Ultrafine Spatial Modulation of Diazapyrene-Based Two-Dimensional Conjugated Covalent Organic Frameworks.

Tailormade bottom-up synthesis of covalent organic frameworks (COFs) from various functional building blocks offer not only tunable topology and pore size but also multidimensional properties. High crystallinity is one of the prerequisites for their structures and associated physicochemical properties. Among different π-conjugated motifs for constructing COFs, pyrene-based tetragonal structures are effective in achieving highly ordered and crystalline states. In the present research, we demonstrated that the substitution of pyrene with 2,7-diazapyrene produces nearly "flat" structures of two-dimensional (2D) COF layers by controlling the torsional angle of linker molecules. Featuring finite pore diameters and excellent thermodynamic stability of ∼500 °C, ordered face-to-face (slipped AA) stacking arrangements were produced. Extended electrical conjugation spanning 2D frames with modest optical bandgaps (Eg) of ∼2.1 eV shows the planar character of diazapyrene-based COFs. The stacking of the conjugated 2D frames with small Eg values is also beneficial for the formation of highly stable conducting pathways in the crystalline state, which was confirmed by the results of the microwave conductivity measurements. Nitrogen centers in diazapyrene units also play a key role as the active sites for proton transfer, and the maximum proton conductivity of σ = 10-2 S cm-1 was achieved along the cocontinuous nanopore structures surrounded by the active sites. Results show that tetragonal COFs based on diazapyrene can be used as a highly crystalline two-dimensional material with special electrical and proton-conducting capabilities.

Development of an Organic Emitter Exhibiting Reverse Intersystem Crossing Faster than Intersystem Crossing.

In thermally activated delayed fluorescence (TADF)-based organic light-emitting diodes (OLEDs), acceleration of reverse intersystem crossing (RISC) and suppression of intersystem crossing (ISC) are demanded to shorten a lifetime of triplet excitons. As a system realizing RISC faster than ISC, inverted singlet-triplet excited states (iST) with a negative energy difference (ΔEST) between the lowest excited singlet and the lowest triplet states have been gathering much attention recently. Here, we have focused on an asymmetric hexa-azaphenalene (A6AP) core to obtain a new insight into iST. Based on A6AP, we have newly designed A6AP-Cz with the calculated ΔEST of -44 meV. The experimental studies of a synthesized A6AP-Cz revealed that the lifetime of delayed fluorescence (τDF) was only 54 ns, which was the shortest among all organic materials. The rate constant of RISC (kRISC = 1.9×107 s-1) was greater than that of ISC (kISC = 1.0×107 s-1). The negative ΔEST of A6AP-Cz was experimentally confirmed from 1) the kRISC and kISC (-45 meV) and 2) the temperature-dependent τDF. 3) The onsets of fluorescence and phosphorescence spectra at 77 K also supported the evidence of negative ΔEST (-73 meV). This study demonstrated the potential of A6AP as an iST core for the first time.

Torsion Angle Analysis of a Thermally Activated Delayed Fluorescence Emitter in an Amorphous State Using Dynamic Nuclear Polarization Enhanced Solid-State NMR.

The torsion angle between donor and acceptor segments of a thermally activated delayed fluorescence (TADF) molecule is one of the most critical factors in determining the performance of TADF-based organic light-emitting diodes (OLEDs) because the torsion angle affects not only the energy gap between the singlet and triplet but also the oscillator strength and spin-orbit coupling. However, the torsion angle is difficult to analyze, because organic molecules are in an amorphous state in OLEDs. Here, we determined the torsion angle of a highly efficient TADF emitter, DACT-II, in an amorphous state by dynamic nuclear polarization enhanced solid-state NMR measurements. From the experimentally obtained chemical shift principal values of 15N on carbazole, we determined the average torsion angle to be 52°. Such quantification of the torsion angles in TADF molecules in amorphous solids will provide deep insight into the TADF mechanism in amorphous OLEDs.

Robust Spirobifluorene Core Based Hole Transporters with High Mobility for Long-Life Green Phosphorescent Organic Light-Emitting Devices.

