Anionic Hydrogen-Bonded Frameworks Showing Tautomerism and Colorful Luminescence for the Ultrasensitive Detection of Acetone.

Tautomers coexisting in an equilibrium system have significant potential for regulating luminescent properties because of their structural differences. However, separating and stabilizing tautomers at room temperature is a considerable challenge. In this study, it is found that hydrogen-bonded organic frameworks (HOFs) composed of Br- anions can effectively separate and stabilize two proton-transfer tautomers of triarylformamidinium bromide: namely, the nitrogen cation (BA-N) and carbon cation (BA-C). The BA-N crystal consisting of a dense anionic HOF and parallelly aligned organic cations exhibits green thermally activated delayed fluorescence and red room-temperature phosphorescence (RTP). The BA-C crystal contains acetone molecules that induce an antiparallel arrangement of the organic cations to form a loose HOF, producing blue prompt fluorescence and green RTP. Interestingly, switching of the HOFs between BA-N and BA-C can be achieved through the uptake and release of acetone, thereby dynamically adjusting multiple luminescent properties. Consequently, the HOF crystals can be used for the highly sensitive and specific sensing of acetone with a detection limit of 66.74 ppm. This study not only stabilizes tautomeric luminescent materials at room temperature, but also provides a new method for constructing smart HOFs with a sensitive response to a stimulus.

Nearly Unity Quantum Yield Persistent Room-Temperature Phosphorescence from Heavy Atom-Free Rigid Inorganic/Organic Hybrid Frameworks.

Synergism between covalent and non-covalent bonds is employed to fix an organic phosphor guest in a rigid inorganic framework, simulating the stiffening effect seen in the glassy state and realizing efficient and ultralong room-temperature phosphorescence (RTP). Twelve heavy-atom-free composites have been obtained through introducing arylboric or arylcarboxylic acid derivatives into the inorganic boric acid matrix by solid-phase synthesis. Owing to the stiffening effect of multiple bonds, all the composites show highly efficient and persistent RTP of guest molecules with a quantum yield ranging from 39.8 % to ca. 100 % and a lifetime up to 8.74 s, which results in a 55 s afterglow visible to the naked eye after exposure to a portable UV lamp. Interestingly, it is found that the substitution position and quantity of carboxyl in the guest have a great influence on the phosphorescent properties, and that the heavy-atom effect is invalid in such host-guest hybrid systems. The 100 g grade composite is easily prepared because of the solvent-free, green, and simple synthesis method. These results provide an important way for the development of RTP materials with ultrahigh quantum yield and ultralong lifetime, as well as their practical applications in the fields of anti-counterfeiting and information storage, among others.

Light/Force-Sensitive 0D Lead-Free Perovskites: From Highly Efficient Blue Afterglow to White Phosphorescence with Near-Unity Quantum Efficiency.

Herein, new types of zero-dimensional (0D) perovskites (PA6InCl9 and PA4InCl7) with blue room-temperature phosphorescence (RTP) were obtained from InCl3 and aniline hydrochloride. These are highly sensitive to external light and force stimuli. The RTP quantum yield of PA6InCl9 can be enhanced from 25.2 % to 42.8 % upon illumination. Under mechanical force, PA4InCl7 exhibits a phase transform to PA6InCl9, thus boosting ultralong RTP with a lifetime up to 1.2 s. Furthermore, white and orange pure RTP with a quantum yield close to 100 % can be realized when Sb3+ was introduced into PA6InCl9. The white pure phosphorescence with a color-rendering index (CRI) close to 90 consists of blue RTP of PA6InCl9 and orange RTP of Sb3+ . Thus, this work not only overcomes long-standing problems of low quantum yield and short lifetime of blue RTP, but also obtains high-efficiency white RTP. It provides a feasible method to realize near-unity quantum efficiency and has great application potential in the fields of optical devices and smart materials.

Solution-processed, top-emitting, microcavity polymer light-emitting diodes for the pure red, green, blue and near white emission.

