Donor-acceptor Charge Transfer Research Articles

Design of Charge Transfer Donor-Acceptor Co-Crystals with Long Lived Charge Carriers

Organic donor-acceptor co-crystals with long exciton lifetimes have emerged as a promising class of semiconductors for their unique photophysical properties. These are crystalline, single-phase materials composed of two or more different compounds in a stoichiometric ratio, providing a platform for unveiling the structure–property relationships at a molecular level. Importantly, co-crystals that are packed through π stacking interactions have the ability to form charge transfer (CT) excitons within donor-acceptor pairs.1,2,3 We hypothesize that co-crystals with a high degree of CT will have longer exciton lifetimes. Therefore, we design and synthesized of new co-crystals using derivatives of N,N-bis(3-pentyl)-perylene-3,4:9,10-bis(dicarboximide) (PDI, acceptor) with a series of donor molecules, including peri-xanthenoxanthene (PXX), perylene, and triphenylene. High quality single crystals were isolated by slow evaporation at room temperature from suitable solvent mixtures. Their crystal structures were successfully refined by single-crystal X-ray diffraction and the phase purity was validated by powder diffraction. Crystal structures revealed that the driving force for forming these co-crystals is π...π stacking. We measured diffuse reflectance UV/visible spectra of each of these co-crystals and compared with computed spectra to assign the observed electronic transitions. DFT calculations provide additional insights into the nature of the excited state CT interactions which can be derived from ground state electronic structure calculations. Transient absorption measurements were conducted to understand their long exciton lifetime for each of as synthesized co-crystals. We conclude that this study supported our previous hypothesis and such materials are potentially useful in applications ranging from photovoltaics and opto-electronics to photocatalysis. References 1) A. Abou Taka, J. E. Reynolds Iii, N. C. Cole-Filipiak, M. Shivanna, C. J. Yu, P. L. Feng, et al. Phys. Chem. Chem. Phys. 2023, 25, 27065.2) L. Sun, Y. Wang, F. Yang, X. Zhang and W. Hu. Adv. Mater. 2019, 31, 1902328.3) I. Schlesinger, N. E. Powers-Riggs, J. L. Logsdon, Y. Qi, S. A. Miller, R. Tempelaar, et al. Chem. Sci., 2020, 11, 9532–9541.

Charge-Transfer Complexes: Halogen-Doped Anthracene as a Case of Study.

Charge transfer (CT) crystals exhibit unique electronic and magnetic properties with interesting applications. We present a rational and easy guide which allows to foresee the effective charge transfer co-crystal production and that is based on the comparison of the frontier molecular orbital (MO) energies of a donor and acceptor couple. For the sake of comparison, theoretical calculations have been carried out by using the cheap and fast PM6 semiempirical Hamiltonian and pure HF/cc-pVTZ level of the theory. The results are then compared with experimental results obtained both by chemical (bromine and iodine were used as the acceptor) and electrochemical doping (exploiting an original experimental set-up by this laboratory: the electrochemical transistor). Infra-red vibrational experimental results and theoretically calculated spectra are compared to assess both the effective donor-acceptor (D/A) charge-transfer and transport mechanism (giant IRAV polaron signature). XPS spectra have been collected (carbon (1 s) and iodine (3d5/2)) signals, yielding further evidence of the effective formation of the CT anthracene:iodine complex.

A Halogen Bonding [2]Rotaxane Shuttle for Chloride-Selective Optical Sensing.

The first example of a [2]rotaxane shuttle capable of selective optical sensing of chloride anions over other halides is reported. The rotaxane was synthesised via a chloride ion template-directed cyclisation of an isophthalamide macrocycle around a multi-station axle containing peripheral naphthalene diimide (NDI) stations and a halogen bonding (XB) bis(iodotriazole) based station. Proton NMR studies indicate the macrocycle resides preferentially at the NDI stations in the free rotaxane, where it is stabilised by aromatic donor-acceptor charge transfer interactions between the axle NDI and macrocycle hydroquinone moieties. Addition of chloride ions in an aqueous-acetone solvent mixture induces macrocycle translocation to the XB anion binding station to facilitate the formation of convergent XB⋅⋅⋅Cl- and hydrogen bonding HB⋅⋅⋅Cl- interactions, which is accompanied by a reduction of the charge-transfer absorption band. Importantly, little to no optical response was induced by addition of bromide or iodide to the rotaxane, indicative of the size discriminative steric inaccessibility of the interlocked cavity to the larger halides, demonstrating the potential of using the mechanical bond effect as a potent strategy and tool in chloride-selective chemo-sensing applications in aqueous containing solvent environments.

