One- and Two-Dimensional CP/MAS 13C NMR Analyses of Dynamics in Poly(2-hydroxypropyl ether of bisphenol-A) (FUNDAMENTAL MATERIAL PROPERTIES-Molecular Dynamic Characterisitics)

The dynamics of amorphous poly(2-hydroxypropyl ether of bisphenol-A) (PHR), quenched from the melt, has been investigated by one- and two-dimensional solid-state 13C NMR spectroscopy. CP/MAS 13C NMR spectra from .150 to 180 oC give two specific features: (1) below 23 oC, resonance lines for CH carbons of phenylene rings split into two lines; (2) linewidths of resonance lines become broad at 20 - 50 oC above the glass transition temperature. The feature (1) indicates that phenylene C-H carbons exist in chemically different two sites at low temperatures. These two sites are probably associated with OH … hydrogen bond formation. The coalescence of the resonance lines at elevated temperatures is caused by flip motion of phenylene rings, which corresponds to the relaxation for PHR. The correlation time of the flip motion is analyzed by the two-site exchange model, and is found to follow the Arrhenius equation. The apparent activation energy is 51 kJ mol-1 by assuming an inhomogeneous correlation time distribution described by a Kohlrausch-Williams-Watts (KWW) function with an exponent of 0.2. The feature (2) is caused by the so-called motional broadening, which is originated by enhanced segmental motions. This dynamics corresponds to the relaxation for PHR and can be described by William-Landel-Ferry (WLF) equation. Two-dimensional CP/MAS 13C exchange NMR experiments confirm the existence of flip angle distribution as well as the distribution of correlation times of phenylene ring flip motion with a KWW exponent of 0.2

Striatal Cdk5-pTyr15

Striatal functions depend on the activity balance between the dopamine and glutamate neurotransmissions. Glutamate inputs activate cyclin-dependent kinase 5 (Cdk5), which inhibits postsynaptic dopamine signaling by phosphorylating DARPP-32 (dopamine- and cAMP-regulated phosphoprotein, 32 kDa) at Thr75 in the striatum. c-Abelson tyrosine kinase (c-Abl) is known to phosphorylate Cdk5 at Tyr15 (Tyr15-Cdk5) and thereby facilitates the Cdk5 activity. We here report that Cdk5 with Tyr15 phosphorylation (Cdk5-pTyr15) is enriched in the mouse striatum, where dopaminergic stimulation inhibited phosphorylation of Tyr15-Cdk5 by acting through the D2 class dopamine receptors. Moreover, in the 1-methyl-4-phenyl-1,2,4,6-tetrahydropyridine (MPTP) mouse model, dopamine deficiency caused increased phosphorylation of both Tyr15-Cdk5 and Thr75-DARPP-32 in the striatum, which could be attenuated by administration of L-3,4-dihydroxyphenylalanine and imatinib (STI-571), a selective c-Abl inhibitor. Our results suggest a functional link of Cdk5-pTyr15 with postsynaptic dopamine and glutamate signals through the c-Abl kinase activity in the striatum

A donor-acceptor 10-cycloparaphenylene and its use as an emitter in an organic light-emitting diode

We thank JSPS Core-to-Core Program and International Joint Usage/Research Program of Institute for Chemical Research, Kyoto University (grant #2020-37 and 2021-37) for financial support. The St Andrews team would also like to thank EPSRC (EP/P010482/1) for financial support. D.C. thanks the China Scholarship Council (No. 201603780001). The Kyoto team would like to thank JSPS KAKENHI Grant Numbers JP20H05840 (Grant-in-Aid for Transformative Research Areas, “Dynamic Exciton”).Here, we explored the possibility of using cycloparaphenylenes (CPP) within a donor–acceptor TADF emitter design. 4PXZPh-[10]CPP contains four electron-donating moieties connected to a [10]CPP. In the 15 wt % doped in CzSi film, 4PXZPh-[10]CPP showed sky-blue emission with λPL = 475 nm, ΦPL = 29%, and triexponential emission decays with τPL of 4.4, 46.3, and 907.8 ns. Solution-processed OLEDs using 4PXZPh-[10]CPP exhibited sky-blue emission with an λEL of 465 nm and an EQEmax of 1.0%.Publisher PDFPeer reviewe