Top-emitting microcavity polymer light-emitting diodes (TMPLEDs) are of great significance for active matrix PLED displays with high color purity. However, the complex device structures of highly efficient microcavity organic light-emitting diodes fabricated by the full vapor deposition technology are not suitable for solution-processed PLEDs. Solution-processed TMPLEDs with simple device structures are promising candidates for large-area, mass production display techniques. In this work, three strategies were used to apply microcavity into PLEDs: (1) double Ag electrodes performed as the mirrors of cavity, instead of a multi-layer Bragg reflector, which simplified the device structure and fabrication process; (2) three solution-processed functional layers were specially designed for avoiding the inter-infiltration between the different solutions and to improve the interface contacts; (3) high order microcavities were utilized according to the optical simulation results, in which thick EMLs benefited from thickness control and reproductivity. As a result, the full-color emission including pure red, green, blue was realized, and quasi-white light was also achieved from a single polymer emitting material. The achievement of color purity always requires the sacrifice of part of the current efficiency due to the spectra narrowing, while the higher current efficiency of green TMPLED (10.08 cd A-1) compared to that of non-cavity PLED (~8.60 cd A-1) cast a light on future improvements.

Large Changes in Fluorescent Color and Intensity of Symmetrically Substituted Arylmaleimides Caused by Subtle Structure Modifications.

Herein we report on four diarylmaleimides based on 3- or 2-substituted benzothiophene (M3S or M2S) and benzofuran (M3O or M2O), which show very different emission properties: aggregation-caused quenching (ACQ), aggregation-induced emission (AIE), and dual-state strong emission (DSE) in both solution and solid states. Their emission color in the solid state can be adjusted from green-yellow into red. M2O displays strong red solid-state emission at 630 nm with a quantum yield of 46.3 %. Single-crystal X-ray diffraction analysis confirms that their large distinction in solid-state emission originates from their different packing structures: hydrogen-bonded organic frameworks (HOFs) for M3S, a staggered structure for M3O, J-aggregation for M2S, and weak H-aggregation for M2O. HOF of M3S and weak H-aggregation of M2O make them produce inverse-type piezochromic fluorescence: blueshifted "turn-on" and redshifted "turn-off" emission, respectively. These results provide new insight in fluorescence manipulated by subtle structure modification.

Fused Nonacyclic Electron Acceptors for Efficient Polymer Solar Cells.

We design and synthesize four fused-ring electron acceptors based on 6,6,12,12-tetrakis(4-hexylphenyl)-indacenobis(dithieno[3,2-b;2',3'-d]thiophene) as the electron-rich unit and 1,1-dicyanomethylene-3-indanones with 0-2 fluorine substituents as the electron-deficient units. These four molecules exhibit broad (550-850 nm) and strong absorption with high extinction coefficients of (2.1-2.5) × 105 M-1 cm-1. Fluorine substitution downshifts the LUMO energy level, red-shifts the absorption spectrum, and enhances electron mobility. The polymer solar cells based on the fluorinated electron acceptors exhibit power conversion efficiencies as high as 11.5%, much higher than that of their nonfluorinated counterpart (7.7%). We investigate the effects of the fluorine atom number and position on electronic properties, charge transport, film morphology, and photovoltaic properties.

Diarylmaleimide-based branched oligomers: strong full-color emission in both solution and solid films.

Maleimide and benzene are employed as a dendron and a core, respectively, to construct two series of non-conjugate branched oligomers (B3G1 and B1G2) based on diarylmaleimide fluorophores by an alkylation reaction. Surface aryl groups are changed to tune the emissive color of branched oligomers from blue (λem = 480 nm) to red (λem = 651 nm), realizing full-color emission. The investigation on the photophysical properties of the oligomers indicates that they display intense emission in both solution and solid films, due to the suppression of intramolecular rotation and intermolecular interaction. Molecular simulation and natural transition orbital analysis show that the electron transition takes place in the individual arylmaleimide for the non-conjugate linkage of fluorophores in branched oligomers. It can avoid the unpredictability of the luminescence properties caused by the interaction of fluorophores. In addition, the good solubility, thermostability and oxidative stability of the branched oligomers make them have huge potential in the solution-processable photonic application. These results demonstrate that such a design strategy of non-conjugate branched oligomers is a very efficient and constructive method to obtain high-performance light-emitting materials in both solution and solid films.

