Intermolecular donor-acceptor stacking to suppress triplet exciton diffusion for long-persistent organic room-temperature phosphorescence.

Controlling triplet states is crucial to improve the efficiency and lifetime of organic room temperature phosphorescence (ORTP). Although the intrinsic factors from intramolecular radiative and non-radiative decay have been intensively investigated, the extrinsic factors that affect triplet exciton quenching are rarely reported. Diffusion to the defect sites inside the crystal or at the crystal surface may bring about quenching of triplet exciton. Here, the phosphorescence lifetime is found to have a negative correlation with the triplet exciton diffusion coefficient based on the density functional theory (DFT)/time-dependent density functional theory (TD-DFT) calculations on a series of ORTP materials. For systems with a weak charge transfer (CT) characteristic, close π-π stacking will lead to strong triplet coupling and fast triplet exciton diffusion in most cases, which is detrimental to the phosphorescence lifetime. Notably, for intramolcular donor-acceptor (D-A) type systems with a CT characteristic, intermolecular D-A stacking results in ultra-small triplet coupling, thus contributing to slow triplet diffusion and long phosphorescence lifetime. These findings shed some light on molecular design toward high-efficiency long persistent ORTP.

Interference-Free Detection of Hydroxyl Radical and Arthritis Diagnosis by Rare Earth-Based Nanoprobe Utilizing SWIR Emission as Reference.

Due to the high oxidative potential of the hydroxyl radical (•OH), the accumulation of •OH in tissues can cause inflammation, such as that in arthritis. Therefore, the development of •OH detection with high efficiency and sensitivity is important for the treatment of related diseases. In this work, a cypate-modified core-shell NaErF4@NaLuF4 nanoprobe (csEr-Cy) was designed for detecting •OH on the basis of a typical reaction between cypate and •OH. The process resulted in the recovery of 654 nm upconversion luminescence emission of csEr because of a weakened inner filter effect (IFE) and Förster resonance energy transfer (FRET). The short-wavelength infrared (SWIR) emission at 1550 nm was not affected by •OH addition, thus enabling interference-free detection. Density functional theory (DFT) calculations were performed to explain the underlying mechanism. With the SWIR signal used as a reference for •OH detection, the csEr-Cy nanoprobe showed higher sensitivity and penetration than visible reference. This method was successfully used in mice for the diagnosis of arthritis in vivo. Our results provide novel insights into improving the sensitivity of nanoprobes for molecule detection and disease diagnosis.

Theoretical study on the charge transfer mechanism at donor/acceptor interface: Why TTF/TCNQ is inadaptable to photovoltaics?

A combined molecular dynamics (MD) and quantum chemical (QC) simulation method is utilized to investigate charge generation mechanism at TTF/TCNQ (tetrathiafulvalene/tetracyanoquinodimethane) heterojunction, which is a controversial donor/acceptor (D/A) interface for organic photovoltaic (OPV) devices. The TTF/TCNQ complexes extracted from MD simulation are classified into parallel and herringbone packings. And then, the amounts of charge transferred from ground states to different excited states and the corresponding energies of charge transfer (CT) state are compared and analyzed using QC simulation. Moreover, the electron transfer/recombination rates for these interfacial configurations are also studied. From these data, we have elucidated the underlying reason why TTF/TCNQ heterojunction is inadaptable to OPV application. One main reason is that large |ΔGCT| (the absolute value of Gibbs free energy change of CT) forms a large energy barrier, limiting exciton dissociation at the TTF/TCNQ heterojunction, and small |ΔGCR| (the absolute value of Gibbs free energy change of charge recombination) performs the easy recombination to the ground state.

A designed bithiopheneimide-based conjugated polymer for organic photovoltaic with ultrafast charge transfer at donor/PC(71)BM interface: theoretical study and characterization.

