Donor Acceptor Stacks Research Articles

Transforming Thermally Activated Delayed Fluorescence to Room-Temperature Phosphorescence through Modulation of the Donor in Charge-Transfer Cocrystals.

A cocrystallization strategy is used through incorporation of 1,2,4,5-tetracyanobenzene (TCNB) as an acceptor with halogen-substituent thioxanthone (TX) derivatives as donors. The resulting cocrystals TT-R (R = H, F, Cl, Br, or I) transform the thermally activated delayed fluorescence emission in the TT-H, TT-F, and TT-Cl cocrystals to room-temperature phosphorescence in the TT-Br and TT-I cocrystals. Definite crystal packing structures demonstrate a 1:1 alternative donor-acceptor stacking in the TT-H cocrystal, a 2:1 alternative donor-acceptor stacking in the TT-F and TT-Cl cocrystals, and a separate stacking of donor and acceptor in the TT-Br and TT-I cocrystals. A transformation law can be revealed that with an increase in atomic number from H, F, Cl, Br, to I, the cocrystals show the structural transformation of the number of aggregated TX-R molecules from monomers to dimers and finally to multimers. This work will facilitate an understanding of the effect of halogen substituents on the crystal packing structure and luminescence properties in the cocrystals.

Fully space-confined donor-acceptor interaction for highly efficient thermally activated delayed fluorescence emitters

The emerging through-space charge transfers (TSCT) emitters with thermally activated delayed fluorescence (TADF) have drawn increasing interest. However, the low luminescence efficiency and slow reverse intersystem crossing (RISC) always limit their device performances. A new molecular design strategy for TSCT-TADF emitters with a fully space-confined donor/acceptor conformation that integrates high luminescence efficiency and fast RISC is proposed herein. Two new TSCT-TADF emitters, TRZ-STFMe and TRZ-STFPh, are developed by introducing the methyl and phenyl substituents at the C2 of the rigid fluorene scaffold, respectively. The repulsive interaction between methyl and the acceptor induces a close and face-to-face donor–acceptor stacking to generate highly efficient TADF and suppress structural changes during the RISC process in TRZ-STFMe. In contrast, TRZ-STFPh shows relatively low luminescence efficiency and slow RISC because of its conformationally unstable phenyl substituent. With a high luminescence efficiency of 97 % and a significant RISC rate of 5.23 × 105 s−1, TRZ-STFMe demonstrates a high electroluminescence performance with a maximum external quantum efficiency (EQE) of 29.6 % and an EQE of 26.5 % at 1000 cd m−2.

Preparation and Physicochemical Properties of Organic Semiconducting Materials from the Reaction of Imidazo[1,2‐a]pyridines with Tetracyanoethylene

AbstractOrganic donor‐acceptor (DA) complexes have emerged in recent years as materials of choice for organic binary electronics. The reactivity descriptors derived from the conceptual DFT reveal imidazo[1,2‐a]pyridines as potential donors. Thus, four imidazo[1,2‐a]pyridines were reacted with tetracyanoethylene (TCNE) in 1 : 2 molar ratio to afford four new DA complexes. The spectral studies, namely IR, 1H, 13C, DEPT 135, 2D HMQC NMR, and HRMS were used to establish structures of the products. The UV‐vis. spectroscopy reveals intramolecular charge transfer. All the four compounds fluoresce giving excitation emission fluorescence spectra with a red shift ranging from 64 to 151 nm and quantum yields from 0.004 to 16.35. Unexpectedly, nitro group in one of the products does not act as quencher; instead, it enhances the quantum yield to make it highest in this series. The products exhibit electrical conductivity which increases with temperature. The FESEM and HRTEM images reveal distinct and homogenous surface morphology with holes which facilitate flow of electrons as manifested by electrical conductivity. The powder XRD and SAED results establish the polycrystalline nature of the products. The theoretical studies indicate an alternate donor acceptor stacking pattern.

Highly stable and isomorphic donor–acceptor stacking in a family of n-type organic semiconductors of BTBT–TCNQ derivatives

Unsymmetrically substituted donor–acceptor type compounds exhibit an isomorphous layered packing structure, which is discussed in terms of DFT-based quantum chemical calculations.