Dual-core star-shaped single white polymers: the effect of host structure on luminescence properties.

The non-emissive benzene ring and green-emissive arylmaleimide are employed as two independent cores to construct dual-core white star-shaped polymers (DC-PFMs). Due to the totally star-shaped structure, DC-PFMs display a higher quantum yield and electroluminescence efficiency for a more efficient energy transfer from the host to the guest than traditional single-core polymers (SC-PFMs).

Study of yellow luminescence of binary terbium complexes based on 3,3',4,4'-biphthalic anhydride.

Three novel binary Tb(III) complexes (TbL2, TbL, and Tb2L; L=3,3',4,4'-biphenyl tetracarboxylic ligand) were synthesized by changing the molar ratio of Tb(III) to 3,3',4,4'-biphthalic anhydride (BPDA) (1∶2, 1∶1, and 2∶1, respectively). IR spectra indicate that there are two coordination modes of the carboxylate ligands with Tb3+ ions in the complexes. Most of them are in bridging mode; the others are in chelating mode. These complexes all have good thermal stability. The photophysical properties of these complexes are studied in detail using UV absorption spectra, fluorescence spectra, and transient fluorescence spectra. The results indicate that the photoluminescence properties of the complexes depend strongly on the molar ratio of Tb(III) to BPDA. When the molar ratio of Tb(III) to BPDA is 1∶1, complex TbL exhibits the strongest yellow light emission among the three Tb(III) complexes. However, complex Tb2L exhibits a weaker yellowish-green light emission when the molar ratio of Tb(III) to BPDA is 2∶1. The phenomenon of the yellow emission from terbium complexes is rarely reported.

Photoinduced π-Bond breakage causing dynamic closing-opening shell transition of Z-type Diphenylmaleonitriles molecules.

Organic molecules with dynamic covalent-bonding characteristics have attracted much attention for their important role in constructing stimulus-responsive smart materials. However, it is difficult to realize sensitive and reversible covalent bond cleavage/formation through external stimuli in the aggregated state of molecules. Herein, a series of 2,3-diphenylmaleonitriles (DPMNs) with photoinduced π-bond cleavage properties have been designed and synthesized to construct the dynamic covalent bond materials. The cis-form 2,3-diphenylmaleonitriles (Z-DPMNs) exhibit significant photochromism in both solid and solution states under ultraviolet light and visible light. The photochromism stems from the photoinduced π-bond splitting of Z-DPMNs, resulting in a transition from the closed-shell to open-shell structure. Moreover, the twisted structure and molecular stacking of Z-DPMNs, the push-pull electron effect of substituents, and the external factors including temperature and solvent polarity have important effects on the dynamic conversion of π-bonds. Based on the sensitive and reversible optical performance transformation, Z-DPMNs can be applied as safety ink in anti-counterfeiting, information encryption and storage systems. This work not only provides an approach for constructing dynamic covalent bonds but also greatly enriches stimulus-responsive materials.

Synthesis of MXene-based nanocomposite electrode supported by PEDOT:PSS-modified cotton fabric for high-performance wearable supercapacitor.

The rapid development of wearable and portable electronic devices prompts the ever-growing demand for wearable, flexible, and light-weight power sources. In this work, a MXene/GNS/PPy@PEDOT/Cotton nanocomposite electrode with excellent electrochemical performances was fabricated using cotton fabric as a substrate. Poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS) was coated on the cotton fabric to obtain a conductive substrate through a controllable dip-drying coating process, while a nanocomposite consisting of MXene, Graphene nanoscroll (GNS), and polypyrrole (PPy) was directly synthesized and deposited on the PEDOT:PSS-modified cotton fabric via a one-step in situ polymerization method. The resultant MXene/GNS/PPy@PEDOT/Cotton electrode delivers excellent electrochemical performances including an ultra-high areal capacitance of 4877.2 mF·cm-2 and stable cycling stability with 90 % capacitance retention after 3000 cycles. Moreover, the flexible symmetrical supercapacitor (FSC) assembled with the MXene/GNS/PPy@PEDOT/Cotton electrodes demonstrates a prominent areal capacitance (2685.28 mF·cm-2 at a current density of 1 mA·cm-2) and a high energy density (322.15 µWh·cm-2 at a power density of 0.46 mW·cm-2). In addition, the application of the FSC for wearable electronic devices was demonstrated.

