalization and enables the retention of halide handles.