Co-assembly of functionalized donor-acceptor molecules within block copolymer microdomains via the supramolecular assembly approach with an improved charge carrier mobility.

Here, we demonstrate the three-component self-assembly of functionalized small molecules (donor and acceptor) and a polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer using the supramolecular approach. The introduction of functional groups on both the donor (1-pyrenebutyric acid, PBA) and acceptor (functionalized naphthalene diimide, FNDI) molecules can form stable charge-transfer (CT) complexes within the block copolymer domains and these supramolecules exhibited a charge carrier mobility of around 1.01 × 10-4 cm2 (V s)-1. In this case, both the molecules can form H-bonding with P4VP chains, and as well as π-π stacking between the PBA and FNDI molecules is also possible within the block copolymer domains. These noncovalent interactions lead to the formation of stable hierarchical structures and CT complexes between PBA and FNDI, where bilayer donor-acceptor (D-A) stacks formed within the block copolymer microdomains. Overall, the organization of both functionalized donor and acceptor molecules within the block copolymer domain exhibits an enhanced charge carrier mobility, which is potentially useful in the fabrication of organic photovoltaic cells and organic light-emitting diodes.

Controlling the Supramolecular Polymerization of Donor-Acceptor π-Systems through Hydrogen Bond Intervention.

Supramolecular polymerization of donor-acceptor type molecules leads to mixed or self-sorted assemblies depending on the donor-acceptor strength and extent of noncovalent interactions between the components. Herein, we discuss how competing hydrogen bonding motifs control the supramolecular polymerization pathway of a two-component molecular π-system of oligo(p-phenylenevinylene) (OPV-B and OPV-P) donors and perylene bisimide (PBI-B and PBI-A) acceptors. It is shown that among the four different binary combinations (M1-M4) studied, the carboxylic acid/pyridine heterosystem (1 : 2 molar ratio) in M4 favors the coassembled donor-acceptor stacks with a distinct morphology, whose aggregation pathways in toluene/THF (v/v : 9/1) is different from that of the individual components. The nanoscopic molecular arrangement of OPV-P driven by PBI-A in M4 was found to influence the bulk properties such as, morphology, thermomechanical stability and electrical conductivity. For example, the G' and G'' values of M4 is an order of the magnitude higher and exhibited a four-probe electrical conductivity (11.93 Scm-1 ) higher than that of its individual components. Thus, hydrogen-bond intervention is a powerful strategy to control the supramolecular polymerization of two-component donor-acceptor π-systems.

Substituent effects in solid-state assembly of activated benzotriazoles

Aromatic donor–acceptor stacking involving electron-rich π-donors and electron-deficient π-acceptors has been utilized in a broad spectrum of diverse applications to great effect.