Charge Transfer-Promoted Excited State of a Heavy-Atom-Free Photosensitizer for Efficient Application of Mitochondria-Targeted Fluorescence Imaging and Hypoxia Photodynamic Therapy.

Conventional photosensitizers (PSs) used in photodynamic therapy (PDT) have shown preliminary success; however, they are often associated with several limitations including potential dark toxicity in healthy tissues, limited efficacy under acidic and hypoxic conditions, suboptimal fluorescence imaging capabilities, and nonspecific targeting during treatment. In response to these challenges, we developed a heavy-atom-free PS, denoted as Cz-SB, by incorporating ethyl carbazole into a thiophene-fused BODIPY core. A comprehensive investigation into the photophysical properties of Cz-SB was conducted through a synergistic approach involving experimental and computational investigations. The enhancement of intersystem crossing (kISC) and fluorescence emission (kfl) rate constants was achieved through a donor-acceptor pair-mediated charge transfer mechanism. Consequently, Cz-SB demonstrated remarkable efficiency in generating reactive oxygen species (ROS) under acidic and low-oxygen conditions, making it particularly effective for hypoxic cancer PDT. Furthermore, Cz-SB exhibited good biocompatibility, fluorescence imaging capabilities, and a high degree of localization within the mitochondria of living cells. We posit that Cz-SB holds substantial prospects as a versatile PS with innovative molecular design, representing a potential "one-for-all" solution in the realm of cancer phototheranostics.

Low Bandgap Organic Semiconductors for Photovoltaic Applications

Photovoltaic is one of the best low-cost alternative energy sources. In this paper, organic semiconductors were explored as light harvesters due to their extraordinary properties, but initially, the scientific community focused on synthesizing the large bandgap organic semiconductors, which were unsuitable for photovoltaic applications. Wide bandgap organic semiconductors can capture light only from the UV–Vis region of the solar spectrum, thus showing solar cells’ power conversion efficiency (PCE) of less than 5%. By reducing the bandgap, organic semiconductors can show good compatibility with the air mass (AM) of 1.5 solar spectrums. So, the attention came toward synthesizing low bandgap semiconductors, which led to the enhancement of PCE from 5% to 17%. This review summarizes the overall development of the last 15 years in the field of organic photovoltaic semiconductors. The significant parameters in organic semiconductors are their bandgap, the position of the highest occupied molecular orbital (HOMO), and the lowest unoccupied molecular orbital (LUMO) that can easily be tuned chemically by molecular designing. One of the issues in organic photovoltaic solar devices is the need for absorbers with a narrow bandgap to maximize power conversion efficiencies to a great extent. Moreover, several factors, such as conjugation length, bond length alteration, intermolecular interaction, donor–acceptor charge transfer, planarity, and physical states, are responsible for tuning the bandgap. This review also classifies low bandgap semiconductors based on the core skeleton with their bandgaps, structures, and power conversion efficiencies.

Cooperativity in Hydrogen‐Bonded Macrocycles Derived from Nucleobases

AbstractIntroducing a rigid linear π‐conjugated acetylene linker into a supramolecular building block consisting of a hydrogen‐bond donor side and a hydrogen‐bond acceptor side yields a decrease in cooperativity in the resulting formed quartet. This follows from our Kohn‐Sham molecular orbital and Voronoi deformation density analyses of hydrogen‐bonded macrocycles based on guanine and cytosine nucleobases. The acetylene linker abstracts electron density from the hydrogen‐bond acceptor and donor, making the hydrogen‐bond acceptor more negatively charged and the hydrogen‐bond donor more positively charged and hence suppressing the donor–acceptor charge transfer interaction between the interacting fragments. This, ultimately, hampers the cooperativity in the hydrogen‐bonded macrocycle. We envision that these findings could open the door to new design principles for the development of novel hydrogen‐bond supramolecular macrocycles.