Using a tailored high triplet energy hole transport layer (HTL) is a suitable way to improve the efficiency and extend the lifetime of organic light-emitting devices (OLEDs), which can use all molecular excitons of singlets and triplets. In this study, dibenzofuran (DBF)-end-capped and spirobifluorene (SBF) core-based HTLs referred as TDBFSBF1 and TDBFSBF2 were effectively developed. TDBFSBF1 exhibited a high glass transition temperature of 178 °C and triplet energy of 2.5 eV. Moreover, a high external quantum efficiency of 22.0 %, long operational lifetime at 50 % of the initial luminance of 89,000 h, and low driving voltage at 1000 cd m-2 of 2.95 V were achieved in green phosphorescent OLEDs using TDBFSBF1. Further, a high-hole mobility µh value of 1.9×10-3  cm2 V-1 s-1 was recorded in TDBFSBF2. A multiscale simulation successfully reproduced the experimental µh values and indicated that the reorganization energy was the primary factor in determining the mobility differences among these SBF core based HTLs.

Promoting Reverse Intersystem Crossing in Thermally Activated Delayed Fluorescence via the Heavy-Atom Effect.

Thermally activated delayed fluorescence (TADF) molecules are promising for realizing durable organic light-emitting diodes in all color regions. Fast reverse intersystem crossing (RISC) is a way of improving the device lifetime of TADF-based organic light-emitting diodes. To date, RISC rate constants (kRISC) of 108 s-1 have been reported for metal-free TADF molecules. Here, we report the heavy-atom effect on TADF and a molecular design for further promoting RISC. First, we reproduced all the relevant rate constants of a sulfur-containing TADF molecule (with kRISC of 108 s-1) via density functional theory. The role of the heavy-atom effect on the rapid RISC process was clarified. Our calculations also predicted that much larger kRISC (>1010 s-1) will be obtained for selenium- and tellurium-containing TADF molecules. However, a polonium-containing molecule promotes phosphorescence without exhibiting TADF, indicating that a too strong heavy-atom effect is unfavorable for achieving both rapid RISC and efficient TADF.

Near-Unity Singlet Fission on a Quantum Dot Initiated by Resonant Energy Transfer.

The conversion of a high-energy photon into two excitons using singlet fission (SF) has stimulated a variety of studies in fields from fundamental physics to device applications. However, efficient SF has only been achieved in limited systems, such as solid crystals and covalent dimers. Here, we established a novel system by assembling 4-(6,13-bis(2-(triisopropylsilyl)ethynyl)pentacen-2-yl)benzoic acid (Pc) chromophores on nanosized CdTe quantum dots (QDs). A near-unity SF (198 ± 5.7%) initiated by interfacial resonant energy transfer from CdTe to surface Pc was obtained. The unique arrangement of Pc determined by the surface atomic configuration of QDs is the key factor realizing unity SF. The triplet-triplet annihilation was remarkably suppressed due to the rapid dissociation of triplet pairs, leading to long-lived free triplets. In addition, the low light-harvesting ability of Pc in the visible region was promoted by the efficient energy transfer (99 ± 5.8%) from the QDs to Pc. The synergistically enhanced light-harvesting ability, high triplet yield, and long-lived triplet lifetime of the SF system on nanointerfaces could pave the way for an unmatched advantage of SF.

Efficient Direct Reverse Intersystem Crossing between Charge Transfer-Type Singlet and Triplet States in a Purely Organic Molecule.

The front cover artwork is provided by the group of Prof. Hironori Kaji, Dr. Yoshimasa Wada, and Mr. Yasuaki Wakisaka (Institute for Chemical Research, Kyoto University). The image shows our designed emitter molecule, MA-TA, possessing charge-transfer (CT) character in both triplet and singlet states. The dynamic flexibility of molecules allows effective reverse intersystem crossing (RISC) and MA-TA show excellent performances in any kinds of hosts. Read the full text of the Article at 10.1002/cphc.202001013.

Efficient Direct Reverse Intersystem Crossing between Charge Transfer-Type Singlet and Triplet States in a Purely Organic Molecule.