Multicomponent Assembled Systems Based on Platinum(II) Terpyridine Complexes

Platinum(II) terpyridine complexes have received tremendous attention in recent years because of their square-planar geometry and fascinating photophysics. Bottom-up self-assembly represents an intriguing approach to construct well-ordered supramolecular architectures with tunable optical and electronic properties. Until now, much effort has been devoted to the fabrication of monocomponent platinum(II) terpyridine-based assemblies. The next step is to develop multicomponent coassembled systems via the combination of platinum(II) terpyridine complexes with other π-organic and -organometallic molecules. The implementation of electron/energy transfer processes renders advanced functionality to the resulting coassemblies. For the fabrication of discrete multicomponent architectures, a feasible protocol is to construct preorganized molecular tweezers and macrocycles with the involvement of platinum(II) terpyridine complexes as the panel units. In view of their planar surface and positively charged character, such supramolecular receptors are capable of encapsulating electron-rich polyaromatic hydrocarbons and organometallic guests via donor-acceptor charge-transfer and/or metal-metal interactions. Intermolecular hydrogen bonds can be further incorporated between the molecular tweezers receptor and the polyaromatic hydrocarbon guests, giving rise to the strengthened binding affinity and sensitive stimuli-responsiveness. On this basis, multilayer donor-acceptor stacks have been obtained via the precise control over the number of pincers, which feature enhanced complexation strength and superior functionality. Moreover, platinum(II) terpyridine-based macrocycles are more suitable for guest accommodation than the corresponding molecular tweezers receptors in light of their definite size and constrained environment. Stimuli-responsive elements can be conveniently implemented into the rigid spacers of the molecular tweezers and macrocyclic receptors, facilitating the capture and release of the sandwiched guests in a highly controlled manner. On the other hand, long-range-ordered supramolecular polymers have been successfully fabricated with linear, hyperbranched, and cross-linked topologies by employing platinum(II) terpyridine-based molecular tweezers/guest recognition motifs as the non-covalent connecting unit. The degree of polymerization of the resulting donor-acceptor-type supramolecular polymers can be efficiently modulated by incorporating intermolecular hydrogen bonds between the molecular tweezers receptor and the complementary guest unit. An alternative approach toward extended multicomponent donor-acceptor assemblies is to mimic the structure of Magnus' green salt. A delicate balance of non-covalent driving forces between homo- and heterocomplexation processes and a deeper understanding of thermodynamic and kinetic behaviors play the decisive roles in the final arrangement of the coassembled structures. Overall, multicomponent coassembly of platinum(II) terpyridine complexes into well-ordered nanostructures would open up a new avenue toward functional supramolecular materials that are especially promising for sensing, optoelectronics, and catalytic applications.

Supramolecular Organic Photocatalyst Containing a Cubanelike Water Cluster and Donor-Acceptor Stacks: Hydrogen Evolution and Dye Degradation under Visible Light.

Supramolecular organic photocatalysts are scarcely explored for the generation of sustainable energy as well as for environmental remediation purposes. An organic photocatalyst, containing a cubanelike water cluster and donor-acceptor stacks, was efficiently developed through a supramolecular approach. The material exhibited remarkable photocatalytic hydrogen generation, in the absence of any cocatalyst, with excellent stability and recyclability. The photoactivity was further assessed through time-resolved photoluminescence and electrochemical impedance spectroscopy. The material also exhibited highly efficient sunlight-driven photocatalytic activity through the degradation of harmful organic dye methylene blue.

Donor-acceptor stacking arrangements in bulk and thin-film high-mobility conjugated polymers characterized using molecular modelling and MAS and surface-enhanced solid-state NMR spectroscopy.

Conjugated polymers show promising properties as cheap, sustainable and solution-processable semiconductors. A key challenge in the development of these materials is to determine the polymer chain structure, conformation and packing in both the bulk polymer and in thin films typically used in devices. However, many characterisation techniques are unable to provide atomic-level structural information owing to the presence of disorder. Here, we use molecular modelling, magic-angle spinning (MAS) and dynamic nuclear polarisation surface-enhanced NMR spectroscopy (DNP SENS) to characterise the polymer backbone group conformations and packing arrangement in the high-mobility donor-acceptor copolymer diketopyrrolo-pyrrole-dithienylthieno[3,2-b]thiophene (DPP-DTT). Using conventional 1H and 13C solid-state MAS NMR coupled with density functional theory calculations and molecular dynamics simulations, we find that the bulk polymer adopts a highly planar backbone conformation with a laterally-shifted donor-on-acceptor stacking arrangement. DNP SENS enables acquisition of 13C NMR data for polymer films, where sensitivity is limiting owing to small sample volumes. The DNP signal enhancement enables a two-dimensional 1H-13C HETCOR spectrum to be recorded for a drop-cast polymer film, and a 13C CPMAS NMR spectrum to be recorded for a spin-coated thin-film with a thickness of only 400 nm. The results show that the same planar backbone structure and intermolecular stacking arrangement is preserved in the films following solution processing and annealing, thereby rationalizing the favourable device properties of DPP-DTT, and providing a protocol for the study of other thin film materials.

Supercoiled fibres of self-sorted donor-acceptor stacks: a turn-off/turn-on platform for sensing volatile aromatic compounds.