Embedding vertex corrections in GW self-energy: Theory, implementation, and outlook.

The vertex function (Γ) within the Green's function formalism encapsulates information about all higher-order electron-electron interaction beyond those mediated by density fluctuations. Herein, we present an efficient approach that embeds vertex corrections in the one-shot GW correlation self-energy for isolated and periodic systems. The vertex-corrected self-energy is constructed through the proposed separation-propagation-recombination procedure: the electronic Hilbert space is separated into an active space and its orthogonal complement denoted as the "rest;" the active component is propagated by a space-specific effective Hamiltonian different from the rest. The vertex corrections are introduced by a rescaled time-dependent nonlocal exchange interaction. The direct Γ correction to the self-energy is further updated by adjusting the rescaling factor in a self-consistent post-processing cycle. Our embedding method is tested mainly on donor-acceptor charge-transfer systems. The embedded vertex effects consistently and significantly correct the quasiparticle energies of the gap-edge states. The fundamental gap is generally improved by 1-3eV upon the one-shot GW approximation. Furthermore, we provide an outlook for applications of (embedded) vertex corrections in calculations of extended solids.

Permittivity Threshold and Thermodynamics of Integer Charge-Transfer Complexation for an Organic Donor–Acceptor Pair

Molecular charge doping involves the formation of donor-acceptor charge-transfer complexes (CTCs) through integer or partial electron transfer; understanding how local chemical environment impacts complexation is important for controlling the properties of organic materials. We present steady-state and temperature-dependent spectroscopic investigations of the p-dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) complexed with the electron donor and hole transport material N,N'-diphenyl-N,N'-di-p-tolylbenzene-1,4-diamine (MPDA). Equilibrium formation constants (KCT) were determined for donor-acceptor pairs dissolved in a series of solvents covering a range of values of permittivity. A threshold for highly favorable complex formation was observed to occur at ϵ ∼ 8-9, with large (>104) and small (<103) values of KCT obtained in solvents of higher and lower permittivity, respectively, but with chloroform (ϵ = 4.81) exhibiting an anomalously high formation constant. Temperature-dependent formation constants were determined in order to evaluate the thermodynamics of complex formation. In 1,2-dichloroethane (ϵ = 10.36) and chlorobenzene (ϵ = 5.62), complex formation is both enthalpically and entropically favorable, with higher enthalpic and entropic stabilization in the solvent with higher permittivity. Complexation in chloroform is exothermic and entropically disfavored, indicating that specific, inner-shell solvent-solute interactions stabilize the charge-separated complex and result in a net increase in local solution structure. Our results provide insight into how modification to the chemical environment may be utilized to support stable integer charge transfer for molecular doping applications and requiring only modest changes in local permittivity.

Near-IR Absorbers Based on Pt(II)-Dithiolene Donor–Acceptor Charge-Transfer (CT) Systems: A Structural Analysis to Highlight DA Interactions

The packing interactions of a series of electron donor (D) and electron acceptor (A) charge transfer (CT) near-IR absorbers based on platinum-dithiolene complexes are reinvestigated here as a case study also by using the Hirshfeld surface analysis. This analysis on systems, which exhibit the 1:1, 2:1 and 2:2 columnar stacking patterns between D and A, allows us to point out that several interactions of atoms and fragments are involved in the stacking interactions but also that only a limited fraction of these interactions, limited to the 1:1 D/A columnar stacking case, can be relatable to the absorption features of this class of compounds.

Supramolecular Recognition of Phosphodiester-Based Donor and Acceptor Oligomers Forming Gels in Water.