In the current work, a series of bithiopheneimide (BTI)-based D-A copolymers were investigated based on the reported PDTSBTI (1) to screen excellent molecules toward organic photovoltaic (OPV) donor materials. It is found that the PCE based on the proposed derivative 4, where the silicon atom is replaced with vinyl and cyano groups on the DTS unit, shows a 70 percent improvement by Scharber diagrams compared with its prototype 1. Then, the charge transfer dynamics of 1/PC71BM and 4/PC71BM were investigated, including the intermolecular charge transfer (inter-CT) and recombination (inter-CR) rates. The theoretical data demonstrate that the ratio kinter-CT/kinter-CR of 4/PC71BM heterojunction is about 1 × 10(5) times higher than that of 1/PC71BM. These results clearly reveal that the designed donor molecule 4 will be a promising candidate for high-performance OPV device. We expect that this work from electron processing at the D/A interface may provide a theoretical guideline for further optimization and design of organic copolymer donor materials.

Theoretical characterization and design of small molecule donor material containing naphthodithiophene central unit for efficient organic solar cells.

To seek for high-performance small molecule donor materials used in heterojunction solar cell, six acceptor-donor-acceptor small molecules based on naphtho[2,3-b:6,7-b']dithiophene (NDT) units with different acceptor units were designed and characterized using density functional theory and time-dependent density functional theory. Their geometries, electronic structures, photophysical, and charge transport properties have been scrutinized comparing with the reported donor material NDT(TDPP)2 (TDPP = thiophene-capped diketopyrrolopyrrole). The open circuit voltage (V(oc)), energetic driving force(ΔE(L-L)), and exciton binding energy (E(b)) were also provided to give an elementary understanding on their cell performance. The results reveal that the frontier molecular orbitals of 3-7 match well with the acceptor material PC61 BM, and compounds 3-5 were found to exhibit the comparable performances to 1 and show promising potential in organic solar cells. In particular, comparing with 1, system 7 with naphthobisthiadiazole acceptor unit displays broader absorption spectrum, higher V(oc), lower E(b), and similar carrier mobility. An in-depth insight into the nature of the involved excited states based on transition density matrix and charge density difference indicates that all S1 states are mainly intramolecular charge transfer states with the charge transfer from central NDT unit to bilateral acceptor units, and also imply that the exciton of 7 can be dissociated easily due to its large extent of the charge transfer. In a word, 7 maybe superior to 1 and may act as a promising donor candidate for organic solar cell.

Fabricating a photochromic benzonitrile Schiff base into a low-cost reusable paper-based wearable sensor for naked-eye dosimetry of UV radiations.

We report in this study a photochromic benzonitrile Schiff base, (E)-4-((2-hydroxy-4-methoxybenzylidene)amino)benzonitrile (HMBAB). The molecular design, synthesis, aggregation-induced emission (AIE) as well as the quantum chemical calculations were outlined. In particular, HMBAB would undergo a reversible tautomerism in response to UV exposure, exhibiting remarkable changes in both absorption and emission: the compound shows yellow color and green-yellow luminescence; after UV exposure, the changes into orange-red while the luminescence is dramatically quenched, accompanied by a large bathochromic-shift. In addition, the photochromic state can be fully recovered via thermal treatment. Such reversible dual-channel photochromism was investigated using UV-vis reflectance spectroscopy and colorimeter, wherein a gradient change with time and a high fatigue resistance in cycle use was recorded. The photochromism is quantified by well-established RGB and Lab color space, in which the color change can be accurately analyzed by the chromatic aberration (ΔE*Lab). Sensitivity test gives a two-stage linear relation between ΔE*Lab and UV intensity, by which a limit of detection (LOD) as low as 67 µW/cm2 is obtained. HMBAB was further fabricated into a paper-based wearable sensor, capable of being integrated into a chest card or a bracelet. It exhibits various degrees of color change in different sunlight environments, which can be readily observed by naked eyes, providing an early warning for high-dose UV radiations.

Theoretical insight into the origin of large stokes shift and photophysical properties of anilido-pyridine boron difluoride dyes.