In the field of organic light-emitting diodes, thermally activated delayed fluorescence (TADF) materials have achieved great performance. The key factor for this performance is the small energy gap (ΔEST ) between the lowest triplet (T1 ) and singlet excited (S1 ) states, which can be realized in a well-separated donor-acceptor system. Such systems are likely to possess similar charge transfer (CT)-type T1 and S1  states. Recent investigations have suggested that the intervention of other type-states, such as locally excited triplet state(s), is necessary for efficient reverse intersystem crossing (RISC). Here, we theoretically and experimentally demonstrate that our blue TADF material exhibits efficient RISC even between singlet CT and triplet CT states without any additional states. The key factor is dynamic flexibility of the torsion angle between the donor and acceptor, which enhances spin-orbit coupling even between the charge transfer-type T1 and S1  states, without sacrificing the small ΔEST . This results in excellent photoluminescence and electroluminescence performances in all the host materials we investigate, with sky-blue to deep-blue emissions. Among the hosts investigated, the deepest blue emission with CIE coordinates of (0.15, 0.16) and the highest EQEMAX of 23.9 % are achieved simultaneously.

Multichromophore Molecular Design for Thermally Activated Delayed-Fluorescence Emitters with Near-Unity Photoluminescence Quantum Yields.

Three multichromophore thermally activated delayed fluorescence (TADF) molecules, p-di2CzPN, m-di2CzPN, and 1,3,5-tri2CzPN, were synthesized and characterized. These molecules were designed by connecting the TADF moiety 4,5-di(9H-carbazol-9-yl)phthalonitrile (2CzPN) to different positions of a central benzene ring scaffold. Three highly soluble emitters all exhibited near-quantitative photoluminescence quantum yields (ΦPL) in toluene. High ΦPLs were also achieved in doped films, 59 and 70% for p-di2CzPN and m-di2CzPN in 10 wt % DPEPO doped film, respectively, and 54% for 1,3,5-tri2CzPN in 20 wt % doped CBP films. The rate constant of reverse intersystem crossing (kRISC) for p-di2CzPN and m-di2CzPN in DPEPO films reached 1.1 × 105 and 0.7 × 105 s-1, respectively, and kRISC for 1,3,5-tri2CzPN in the CBP film reached 1.7 × 105 s-1. A solution-processed organic light-emitting diode based on 1,3,5-tri2CzPN exhibited a sky-blue emission with CIE coordinates of (0.22, 0.44) and achieved a maximum external quantum efficiency of 7.1%.

Theoretical Determination of Rate Constants from Excited States: Application to Benzophenone.

A cost-effective method of theoretically predicting electronic-transition rate constants from the excited states of molecules is reported. This method is based on density functional theory calculations of electronic states and quantitative rate constant determination with the Fermi golden rule. The method is applied to the theoretical determination of the excited-state decay mechanism of photoexcited benzophenone, a representative molecule in photochemistry and biochemistry. Calculated rate constants for benzophenone are quantitatively consistent with experimental ones, which validates the reliability of our rate constant calculation. The calculated population kinetics indicate that S1 → T2 → T1 → S0 is the predominant decay pathway.

Molecular Vibration Accelerates Charge Transfer Emission in a Highly Twisted Blue Thermally Activated Delayed Fluorescence Material.

In the development of new organic light-emitting diodes, thermally activated delayed fluorescence (TADF) materials have drawn interest because of their ability to upconvert electrically generated triplet excitons into singlets. Efficient TADF requires a well-balanced large transition dipole moment (µ) between the lowest excited singlet state (S1) and the ground state (S0) and a small energy splitting (ΔEST) between S1 and the lowest triplet state (T1). However, a number of highly twisted donor-acceptor-type TADF molecules have been reported to exhibit high performance in OLEDs, although these molecules may sacrifice µ in exchange for a very small ΔEST. Here, we theoretically investigate the origin of efficient emission from a perpendicularly twisted blue emitter, MA-TA. In this system, the µ value almost vanishes in the static approximation; however, vibrational contributions increase µ considerably. Hence, we show that the dynamics of excitons have a critical role in such TADF systems.

Exact Solution of Kinetic Analysis for Thermally Activated Delayed Fluorescence Materials.

The photophysical analysis of thermally activated delayed fluorescence (TADF) materials has become instrumental for providing insights into their stability and performance, which is not only relevant for organic light-emitting diodes but also for other applications such as sensing, imaging, and photocatalysis. Thus, a deeper understanding of the photophysics underpinning the TADF mechanism is required to push materials design further. Previously reported analyses in the literature of the kinetics of the various processes occurring in a TADF material rely on several a priori assumptions to estimate the rate constants for forward and reverse intersystem crossing. In this report, we demonstrate a method to determine these rate constants using a three-state model together with a steady-state approximation and, importantly, no additional assumptions. Further, we derive the exact rate equations, greatly facilitating a comparison of the TADF properties of structurally diverse emitters and providing a comprehensive understanding of the photophysics of these systems.