Inspired by automated DNA synthesis, electron-rich dialkoxynaphthalene (DAN) donor and electron-deficient naphthalene-tetracarboxylic diimide (NDI) acceptor phosphodiester-linked homohexamers were synthesized by the phosphoramidite method. Two types of hexamers were prepared, one with only one phosphodiester between the aromatics (i.e., DAN or NDI) and a second with two phosphodiesters around a propanediol between the aromatics, leading to the latter more flexible and more hydrophilic hexamers. The folding properties of these homohexamers alone or mixed together, in water only, were studied by UV-visible absorption spectroscopy and atomic force microscopy (AFM). AFM imaging revealed that a 1:1 mixture of hexaDAN and hexaNDI formed fibers by charge transfer donor-acceptor recognition leading to a hydrogel after drying. The organization of the resulting structures is strongly dependent on the nature of the complementary partner, leading to the formation of mono- or multilayer hydrogel networks with different compactness.

TDDFT versus GW/BSE Methods for Prediction of Light Absorption and Emission in a TADF Emitter.

Design concepts for organic light emitting diode (OLED) emitters, which exhibit thermally activated delayed fluorescence (TADF) and thereby achieve quantum yields exceeding 25%, depend on singlet-triplet splitting energies of order kT to allow reverse intersystem crossing at ambient temperatures. Simulation methods for these systems must be able to treat relatively large organic molecules, as well as predict their excited state energies, transition energies, singlet-triplet splittings, and absorption and emission cross sections with reasonable accuracy, in order to prove useful in the design process. Here we compare predictions of TDDFT with M06-2X and ωB97X-D exchange-correlation functionals and a GoWo@HF/BSE method for these quantities in the well-studied DPTZ-DBTO2 TADF emitter molecule. Geometry optimization is performed for ground state (GS) and lowest donor-acceptor charge transfer (CT) state for each functional. Optical absorption and emission cross sections and energies are calculated at these geometries. Relaxation energies are on the order of 0.5 eV, and the importance of obtaining excited state equilibrium geometries in predicting delayed fluorescence is demonstrated. There are clear trends in predictions of GoWo@HF/BSE, and TDDFT/ωB97X-D and M06-2X methods in which the former method favors local exciton (LE) states while the latter favors DA CT states and ωB97X-D makes intermediate predictions. GoWo@HF/BSE suffers from triplet instability for LE states but not CT states relevant for TADF. Shifts in HOMO and LUMO levels on adding a conductor-like polarizable continuum model dielectric background are used to estimate changes in excitation energies on going from the gas phase to a solvated molecule.

Controllable Fabrication of Organic Cocrystals with Interior Hollow Structure Based on Donor-Acceptor Charge Transfer Molecules

Fluorescent hollow organic molecular cocrystals comprised of (E)-4-(2(anthracen-9-yl)vinyl)pyridine-1,2,4,5-tetracyanobenzene (APE-TCNB) were prepared via a surfactant-mediated co-precipitation method. The size and morphology of these cocrystals could be easily tuned by varying the type and concentration of the surfactant, incubation time, and temperature. Moreover, optical fluorescence and scanning electron microscopy characterization indicated that the APE-TCNB microcrystals contained two symmetric empty cavities when 3-(N, N-dimethyldodecylammonio)propane sulfonate (BS12) was used as the surfactant. The cross-polarized microscope and powder X-ray diffraction (PXRD) measurements both showed that the prepared microcrystals exhibited high crystallinity. APE and TCNB molecules were found to align parallelly along the crystallographic a-axis in the crystal lattice, and the strong π–π intermolecular interactions facilitated the formation of unique crystal chambers. A series of measurements and characterization, including UV-Vis absorption spectroscopy, infrared spectroscopy, steady-state, and time-resolved fluorescence spectroscopy, also verified that strong charge–transfer (CT) interactions had been established in the APE-TCNB microcrystals. Moreover, these APE-TCNB microcrystals could emit bright red luminescence, which extended to the near-infrared region (~800 nm), displaying a strong charge-transfer property. Here, we have shown a general facile way to make organic cocrystals with complex structures and topologies using a self-assembly method.