The geometric and electronic structures and photophysical properties of anilido-pyridine boron difluoride dyes 1-4, a series of scarce 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) derivatives with large Stokes shift, are investigated by employing density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations to shed light on the origin of their large Stokes shifts. To this end, a suitable functional is first determined based on functional tests and a recently proposed index-the charge-transfer distance. It is found that PBE0 provides satisfactory overall results. An in-depth insight into Huang-Rhys (HR) factors, Wiberg bond indices, and transition density matrices is provided to scrutinize the geometric distortions and the character of excited states pertaining to absorption and emission. The results show that the pronounced geometric distortion due to the rotation of unlocked phenyl groups and intramolecular charge transfer are responsible for the large Stokes shift of 1 and 2, while 3 shows a relatively blue-shifted emission wavelength due to its mild geometric distortion upon photoemission, although it has a comparable energy gap to 1. Finally, compound 4, which is designed to realize the rare red emission in BODIPY derivatives, shows desirable and expected properties, such as high Stokes shift (4847 cm(-1)), red emission at 660 nm, and reasonable fluorescence efficiency. These properties give it great potential as an ideal emitter in organic light-emitting diodes. The theoretical results could complement and assist in the development of BODIPY-based dyes with both large Stokes shift and high quantum efficiency.

A dual-channel indicator of fish spoilage based on a D-π-A luminogen serving as a smart label for intelligent food packaging.

Advances in food monitoring benefit tremendously from the naked-eye observation and device-miniaturization of colorimetric and fluorometric methods. Intelligent food packaging, containing a built-in sensor inside food bags, is capable of real-time monitoring of food quality by visibly discernible out-put signals, which effectively ensures food safety. We synthesized a donor-π-acceptor (D-π-A) compound DPABA, and disclosed its fluorescence response to amines. According to quantum chemical calculations, DPABA is apt to D-A coupling in aggregated state, causing the formation of exciplex/excimer together with intermolecular charge/energy transfer to the disadvantage of light emission; while the evasion of amine vapors would decouple the intermolecular D-A interactions to induce stronger emission with shorter wavelength. Utilizing the amine vapor generated by fish, DPABA can serve as an indicator for freshness monitoring. To create an intelligent food package, the compound was made into cellulose film, which was further cut into smart labels to be encapsulated into food bags. The as-prepared smart label exhibits red color under ambient light and glows weak red emission under UV light, while it turns into faint yellow color in response to putrid fish, and its emission changes to bright cyan. The output signals can be accurately recorded by instrument, and detected by naked eye, suggesting high signal contrast. In addition, the smart label exhibits different changing scope in response to different degree of freshness, showing high potential for in-field detection.

A Novel Strategy toward Thermally Activated Delayed Fluorescence from a Locally Excited State.

It is well-known that thermally activated delayed fluorescence (TADF) is always generated from charge-transfer (CT) excited states in donor-acceptor (D-A) systems, which limits its application owing to a slow radiative process and a small stimulated emission cross section. Herein, a design strategy is proposed for realizing TADF from a locally excited (LE) state without a typical donor-acceptor type structure through controlling the intersystem crossing (ISC) and reverse intersystem crossing (RISC) processes between the lowest excited singlet with LE character and higher triplet states. Using this strategy, a boron difluoride derivative is theoretically predicted and experimentally synthesized to exhibit locally excited TADF (LE-TADF) with a fairly large radiative rate of 1.12 × 108 s-1, extremely fast RISC rate of 5.09 × 1010 s-1, and a large stimulated emission cross section of 4.35 × 10-17 cm2, making this a promising organic amplified spontaneous emission (ASE) material. This work might open a new avenue to extend TADF materials, especially TADF laser emitters.

Uncommon carbene-to-azole ligand rearrangement of N-heterocyclic carbenes in a ruthenium system.

The study of non-innocent behavior of NHCs (NHCs = N-heterocyclic carbenes) has great implications for NHC-involved catalysis. Herein, we report a new type of NHC-to-azole rearrangement, during which process the carbene backbone and the substituent are both non-innocent. To the best of our knowledge, this work also presents the first example of NHC-to-azole rearrangements for aryl-substituted NHCs.

A donor-π-acceptor aggregation-induced emission compound serving as a portable fluorescent sensor for detection and differentiation of methanol and ethanol in the gas phase.