Non-Equivalent Donor-Acceptor Type Polymers as Dopant-Free Hole-Transporting Materials for Perovskite Solar Cells.

Electron donor (D)-electron acceptor (A) type conjugated polymers present bright prospects as dopant-free hole-transporting materials (HTMs) for perovskite solar cells (PVSCs). Most of the reported D-A polymeric HTMs contain equivalent amounts of D and A units, while the appropriate excess proportion of D units could optimize the aggregation state of polymer chains and improve the hole transport properties of the polymers. Herein, a non-equivalent D-A copolymerization strategy was utilized to develop three indacenodithiophene-benzotriazole-based polymeric HTMs for PVSCs, named as F-10, F-15, and F-20, and the equivalent D-A polymer F-00 was studied in parallel. Effects of D : A ratio on the hole transport properties of these D-A type polymeric HTMs, including energy level, molecular stacking, hole mobility, and surface morphology, were investigated by theoretical simulation and test analysis. F-15 performed best due to the appropriate D : A ratio, endowing the PVSCs a champion power conversion efficiency of 20.37 % with high stability, which confirms the fine-tuning D : A ratio via non-equivalent D-A copolymerization strategy is very helpful to construct D-A type polymeric HTMs for high-performance PVSCs.

Multi-functional fluorescent probe for Hg2+, Cu2+ and ClO- based on a pyrimidin-4-yl phenothiazine derivative.

A multi-functional fluorescent probe based on PzDPM (10-ethyl-3,7-di(pyrimidin-4-yl)-10H-phenothiazine) for Hg(2+), Cu(2+) and ClO(-) has been synthesized and characterized. The probe comprises an electron-donating fluorophore core of 10-ethylphenothiazine and two Hg(2+)-specific chelating arms of pyrimidin-4-yl. The 10-ethylphenothiazine also acts as a Cu(2+)/ClO(-)-specific reactive moiety. PzDPM exhibits green fluorescence and selectively senses Hg(2+)/Cu(2+) upon coordination/reaction in acetonitrile (MeCN), and behaves as a turn-off chemosensor or ratiometric chemodosimeter, respectively. On the other hand, PzDPM is very weakly emissive in aqueous solution but acts as an excellent turn-on chemodosimeter for ClO(-) in 1 : 4 (v/v) MeCN : Tris-HCl (10 mM, pH = 7.0) with a maximum fluorescent intensity increase of over 110-fold. The probe PzDPM allows the determination of Hg(2+), Cu(2+) and ClO(-) at 10(-7) M levels with satisfactory selectivity.

Effect of pH on the photophysical properties of two new carboxylic-substituted iridium(III) complexes.

Two cyclometalated iridium(III) complexes have been prepared based on 2-(4-diphenylamino-phenyl)-quinoline and incorporating carboxylic acid ethyl ester (­COOC(2)H(5), (TPAQCE)(2)Irpic and carboxylic acid (­COOH, (TPAQCOOH)(2)Irpic) substituents at the 4-position of the quinoline ligand, respectively. The absorption, emission and (1)H NMR spectra of (TPAQCE)(2)Irpic and (TPAQCOOH)(2)Irpic under alkaline or acidic conditions demonstrate that they respond to the pH of the surrounding solvent environment. The deprotonation of the carboxylic acid group significantly blue-shifts the metal-to-ligand charge transfer absorption band of (TPAQCOOH)(2)Irpic by 48 nm and enhances the emission quantum-yield in DMSO. In addition, (1)H-NMR titration reveals that (TPAQCOOH)(2)Irpic is deprotonated into negatively charged (TPAQCOO(−))(2)Irpic in free DMSO-d(6) solution, and the acid-induced N^O ancillary ligands cleavage or replacement in (TPAQCOOH)(2)Irpic could be ignored. A water-soluble near-neutral optical pH probe (TPAQCOOH)(2)Irpic with pK(a) of ~7 is also reported. In aqueous buffer, (TPAQCOOH)(2)Irpic possesses an obvious emission response with an excellent linearity in the pH range of 6.50­8.00, showing a promising application in bioprocessing.