Effect of a twin-emitter design strategy on a previously reported thermally activated delayed fluorescence organic light-emitting diode.

In this work we showcase the emitter DICzTRZ in which we employed a twin-emitter design of our previously reported material, ICzTRZ. This new system presented a red-shifted emission at 488 nm compared to that of ICzTRZ at 475 nm and showed a comparable photoluminescence quantum yield of 57.1% in a 20 wt % CzSi film versus 63.3% for ICzTRZ. The emitter was then incorporated within a solution-processed organic light-emitting diode that showed a maximum external quantum efficiency of 8.4%, with Commission Internationale de l'Éclairage coordinate of (0.22, 0.47), at 1 mA cm-2.

Identification of Prime Factors to Maximize the Photocatalytic Hydrogen Evolution of Covalent Organic Frameworks.

Visible-light-driven hydrogen (H2) production from water is a promising strategy to convert and store solar energy as chemical energy. Covalent organic frameworks (COFs) are front runners among different classes of organic photocatalysts. The photocatalytic activity of COFs depends on numerous factors such as the electronic band gap, crystallinity, surface area, exciton migration, stability of transient species, charge separation and transport, etc. However, it is challenging to fine tune all of these factors simultaneously to enhance the photocatalytic activity. Hence, in this report, an effort has been made to understand the interplay of these factors and identify the key factors for efficient photocatalytic H2 production through a structure-property-activity relationship. Careful molecular engineering allowed us to optimize all of the above plausible factors impacting the overall catalytic activities of a series of isoreticular COFs. The present study determines three prime factors: light absorption, charge carrier generation, and its transport, which influence the photocatalytic H2 production of COFs to a much greater extent than the other factors.

Lamellar Structure in Alanine-Glycine Copolypeptides Studied by Solid-State NMR Spectroscopy: A Model for the Crystalline Domain of Bombyx mori Silk Fibroin in Silk II Form.

Bombyx mori silk fibroin (SF) fibers with excellent mechanical properties have attracted widespread attention as new biomaterials. However, the structural details are still not conclusive. Here, we propose a lamellar structure for the crystalline domain of the SF fiber based on structural analyses of the Ala Cß peaks in the 13C cross-polarization/magic angle spinning NMR spectra of (Ala-Gly)m (m = 9, 12, 15, and 25) and 13C selectively labeled (Ala-Gly)15 model peptides. Namely, three Ala Cß peaks with relative intensities of 1:2:1 obtained by deconvolution were assigned to two kinds of ß-sheet and a ß-turn, which are interpreted as a lamellar structure formed by repetitive folding using ß-turns every eighth amino acid, for which the basic structure is (Ala-Gly)4 in an antipolar arrangement. The dynamics and intermolecular arrangement were further studied using 13C solid-state spin-lattice relaxation time observations and the rotational echo double resonance experiments, respectively.

Effect of Vibronic Coupling on Correlated Triplet Pair Formation in the Singlet Fission Process of Linked Tetracene Dimers.

Tetracene-based singlet fission (SF) materials show application prospects as triplet sensitizers in organic optoelectronics. SF involves internal conversion from photoexcited singlet states 1(S1S0) to correlated triplet pair states 1(T1T1). We derive an expression for the internal conversion rate on the basis of the Fermi golden rule with an artificial Lorentzian broadening. The internal conversion rate depends on the interstate vibronic couplings (VCs) and energy difference (ΔESF) between 1(S1S0) and 1(T1T1). Therefore, understanding the interplay between interstate VCs and ΔESF is necessary to reveal how the structure-property relationship affects the SF efficiency. Here, we propose a method to quantitatively analyze interstate VCs between 1(S1S0) and 1(T1T1). We apply this method to SF in ortho-, meta-, and para-bis(ethynyltetracenyl)benzene and identify an effect of interstate VCs on the 1(T1T1) formation rate. The interstate VCs of the meta dimer are remarkably weak, which reasonably explains the experimentally obtained slow 1(T1T1) formation rate. The weak VCs result from a very small overlap density between 1(S1S0) and 1(T1T1) of the meta dimer. Furthermore, we investigate structure-dependence of the 1(T1T1) formation rate of the para dimer and find that the para dimer shows large VCs and small ΔESF when the rotational angle between the two tetracene units is large, which leads to the faster 1(T1T1) formation rate than those of the ortho and meta dimers. The rotation of the tetracene units is the origin of the experimentally observed fast 1(T1T1) formation rate of the para dimer.