The design strategy of aggregation-induced emission (AIE) fluorophores with donor-π-acceptor (D-π-A) conjugation structure has greatly contributed to the development of luminescent materials and devices, including volatile organic compounds (VOCs) sensors. In this work, a D-π-A fluorophore DEBAB was synthesized, showing both AIE and intramolecular charge transfer (ICT) properties as confirmed by spectroscopic data and quantum chemical calculations. Furthermore, there is notable emission-enhancement when DEBAB is exposed to small-molecule alcohols, such as methanol and ethanol. Based on this phenomenon, a portable film sensor was fabricated, capable of detecting methanol and ethanol in gas phase, with detection limit (DL) as low as 8.02 ppm. Our systematic investigation suggests that hydrogen-bonding may be formed between DEBAB and alcohols, intensifying the AIE efficacy while influencing the ICT process. This working mechanism is supported by density functional theory (DFT) calculations including electrostatic potential mapping and molecular total energy. In addition, a sensor array was fabricated on a cellulose paper strip, showing different levels of emission changing in response to alcohols. Thus the detection and differentiation of methanol and ethanol are enabled.

Molecular Design Strategy for Simultaneously Strong Luminescence and High Mobility: Multichannel CH-π Interaction.

It is a big challenge to achieve high-performance organic semiconductor materials integrating both high luminescence efficiency and carrier mobility, because they are commonly regarded as a pair of contradiction. Here, combining a tight-binding model and density functional theory/time-dependent density functional theory, we propose a theoretical protocol to characterize the luminescence efficiency via an excitonic effective mass and charge transport ability via charge effective mass at the same level. Applying this protocol to a series of organic semiconductor materials, we find that the multichannel CH-π interaction can induce a heavy excitonic effective mass and light charge effective mass, which effectively balance the light-emitting efficiency and carrier mobility. Thus, a practical molecular design strategy is figured out to exploit novel organic semiconductor materials with strong luminescence and fast carrier transport simultaneously.

Strategy for optical data encryption and decryption using a D-A type stimuli-responsive AIE material.

In this study, we report a new donor-acceptor (D-A) type stimuli-responsive material, (E)-4-(((9-ethyl-9H-carbazol-2-yl)methylene)amino)benzoic acid (C1), which possesses both aggregation-induced emission (AIE) and intramolecular charge transfer (ICT) natures. It glows green photoluminescence which changes into yellow color in response to mechanical stimuli, and fumigation in volatile organic compounds (VOCs) can switch the emission back to the initial state with high reversibility. In addition, the C1 film glows yellow-orange light, but turns into blue emission under continuous fumigation in ethyl acetate vapor. However the vapochromism behaves different when the C1 film is smeared: The emission of the smeared film is similar to the unsmeared but changes into cyan color after fumigation. The differences in vapochromism between smeared and unsmeared film can be easily distinguished by naked eyes. As revealed by SEM, the as-prepared film undergoes a morphology change from ill-shaped particles to microspheres in response to organic vapor, while the smeared film with scratched surface changes into dendritic patterns. According to the morphology study, the vapochromic luminescence can be ascribed to the physical adsorption of ethyl acetate vapor and the resulting change in the ICT process. In light of the unique vapochromism of C1, a new encryption-decryption technique for data recording was developed. Information can be recorded on the C1 film by mechanical writing and simultaneously concealed. It can be only accessed via fumigation in organic vapor, demonstrating a reliable steganography technology.

Toward a simple way for a mechanochromic luminescent material with high contrast ratio and fatigue resistance: Implication for information storage.

In this work, we present the synthesis and photoluminescence (PL) behaviour of a new compound, DHNC. The molecular design includes twisted conformation and the incorporation of electron donor (D) and acceptor (A) pairs, which endows the compound with both twisted intramolecular charge transfer (ICT) and aggregation-induced emission (AIE) properties. Importantly, the compound exhibits mechanochromic luminescence (MCL): The emission of the crystalline powder shows strong green emission but turns into orange-red with an obvious quenching effect after grinding, demonstrating a high contrast ratio. The emission of the ground sample can be rejuvenated though recrystallization by either immersion or fumigation in common organic solvents. The emission can be reversibly switched between two states for more than 10 cycles, showing fatigue resistance. In a quantitative mechanical experiment, the DHNC-loaded film has a remarkable emission loss with the external force up to 67.9 Mpa, showing high sensitivity. An archetype of information storage is developed based on this MCL material, which uses mechanical force to write information and organic vapour to erase. Letters and cartoon pictures can be written and erased repeatedly on the DHNC-loaded film, indicating high contrast ratio and fatigue resistance.