Multiexciton Generation from a 2D Organic-Inorganic Hybrid Perovskite with Nearly 200% Quantum Yield of Red Phosphorescence.

2D organic-inorganic hybrid perovskites (OIHPs) show obvious advantages in the field of optoelectronics due to their high luminescent stability and good solution processability. However, the thermal quenching and self-absorption of excitons caused by the strong interaction between the inorganic metal ions lead to a low luminescence efficiency of 2D perovskites. Herein, a 2D Cd-based OIHP phenylammonium cadmium chloride (PACC) with a weak red phosphorescence (ΦP  < 6%) at 620 nm and a blue afterglow is reported. Interestingly, the Mn-doped PACC exhibits very strong red emission with nearly 200% quantum yield and 15 ms lifetime, thus resulting in a red afterglow. The experimental data prove that the doping of Mn2+ not only induces the multiexciton generation (MEG) process of the perovskite, avoiding the energy loss of inorganic excitons, but also promotes the Dexter energy transfer from organic triplet excitons to inorganic excitons, thus realizing the superefficient red-light emission of Cd2+ . This work suggests that guest metal ions can induce host metal ions to realize MEG in 2D bulk OIHPs, which provides a new idea for the development of optoelectronic materials and devices with ultrahigh energy utilization.

Greatness in Simplicity: Efficient Red Room-Temperature Phosphorescence from Simple Halogenated Maleimides with a 2D Layered Structure.

Herein, two maleimide derivatives substituted by Br (DBM) and I (DIM) with a two-dimensional (2D) layered structure are found to have highly efficient red room-temperature phosphorescence (RTP) at 660 nm in solid state, which is independent of their morphology (crystal, powder, and film). The red RTP of DBM and DIM is closely related to the synergism of nπ-ct-π* transitions and the 2D halogen-bonded network. Interestingly, the red RTP can be excited by visible light of 500 nm, which should be ascribed to the forbidden absorption from the ground state to the triplet state activated in the layered halogen-bonded framework. Due to the rich intermolecular interactions in the rigid layered structure, the red RTP of DBM is very stable under water or external force stimulation. Notably, Hg(II) and Cd(II) ions in a pure aqueous solution result in an opposite change in the RTP intensity of the DBM film. The detection limit of Hg(II) ion is as low as 2.5 × 10-5 nM, lesser than all reported values. The above results not only provide a new idea for the design of simple and efficient red RTP materials but also make it possible to develop solid-state phosphorescent probes for toxic heavy metal ions in environmental sewage with high sensitivity and selectivity.

Theoretical studies of electron transport in thiophene dimer: effects of substituent group and heteroatom.

The electron-transport properties of various substituted molecules based on the thiol-ended thiophene dimer (2Th1DT) are investigated through density functional theory (DFT) combined with nonequilibrium Green's function (NEGF) method. The current-voltage (I-V) curves of all the Au/2Th1DT/Au systems in this work display similar steplike features, while their equilibrium conductances show a large difference and some of these I-V curves are asymmetric distinctly. The results reveal the dependence of conductance on the energy level of the substituted 2Th1DT molecules. Rectification ratios are computed to examine the asymmetric properties of the I-V curves. The rectifying behavior in the 2Th1DT molecule containing the amino group close to the molecular end is more prominent than that in the other molecules. The rectifying behavior is analyzed through transmission spectra and molecular projected self-consistent Hamiltonian (MPSH) states. Slight negative differential resistance (NDR) can be observed in some of the systems. The electron-transport properties of 2Th1DT molecules containing different heteroatoms are also investigated. The results indicate that the current in heteroatom-containing molecules is larger than that in their pristine analogues, and lighter heteroatoms are more favorable than heavier heteroatoms for electron transport of the thiophene dimer.