Cocrystal engineering: towards high-performance near-infrared organic phototransistors based on donor-acceptor charge transfer cocrystals

Cocrystal engineering: towards high-performance near-infrared organic phototransistors based on donor-acceptor charge transfer cocrystals

Enhanced blue thermally activated delayed fluorescence with rigid adamantane as non-conjugated linker for space-confined donor-acceptor charge transfer: a theoretical study

A lack of control over the relative orientation of donor and acceptor moieties in solid films is the main reason for poor electroluminescence efficiency found in most D-σ-A patterns. In this study, adamantane was introduced as the linker for the construction of a D-σ-A system since its rigid but non-conjugated nature. For a systematic study, the same donor (9,9-dimethyl-10-phenyl-9,10-dihydroacridine, DMTPA) and acceptor (2,4,6-triphenyl-1,3,5-triazine, TPZ) block were attached at different sites of the adamantine molecule, forming three kinds of configuration including face-to-face (FF), head-to-tail (HT), and chair (CH) style. DFT/TD-DFT simulation was carried out to investigate the electronic structures, optical characteristics, and charge transfer (ICT) properties of these three designed molecules. Attributed to a non-conjugated adamantane linker, the conjugation between donor and acceptor was disrupted for either of these molecules, resulting in high triplet energy of 2.79, 2.99, and 3.10 eV, respectively. Among them, the face-to-face style molecule presents the smallest ΔEST and greatest charge transfer excitation from donor to acceptor, suggesting an excellent potential for thermal activated delayed fluorescence (TADF). Face-to-face type molecule is a good option for a high-performance blue organic light-emitting diode (OLED) host material based on these results. Our investigation may open a door for designing new host molecule with other donor and acceptor groups to further enhance the efficiency and longevity of OLEDs.

Cycloaddition Reactivities Analyzed by Energy Decomposition Analyses and the Frontier Molecular Orbital Model.

This Account describes our quest to understand and predict organic reactivity, a principal goal of physical and theoretical organic chemistry. The focus is on the development and testing of models for the prediction of cycloaddition reactivities and selectivities. We describe the involvement of the Houk group, and other groups, in the evolution of theoretical models that can achieve ever greater accuracy as well as provide practical heuristic models for understanding and prediction.Is the venerable frontier molecular orbital (FMO) model, the basis of Kenichi Fukui's 1981 Nobel Prize, still useful, or must it be replaced with more advanced models? In particular, models such as Conceptual Density Functional, the Pauli Exclusion Model, and the recent popularity of Electrostatic Potential Plots and Dispersion Energies have not only added to our understanding, but they have also created uncertainty about whether the simple FMO heuristic model has a place in 21st century discussions. This Account addresses this issue and asserts the value of the FMO model.Beginning with brief descriptions of selected models for cycloaddition reactivity starting with early donor-acceptor (nucleophile-electrophile) charge-transfer concepts, this Account reviews Fukui's frontier molecular orbital model, Salem and Klopman's orbital, electrostatic and Pauli repulsion model, the conceptual DFT model by Parr and later by Domingo and others, the recent Houk and Bickelhaupt Distortion/Interaction Activation Strain model, and the Bickelhaupt-Hamlin's Pauli-repulsion lowering model.Computations and analyses of four well-studied Diels-Alder cycloadditions, both normal and inverse electron-demand types, are presented. Most were studied earlier in our published work but are presented here with new insights from calculations with modern methods. Depending on the types of substrates (cycloaddends), the dominant factors controlling reactivity can be orbital interactions, electrostatics and polarization, or Pauli repulsion and dispersion effects, or a combination of all of these.By comparing orbital interactions, especially the frontier molecular orbital interactions, with the other factors that influence reactivity, we show why the FMO model is such a powerful─and theoretically meaningful─heuristic for understanding and predicting reactivity. We also present a method to understand Pauli repulsion effects on activation barriers, ρ(1.1). The use of a new reaction coordinate, the extent of Pauli repulsion along the reaction path, is advocated to emphasize the role of repulsive occupied orbital interactions on reactivity.Fukui's frontier molecular orbital model is effective because FMO interactions parallel all the quantities that influence reactivity. The FMO model continues to provide a practical model to understand and guide experiments.