A mechanochromic luminescent material with aggregation-induced emission: Application for pressure sensing and mapping.

In this study, we report a new compound, (E)-4-(((2-hydroxynaphthalen-1-yl)methylene)amino)-3-methylbenzoic acid (HNMB), which shows aggregation-induced emission property as well as intramolecular charge transfer (ICT) nature. In addition, it exhibits unique mechanochromic luminescence (MCL). The HNMB solid powder emits strong emission but shows quenching effect together with bathochromic-shift after grinding, suggesting a high contrast ratio up to 1420%. Through crystallographic analysis, the relationship between MCL nature and molecular packing mode is verified: Molecules in crystalline phase adopt the J-type coupling based on less overlapped π⋯π stacking, in which multiple intermolecular interactions mainly including C-H⋯π, C-H⋯O and hydrogen bonding, help to stabilize such packing mode. When these interactions are destructed by mechanical force, the packing would be disassembled, activating the MCL behavior. Such working mechanism only needs weak external force capable of destructing intermolecular interactions, rendering the MCL material highly sensitive to pressure. As a practical application, a film sensor for pressure detection is designed based on HNMB, which gives a linear relation between the emission intensity and the external pressure in a lower range. The detection limit of the film sensor is 27.24 Mpa, suggesting high sensitivity. In addition, pressure mapping with high contrast ratio is obtained by surface plot, making this pressure sensor a reliable candidate to be instrumented for various applications.

Effect of substituent position on aggregation-induced emission, customized self-assembly, and amine detection of donor-acceptor isomers: Implication for meat spoilage monitoring.

We synthesized a class of positional isomers by attaching electron donor and acceptor units in different sites of a conjugated core. These isomers exhibit both aggregation-induced emission (AIE) and intramolecular charge transfer (ICT) effects, which are proved by adequate spectroscopic analysis. Their structure-property relationships were systematically studied. We found that relocation of the D/A units would have remarkable impact on the intermolecular dipole-dipole interaction, further controlling the shape and color of the self-assembled architectures. With D/A units shifting to different sites, four types of the structures appear sequentially, including quadrate microsheets, microrods, nanofilaments and nanowires. Furthermore, the A unit (benzoic acid moiety) of the AIE isomers is easy to adsorb amines, leading to changes in both emission wavelength and intensity. Then a portable sensor is prepared on solid support based on the self-assembled architecture of HMBA-4, which has been proved to be the most sensitive to amines. It affords fast spectral responses as well as a low detection limit of 186 Pa (vapour pressure). The sensing mechanism was revealed by density functional theory (DFT) calculation, which indicates that the spectral responses stem from the weakened ICT effect. The sensor is able to detect amine vapours generated by meat, and thus succeeds in detecting the spoiled pork samples, offering high potential for meat spoilage monitoring in real-world applications.

Solid-supported synergistic twain probes with aggregation-induced emission: A sensing platform for fingerprinting volatile amines.

Two solid emitters DMA and HBA were synthetized, showing aggregation-induced emission (AIE) phenomenon. Incorporation of electron donor-acceptor (D-A) pairs endows the solid emitters with both charge transfer (CT) state emission and distinct solvatochromic effect. The compounds undergo a rapid interaction with amines followed by the resulting weakened electron withdrawing ability to yield florescent products with either hypochromatic shift or decrease in the emission intensity. DFT calculations on HOMO and LUMO electronic cloud distribution and energy levels have demonstrated that the transition from CT state to locally excited (LE) state is mainly responsible for the spectral changes. The AIE compounds were thus developed into solid-supported amine sensor and show nice linear relationship. The detection limits of DMA- and HBA-based sensing film to ammonia gas are 2.61Pa and 2.63Pa, respectively. Time-dependent emission spectra upon treating with a variety of amines exhibited differential responses, in which two factors were defined accordingly, including maximum emission wavelength and quenching efficiency. Two-dimensional coordinate system was then built on the basis of the two factors, creating a fingerprint data base for the involved amines. The fingerprint map shows a clear differentiation of the tested amines, making DMA and HBA synergistic twain probes for identification of diverse amines.