First-principles study of rectification in bis-2-(5-ethynylthienyl)ethyne molecular junctions.

Using density functional theory (DFT) combined with the first-principles nonequilibrium Green's function (NEGF), we investigated the electron-transport properties and rectifying behaviors of several molecular junctions based on the bis-2-(5-ethynylthienyl)ethyne (BETE) molecule. To examine the roles of different rectification factors, asymmetric electrode-molecule contacts and donor-acceptor substituent groups were introduced into the BETE-based molecular junction. The asymmetric current-voltage characteristics were obtained for the molecular junctions containing asymmetric contacts and donor-acceptor groups. In our models, the computed rectification ratios show that the mode of electrode-molecule contacts plays a crucial role in rectification and that the rectifying effect is not enhanced significantly by introducing the additional donor-acceptor components for the molecular rectifier with asymmetric electrode-molecule contacts. The current-voltage characteristics and rectifying behaviors are discussed in terms of transmission spectra, molecular projected self-consistent Hamiltonian (MPSH) states, and energy levels of MPSH states.

A metal-free 2D layered organic ammonium halide framework realizing full-color persistent room-temperature phosphorescence.

Organic-inorganic hybrid metal halides have attracted intensive attention because of their unique electronic structure and solution processability. They have a rigid micro/nano-structure and heavy atom effect, which has obvious advantages in promoting organic room temperature phosphorescence (RTP). However, the toxicity of heavy metals has limited their further development. Herein, two metal-free 2D layered ammonium halides, homopiperonylammonium bromide and chloride (HLB and HLC), are described for the first time. Their layered structure consists of rigid inorganic ammonium halide laminates and neatly stacked organic layers. The rigid laminates and external heavy atom effect of halogen atoms make HLB and HLC produce green RTP. When phosphor guests with different triplet energies are doped into HLB, HLC, or phenylethylamine salt hosts, effective full-color and even white ultra-long RTP with phosphorescence quantum yield up to 18.7% and lifetime up to 1.7 s is realized through energy transfer between the host and guest. Due to the simple solution synthesis, 10 g-level doped layered organic ammonium halides with the same phosphorescence properties can be easily obtained. The information ink based on these doped halides and non-toxic ethanol solvent can form various patterns on filter paper. The fluorescence and phosphorescence of these patterns are sensitive to the excitation wavelength and acid-base vapor. Consequently, they can be applied to multiple complex anti-counterfeiting and fluorescence/phosphorescence dual-mode chemical sensors.

Multicolor Output from 2D Hybrid Perovskites with Wide Band Gap: Highly Efficient White Emission, Dual-Color Afterglow, and Switch between Fluorescence and Phosphorescence.

Herein, an organic fluorophore termed NLAC is introduced into 2D hybrid perovskites with wide band gap (>3.54 eV) to give a green emission with quantum yield up to 81%. The highly efficient luminescence is ascribed to avoiding the aggregation of NLAC and formation of an inorganic free exciton which is easy to thermally quench. On this basis, a new strategy to generate efficient white emission with afterglow has been proposed by codoping a short-wavelength fluorophore and long-wavelength phosphor into 2D organic-inorganic hybrid perovskites (OIHPs). As a result, a single-component white-light-emitting material PEPC-3N based on NLAC with CIE of (0.33, 0.36) and quantum yield up to 43% can be obtained. Interestingly, PEPC-3N shows a dual-color organic afterglow and excitation-wavelength-dependent emission, consequently forming a switch between green fluorescence and yellow afterglow. This unique performance indicates PEPC-3N has huge potential in afterglow WLEDs and information storage.