To ensure the comfortable survival of living organisms, detection of different life threatening volatile organic compounds (VOCs) such as biological metabolites and carcinogenic molecules is of prime importance. Herein, we report the use of supercoiled supramolecular polymeric fibres of self-sorted donor-acceptor molecules as "turn-off/turn-on" fluorescent sensors for the detection of carcinogenic VOCs. For this purpose, a C3-symmetrical donor molecule based on oligo(p-phenylenevinylene), C3OPV, and a perylene bisimide based acceptor molecule, C3PBI, have been synthesized. When these two molecules were mixed together in toluene, in contrast to the usual charge transfer (CT) stacking, supramolecular fibres of self-sorted stacks were formed at the molecular level, primarily driven by their distinct self-assembly pathways. However, CT interaction at the macroscopic level allows these fibres to bundle together to form supercoiled ropes. An interfacial photoinduced electron transfer (PET) process from the donor to the acceptor fibres leads to an initial fluorescence quenching, which could be modulated by exposure to strong donor or acceptor type VOCs to regenerate the respective fluorescence of the individual molecular stacks. Thus, strong donors could regenerate the green fluorescence of C3OPV stacks and strong acceptors could reactivate the red fluorescence of C3PBI stacks. These supercoiled supramolecular ropes of self-sorted donor-acceptor stacks provide a simple tool for the detection of donor- or acceptor-type VOCs of biological relevance, using a "turn-off/turn-on" fluorescence mechanism as demonstrated with o-toluidine, which has been reported as a lung cancer marker.

Structural Diversity in the Complexes of Trimeric Perfluoro-o-phenylene Mercury with Tetrathia- and Tetramethyltetraselenafulvalene

Five potential charge transfer complexes of trimeric perfluoro-o-phenylene mercury (I) with tetrathiafulvalene (TTF) and tetramethyltetraselenefulvalene (TMTSF) were grown from different solvent mixtures. The adducts (I)2·TTF (1) and I·TTF (2) were grown by slow evaporation from the 1:1 mixture of dichloromethane (CH2Cl2, DCM) and carbon disulfide (CS2). Use of the different 1:1 solvent mixtures of dichloromethane (CH2Cl2, DCM) and dichloroethane (C2H4Cl2, DCE) has led to the crystalline adducts I·TTF (3) and I·TTF·DCE (4). Adduct I.TMTSF (5) was grown by the interface crystallization on the border of two immiscible layers, ethyl acetate, and carbon disulfide. The cocrystals differ by the donor–acceptor ratio, molecular packing, and the solvent inclusion. The components in 1–5 form mixed donor–acceptor stacks. The stacks are stabilized by Hg···S and Hg···C short contacts, while the lateral interactions between stacks include F···F, CH···F, and S/Se···F short contacts.

Synthesis, spectroscopic properties, and photoconductivity of black absorbers consisting of pt(bipyridine)(dithiolate) charge transfer complexes in the presence and absence of nitrofluorenone acceptors.

The diimine-dithiolato ambipolar complexes Pt(dbbpy)(tdt) and Pt(dmecb)(bdt) (dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine; tdt(2-) = 3,4-toluenedithiolate; dmecb = 4,4'-dimethoxyester-2,2'-bipyridine; bdt(2-) = benzene-1,2-dithiolate) are prepared herein. Pt(dmecb)(bdt) exhibits photoconductivity that remains constant (photocurrent density of 1.6 mA/cm(2) from a 20 nm thin film) across the entire visible region of the solar spectrum in a Schottky diode device structure. Pt(dbbpy)(tdt) acts as donor when combined with the strong nitrofluorenone acceptors 2,7-dinitro-9-fluorenone (DNF), 2,4,7-trinitro-9-fluorenone (TRNF), or 2,4,5,7-tetranitro-9-fluorenone (TENF). Supramolecular charge transfer stacks form and exhibit various donor-acceptor stacking patterns. The crystalline solids are "black absorbers" that exhibit continuous absorptions spanning the entire visible region and significant ultraviolet and near-infrared wavelengths, the latter including long wavelengths that the donor or acceptor molecules alone do not absorb. Absorption spectra reveal the persistence of donor-acceptor interactions in solution, as characterized by low-energy donor/acceptor charge transfer (DACT) bands. Crystal structures show closely packed stacks with distances that underscore intermolecular DACT. (1)H NMR provides further evidence of DACT, as manifested by upfield shifts of aromatic protons in the binary adducts versus their free components, whereas 2D nuclear Overhauser effect spectroscopy (NOESY) spectra suggest coupling between dithiolate donor protons with nitrofluorenone acceptor protons, in correlation with the solid-state stacking. The NMR spectra also show significant peak broadening, indicating some paramagnetism verified by magnetic susceptibility data. Solid-state absorption spectra reveal further red shifts and increased relative intensities of DACT bands for the solid adducts vs solution, suggesting cooperativity of the DACT phenomenon in the solid state, as further substantiated by νC-O and νN-O IR bands and solid-state tight-binding computational analysis.