DFT insight into Cd2+, Hg2+, Pb2+, Sn2+, As3+, Sb3+, and Cr3+ heavy metal ions adsorption onto surface of bowl-like B30 nanosheet

Contamination of water resources by heavymetal ions, is a drastic environmental concern. In this study, the interaction of Cd2+, Hg2+, Pb2+, Sn2+, As3+, Sb3+, and Cr3+ metal ions onto surface of the bowl-like B30 nanosheet was scrutinized based on density functional theory (DFT) calculations. Adsorption energy (Eads) values revealed that the As3+ interacted better with bowl-like B30 nanosheet in comparison to other metal ions, having adsorption energy values of −299.57 and −628.56 kcal mol−1in the gas phase and aqueous media, respectively. However, Hg2+, Pb2+, and Sn2+ metal ions physically adsorbed onto bowl-like B30 nanosheet in the gas phase because of their much less value of adsorption energy. The sign of adsorptionGibbs free energy change(ΔGads) and adsorption enthalpy change (ΔHads) values for all complexes was found to be negative in the gas phase and aqueous media, which indicated that the adsorption process is spontaneous and exothermic. Frontier molecular orbital (FMO) analysis exhibited a decrease in the HOMO-LUMO energy gap of studied complexes, boosting the electrical conductivity of these complexes. Natural bond orbital (NBO) analysis and charge decomposition analysis (CDA) revealed donor–acceptor charge transfer interactions in the complexes. The UV–vis results depicted that λmax was red-shifted during interactions of meal ions with bowl-like B30 nanosheet. Finally,quantum theoryof atoms in molecules (QTAIM) exhibited that the interaction between As3+ metal ion and the nanosheet is covalent in nature, while the other metal ions have predominantly electrostatic with partially covalent and non-covalent characters. The theoretical results of the study represented the feasibility of applying bowl-like B30 nanosheet to remove heavy metal ions, especially As3+ and providing information for experimental researchers to treat wastewaters.

Near-Infrared Light Triggered a High Temperature Utilizing Donor-Acceptor Cocrystals.

Developing a suitable initiation for the energetic materials that respond to a low-power near-infrared laser can aid in replacing the current expensive and bulky laser-initiation systems. Here, we report on a system of molecularly tailored 1:1 donor-acceptor (D-A) charge-transfer (CT) cocrystals that manifest ultrabroad absorption (200-2500 nm) characteristics as well as noteworthy very fast self-assembly behaviors. The very narrow highest occupied molecular orbital-lowest unoccupied molecular orbital gap enables N,N,N',N'-tetramethyl-p-phenylenediamine and tetrahalo-1,4-benzoquinones (TMPD-TXBQ) cocrystals to have a great light-harvesting ability in the near-infrared range. When irradiated with a low-power hand-held 808 nm laser with an input energy of only 40 mJ or a power density of 260 mW·cm-2, these TMPD-TXBQ cocrystals immediately undergo an efficient photothermal conversion followed by a dramatic exothermic thermal polymerization reaction due to the face-to-face D-A-D-A stacking in these cocystals to achieve a temperature as high as 318.9 °C. This temperature is high enough for a thermal initiation of most common energetic materials, and thus this TMPD-TXBQ cocrystal can potentially act as a near-infrared laser initiator that is compact, lightweight, and cost-effective.

Enhancement of Haloperidol Binding Affinity to Dopamine Receptor via Forming a Charge-Transfer Complex with Picric Acid and 7,7,8,8-Tetracyanoquinodimethane for Improvement of the Antipsychotic Efficacy.

Haloperidol (HPL) is a typical antipsychotic drug used to treat acute psychotic conditions, delirium, and schizophrenia. Solid charge transfer (CT) products of HPL with 7,7,8,8-tetracyanoquinodimethane (TCNQ) and picric acid (PA) have not been reported till date. Therefore, we conducted this study to investigate the donor–acceptor CT interactions between HPL (donor) and TCNQ and PA (π-acceptors) in liquid and solid states. The complete spectroscopic and analytical analyses deduced that the stoichiometry of these synthesized complexes was 1:1 molar ratio. Molecular docking calculations were performed for HPL as a donor and the resulting CT complexes with TCNQ and PA as acceptors with two protein receptors, serotonin and dopamine, to study the comparative interactions among them, as they are important neurotransmitters that play a large role in mental health. A molecular dynamics simulation was ran for 100 ns with the output from AutoDock Vina to refine docking results and better examine the molecular processes of receptor–ligand interactions. When compared to the reactant donor, the CT complex [(HPL)(TCNQ)] interacted with serotonin and dopamine more efficiently than HPL only. CT complex [(HPL)(TCNQ)] with dopamine (CTtD) showed the greatest binding energy value among all. Additionally, CTtD complex established more a stable interaction with dopamine than HPL–dopamine.