Noise Reduction in Solid-State NMR Spectra Using Principal Component Analysis.

A noise reduction method was developed for solid-state nuclear magnetic resonance spectroscopy using multivariate analysis. Principal component analysis was first applied for cross-polarization/magic angle spinning and 13C spin-lattice relaxation measurements of solid-state nuclear magnetic resonance array spectra. The contact time of cross-polarization/magic angle spinning and the delay time in spin-lattice relaxation measurements were continuously changed to obtain a series of spectra, which were used for noise reduction using principal component analysis. The noise reduction method successfully produced spectra with improved signal-to-noise ratios. This noise reduction method shortens the measurement time and allows for detection of components with minute signals.

Superflexible Multifunctional Polyvinylpolydimethylsiloxane-Based Aerogels as Efficient Absorbents, Thermal Superinsulators, and Strain Sensors.

Aerogels are porous materials but show poor mechanical properties and limited functionality, which significantly restrict their practical applications. Preparation of highly bendable and processable aerogels with multifunctionality remains a challenge. Herein we report unprecedented superflexible aerogels based on polyvinylpolydimethylsiloxane (PVPDMS) networks, PVPDMS/polyvinylpolymethylsiloxane (PVPMS) copolymer networks, and PVPDMS/PVPMS/graphene nanocomposites by a facile radical polymerization/hydrolytic polycondensation strategy and ambient pressure drying or freeze drying. The aerogels have a doubly cross-linked organic-inorganic network structure consisting of flexible polydimethylsiloxanes and hydrocarbon chains with tunable cross-linking density, tunable pore size and bulk density. They have a high hydrophobicity and superflexibility and combine selective absorption, efficient separation of oil and water, thermal superinsulation, and strain sensing.

Gram-Scale Syntheses and Conductivities of [10]Cycloparaphenylene and Its Tetraalkoxy Derivatives.

[10]Cycloparaphenylene ([10]CPP) and its tetraalkoxy derivatives were synthesized on the gram scale in 7 steps starting from 1,4-benzoquinone or 2,5-dialkoxy-1,4-benzoquinone. The key steps involve the highly cis-selective bis-addition of 4-bromo-4'-lithiobiphenyl to the quinones to produce a five-ring unit containing cyclohexa-1,4-diene-3,6-diol moiety, the platinum-mediated dimerization of the five-ring unit, and the H2SnCl4-mediated reductive aromatization of cyclohexadienediol. The tetraalkoxy substituents increased the solubility of [10]CPP in common organic solvents. The carrier-transport properties of thin films of [10]CPP and its derivatives were measured for the first time and indicated that [10]CPP derivatives could rival phenyl-C61-butyric acid methyl ester, which is used widely as an n-type active layer in bulk heterojunction photovoltaics.

Aerogels from Chloromethyltrimethoxysilane and Their Functionalizations.

Reactions of chloromethyltrimethoxysilane (CMTMS) and its derived colloidal network polychloromethylsilsesquioxane (PCMSQ) have been investigated to extend the material design strategy toward functionalized and mechanically reinforced aerogels. In a carefully designed sol-gel system, CMTMS has afforded transparent aerogels in the presence of cationic surfactant. The surface chloromethyl groups with polarity and reactivity are shown to be useful for supporting nanostructures, with photoluminescent carbon dots (C-dots) prepared from polyethylenimine and citric acid as an example. Furthermore, since nucleophilic substitution (SN2) reactions on the surface chloromethyl groups are found to control the equilibrium of formation/dissociation of siloxane bonds, a new gelation strategy triggered by SN2 reactions in sol-gel has been developed. In the presence of nucleophilic organic species such as polyamines, a hybrid network consisting of PCMSQ cross-linked with a polyamine nucleophile can be prepared to enhance mechanical properties of aerogel.