Control of Luminescence Properties in Naphthalene Diimide-Based Gel with Azodibenzoic Acid by Charge Transfer Interaction

The self-sorting between aromaticcompounds that can serve as electron donors and electronacceptors allows the formation of distinct p- and n-typebundles of fibers that further intermix and generate multiplejunction points for efficient electron transfer and transport ofthe charge carriers. However, a difficulty associated withsimple mixing of such compounds is the possibility of adifferent mode of assembly, i.e., charge-transfer interactionmediated by alternate donor–acceptor stacking. Thus, ex-amples related to self-sorting among donor–acceptor chromo-phores have been limited.

Adducts of Trimeric Perfluro-o-Phenylene Mercury with TTF or DTT

Since the discovery of metallic conductivity in the TTF-TCNQ complex, the charge transfer (CT) complex materials have been studied for such properties as semiconductivity or superconductivity. The synthesis of new CT materials using trimeric perfluoro-ortho-phenylene mercury (Hg3) as electron acceptor compound was done first by Haneline and Gabaï [1]. A series of studies of CT materials containing Hg3 and tetrathiafulvalene (TTF) or dithieno thiophene (DTT) as an electron donor compounds was carried out by different methods. Co-crystalzation with TTF gave a larger variety of co-crystals than with DTT, producing three polymorphs and one pseudo-polymorph. One pot crystal growth of TTF and Hg3 in a 1:1 mixture of solvents dichloromethane (DCM) and dichloroethane (DCA) has led to the formation of TTF polymorphs 1 and 2 with same 1:1 donor acceptor ratio [Hg3·TTF] as well a pseudopolymorph [Hg3·TTF·DCA] 3 that contains the solvent DCA in the asymmetric unit. Slow evaporation in a 1:1 mixture of dichloromethane and carbon disulfide was used to obtain the previously reported CT [(Hg3)2·TTF] (4)1. By slow evaporation as well in pure dichloromethane was obtained the CT material [Hg3·DTT·DCM] 5. All these five CT co-crystals contain mixed donor acceptor stacks, however only in 3, 4 and 5 these stacks are parallel to each other. In the packing of 1 and 2 these stacks are in herringbone arrangement. Polymorphs 1 and 2 differ in crystal shape and color. Contacts Hg···S shorter than the sum of the Van Der Walls radii were observed in the five CTs materials reported, however only 1, 2, 3, and 5 have extended short donor acceptor molecular associates. Moreover only 3, and 5 has these extended donor acceptor associates along one direction.

Three‐Dimensional Architectures Incorporating Stereoregular Donor–Acceptor Stacks