BODIPY-Based Polymers of Intrinsic Microporosity for the Photocatalytic Detoxification of a Chemical Threat.

Effective heterogeneous photocatalysts capable of detoxifying chemical threats in practical settings must exhibit outstanding device integrity. We report a copolymerization that yields robust, porous, processible, chromophoric BODIPY (BDP; boron-dipyrromethene)-containing polymers of intrinsic microporosity (BDP-PIMs). Installation of a pentafluorophenyl at the meso position of a BDP produced reactive monomer that when combined with 5,5,6,6-tetrahydroxy-3,3,3,3-tetramethyl-1,1-spirobisindane (TTSBI) and tetrafluoroterephthalonitrile (TFTPN) yields PIM-1. Postsynthetic modification of these polymers yields Br-BDP-PIM-1a and -1b─polymers containing bromine at the 2,6-positions. Remarkably, the brominated polymers display porosity and processability features similar to those of H-BDP-PIMs. Gas adsorption reveals molecular-scale porosity and Brunette-Emmet-Teller surface areas as high as 680 m2 g-1. Electronic absorption spectra reveal charge-transfer (CT) bands centered at 660 nm, while bands arising from local excitations, LE, of BDP and TFTPN units are at 530 and 430 nm, respectively. Fluorescence spectra of the polymers reveal a Förster resonance energy-transfer (FRET) pathway to BDP units when TFTPN units are excited at 430 nm; weak phosphorescence at room temperature indicates a singlet-to-triplet intersystem crossing. The low-lying triplet state is well positioned energetically to sensitize the conversion of ground-state (triplet) molecular oxygen to electronically excited singlet oxygen. Photosensitization capabilities of these polymers toward singlet-oxygen-driven detoxification of a sulfur-mustard simulant 2-chloroethyl ethyl sulfide (CEES) have been examined. While excitation of CT and LEBDP bands yields weak catalytic activity (t1/2 > 15 min), excitation to higher energy states of TFTPN induces significant increases in photoactivity (t1/2 ≅ 5 min). The increase is attributable to (i) enhanced light collection, (ii) FRET between TFTPN and BDP, (iii) the presence of heavy atoms (bromine) having large spin-orbit coupling energies that can facilitate intersystem crossing from donor-acceptor CT-, FRET-, or LE-generated BDP singlet states to BDP-related triplet states, and (iv) polymer triplet excited-state sensitization of the formation of CEES-reactive, singlet oxygen.

Oligotriarylamine-Extended Organoboranes with Tunable Electron-Donating Strength by Changing the Number of Donor Units.

Triarylborane (Ar3B) and triarylamine (Ar3N) have been widely employed to construct electronically different donor-acceptor (D-A) systems. Herein, we describe a series of A-D-A-type luminescent organoboranes L-B2Nn (n = 1, 3, 5) that show an increased number of Ar3N units as electron donors and two terminal Ar3B as acceptors. When the Ar3N moieties were extended from one to five units, their electron-donating strength was gradually enhanced and the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps could also be tuned, which was further reflected in the red-shifted emissions from blue (λem = 458 nm) to orange (λem = 595 nm) with a decrease in Egap(elect) from 3.19 to 2.61 eV. L-B2N5 showed a huge Stokes shift (∼14 057 cm-1) and a considerably bright emission with an enhanced solid-state quantum efficiency (ΦS = 98%) compared with the other members. L-B2N3 and L-B2N5 exhibited aggregation-induced emissions (AIEs), and an apparent solvatochromic shift was also observed in the emission spectra as the solvent was changed from hexane to tetrahydrofuran (THF) (430 → 595 nm). In addition, the donor-acceptor charge-transfer character in these organoboranes caused a thermally responsive emission over a broad range.