A turn-on type stimuli-responsive fluorescent dye with specific solvent effect: Implication for a new prototype of paper using water as the ink.

In this study, we reported the photoluminescence (PL) behaviour of a new intramolecular charge transfer (ICT) compound, ((E)-2-(((2-hydroxynaphthalen-1-yl)methylene)amino)benzoic acid, (HABA), which shows ICT solvent effect in aprotic solvents as confirmed by absorption and emission spectra. While in protic solvents including water and ethanol, the charge transfer (CT) band significantly reduces. Remarkable fluorescence enhancement in the blue region was also observed for HABA in polar protic solvents. We described such phenomena as "specific solvent effect". It can be ascribed to the hydrogen bonding formation between HABA and protic solvents, which not only causes significant reduction in the rate of internal conversion but also elevates the energy gap. Density functional theory (DFT) calculations as well as the dynamics analysis were performed to further verify the existence of hydrogen bonding complexes. Stronger emission turn-on effect was observed on HABA solid film when it is treated with water and base solution. The stimuli-responsive fluorescence of HABA enables a new green printing technique that uses water/base as the ink, affording fluorescent handwritings highly distinct from the background. Thermoanalysis of the dye suggests the nice thermostability, which is highly desired for real-world printing in a wide temperature range.

A theoretical exploration of the effect of fluorine and cyano substitutions in diketopyrrolopyrrole-based polymer donor for organic solar cells.

A series of polymer donor materials 1-5 based on diketopyrrolopyrrole and thiophene unit which have been widely used in organic solar cells (OSCs) were investigated based on quantum chemical calculations. The effect of fluorine and cyano substitutions in polymer donor materials was focused on. Based on the investigation on electronic structures and optical properties of the reported molecules 1 and 2 and the analysis on some parameters relevant to charge dissociation ability at donor/acceptor interface constituted by 1 and 2 with PC61BM such as intermolecular charge transfer and recombination, driving force and Coulombic bound energy, we explained why fluorine substitution can improve OPV efficiency through strengthening eletron-withdrawing ability from a theoretical perspective. Then we designed cyano-substituted polymers 3-5 with the aim of obtaining better photovoltaic donor materials. The results reveal that our attempt to design donor materials which can balance large open-circuit voltage (Voc) and high short-circuit current (Jsc) in OSCs has worked out. It is worth noting that the substitutions of fluorine and cyano groups synergistically reduce energy gap and HOMO energy level of polymers 3 and 4. Moreover, 3/PC61BM and 4/PC61BM heterojunctions show over 107 and 104 times higher than 1/PC61BM on the ratios of intermolecular charge transfer and recombination rates (kinter-CT/kinter-CR). Thus, our work here may provide an efficient strategy to design promising donor materials in OPVs and we hope it could be useful in the future experimental synthesis.

Solvent-assistant self-assembly of an AIE+TICT fluorescent Schiff base for the improved ammonia detection.

Solvent-assistant self-assembly of an AIE+TICT fluorescent Schiff base into one-dimensional nanofilaments has been developed. The orientation of the assemblies can be controlled by a simple dewetting process: the filaments are interweaved when the self-assembly process is performed on a horizontal substrate, while tilting the substrate to a tiny angle results in the formation of highly oriented ones with long-range order as verified by microscopic examination. The compound shows remarkable fluorescent response to ammonia gas based on a TICT-LE transition. The self-assembled film presents higher detection sensitivity compared with the non-assembled test paper: the former enables 4.75 times faster response time and 6.86 times lower detection limit than the latter. Furthermore, the former demonstrates better selectivity toward ammonia gas in the presence of various organic amines. The sensing devices also enjoy the advantage of cyclic utilization. The fluorescence of the fumed devices can be converted back into the original state when they are heated at 100 °C for 5 min, as thermal treatment can desorb the ammonia gas that adsorbed in the sensing devices.