We report the synthesis of two [2]catenane-containing struts that are composed of a tetracationic cyclophane (TC(4+)) encircling a 1,5-dioxynaphthalene (DNP)-based crown ether, which bears two terphenylene arms. The TC(4+) rings comprise either 1) two bipyridinium (BIPY(2+)) units or 2) a BIPY(2+) and a diazapyrenium (DAP(2+)) unit. These degenerate and nondegenerate catenanes were reacted in the presence of Cu(NO3)2⋅2.5 H2O to yield Cu-paddlewheel-based MOF-1050 and MOF-1051. The solid-state structures of these MOFs reveal that the metal clusters serve to join the heptaphenylene struts into grid-like 2D networks. These 2D sheets are then held together by infinite donor-acceptor stacks involving the [2]catenanes to produce interpenetrated 3D architectures. As a consequence of the planar chirality associated with both the DNP and hydroquinone (HQ) units present in the crown ether, each catenane can exist as four stereoisomers. In the case of the nondegenerate (bistable) catenane, the situation is further complicated by the presence of translational isomers. Upon crystallization, however, only two of the four possible stereoisomers--namely, the enantiomeric RR and SS forms--are observed in the crystals. An additional element of co-conformational selectivity is present in MOF-1051 as a consequence of the substitution of one of the BIPY(2+) units by a DAP(2+) unit: only the translational isomer in which the DAP(2+) unit is encircled by the crown ether is observed. The overall topologies of MOF-1050 and MOF-1051, and the selective formation of stereoisomers and translational isomers during the kinetically driven crystallization, provide evidence that weak noncovalent bonding interactions play a significant role in the assembly of these extended (super)structures.

Conjugated NDI–Donor Polymers: Exploration of Donor Size and Electrostatic Complementarity

Conjugated donor–acceptor copolymers comprised of electron-deficient 1,4,5,8-naphthalenetetracarboxylic diimide (NDI) linked to a series of relatively electron-rich aromatics via ethynyl spacers were synthesized and characterized. While LUMO levels remained constant at −3.75 eV, HOMO levels were sensitive to the relatively electron-rich aromatic donors and systematically tuned from −5.68 to −5.17 eV. Regardless of the electron-rich comonomer, fluorescence and X-ray diffraction data were consistent with the polymer chains being assembled through the stacking of NDI moieties in an offset face-to-face fashion rather than alternating donor–acceptor stacks.

Density functional theory for the description of charge-transfer processes at TTF/TCNQ interfaces

In the field of organic electronics, a central issue is to assess how the frontier electronic levels of two adjacent organic layers align with respect to one another at the interface. This alignment can be driven by the presence of a partial charge transfer and the formation of an interface dipole; it plays a key role for instance in determining the rates of exciton dissociation or exciton formation in organic solar cells or light-emitting diodes, respectively. Reliably modeling the processes taking place at these interfaces remains a challenge for the computational chemistry community. Here, we review our recent theoretical work on the influence of the choice of density functional theory (DFT) methodology on the description of the charge-transfer character in the ground state of TTF/TCNQ model complexes and interfaces. Starting with the electronic properties of the isolated TTF and TCNQ molecules and then considering the charge transfer and resulting interface dipole in TTF/TCNQ donor–acceptor stacks and bilayers, we examine the impact of the choice of DFT functional in describing the interfacial electronic structure. Finally, we employ computations based on periodic boundary conditions to highlight the impact of depolarization effects on the interfacial dipole moment.

A complementary disk-shaped π electron donor–acceptor pair with high binding affinity

Hexaazatriphenylene triimides (HAT) have been shown to be a novel class of disk-shaped π electron acceptors that pair with donors with complementary shape and electron demands, such as triphenylene (TP) derivatives. The donor–acceptor (DA) pair forms a strong charge-transfer complex in CH2Cl2 with an association constant of 2.6 × 104 M−1, which is remarkable for a recognition system that is solely based on electrostatic interactions between two π systems. NMR studies, along with molecular modelling, have revealed a complementary charge distribution and an “eclipsed” conformation in the DA complex. The strong DA interaction results in extended alternating DA stacks in the thin film and mesophases.

Structural properties of charge-transfer complexes of multilayered [3.3]paracyclophanes

In the solid state, multilayered [3.3]paracyclophanes (PCPs) 2–6 and tetracyanoethylene (TCNE) form charge-transfer (CT) complexes with a 1:1 stoichiometry. All the benzene rings overlapped each other. All the [3.3]PCP units and dione units assume chair conformations and the transannular distances are shorter than those of the corresponding free multilayered [3.3]PCP except for the dione unit in the four-layered dione 6. In the crystal-packing diagrams, the PCP and TCNE are located in alternating donor-acceptor stacking in columns, and effective short contacts are observed in the neighboring molecules.