Exploring the capability of mayenite (12CaO·7Al₂O₃) as hydrogen storage material

We utilized nanoporous mayenite (12CaO·7Al₂O₃), a cost-effective material, in the hydride state (H⁻) to explore the possibility of its use for hydrogen storage and transportation. Hydrogen desorption occurs by a simple reaction of mayenite with water, and the nanocage structure transforms into a calcium aluminate hydrate. This reaction enables easy desorption of H⁻ ions trapped in the structure, which could allow the use of this material in future portable applications. Additionally, this material is 100% recyclable because the cage structure can be recovered by heat treatment after hydrogen desorption. The presence of hydrogen molecules as H⁻ ions was confirmed by ¹H-NMR, gas chromatography, and neutron diffraction analyses. We confirmed the hydrogen state stability inside the mayenite cage by the first-principles calculations to understand the adsorption mechanism and storage capacity and to provide a key for the use of mayenite as a portable hydrogen storage material. Further, we succeeded in introducing H⁻ directly from OH⁻ by a simple process compared with previous studies that used long treatment durations and required careful control of humidity and oxygen gas to form O₂ species before the introduction of H⁻

Exact solution of kinetic analysis for thermally activated delayed fluorescence materials

Research at Kyushu, Kyoto and St Andrews Universities was supported by EPSRC and JSPS Core to Core grants (JSPS Core-to-core Program; EPSRC grant number EP/R035164/1). Authors are also grateful for financial support from the Program for Building Regional Innovation Ecosystems of the Ministry of Education, Culture, Sports, Science and Technology, Japan, JST ERATO Grant JPMJER1305, JSPS KAKENHI JP20H05840, and Kyulux Inc.The photophysical analysis of thermally activated delayed fluorescence (TADF) materials has become instrumental to providing insight into their stability and performance, which is not only relevant for organic light-emitting diodes (OLED), 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 (ISC and RISC, respectively). 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.PostprintPostprintPeer reviewe

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

Authors thank EU Horizon 2020 Grant Agreement No. 812872 (TADFlife) for funding this project. Further support was obtained by the Helmholtz Association Program at the Karlsruhe Institute of Technology (KIT). The German Research Foundation (formally Deutsche Forschungsgemeinschaft DFG) in the framework of SFB1176 Cooperative Research Centre "Molecular Structuring of Soft Matter" (CRC1176, A4, B3, C2, C6) and the cluster 3D Matter Made To Order all funded under Germany’s Excellence Strategy 2082/1--390761711 are greatly acknowledged for financial contributions. We acknowledge support from the Engineering and Physical Sciences Research Council of the UK (grant EP/P010482/1), from the International Collaborative Research Program of Institute for Chemical Research, Kyoto University (grant # 2020-37 and 2021-37), and from JSPS KAKENHI Grant Number JP20H05840 (Grant-in-Aid for Transformative Research Areas, “Dynamic Exciton”). ZZ acknowledges the financial support from the China Scholarship Council (CSC, 201606890009) for his PhD studies. EZ-C is a Royal Society Leverhulme Trust Senior Research fellow (SRF\R1\201089).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 redshifted 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.Publisher PDFPeer reviewe

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.acceptedVersionPeer reviewe

Solid-State 29Si NMR Analyses of the Structure and Dynamics of Solid Poly(di-n-alkylsilane)s (FUNDAMENTAL MATERIAL PROPERTIES-Molecular Dynamic Characteristics)

Solid-state 29Si NMR analyses of the solid structure and dynamics have been performed for poly(di-n-butylsilane) with the order-disorder transition at 76 °C. 29Si chemical shift anisotropy (CSA) spectra are measured with an ultraslow magic angle spinning at a rate less than 100 Hz. Almost rigid CSA spectra for the 7/3 helical structure are observed below the transition temperature. In contrast, axially symmetric CSA spectra with different principal values appear above the transition temperature, suggesting the onset of the rotational motion around the molecular chain axis with trans-rich conformation. The changes of the conformation and dynamics around the transition are also discussed for other poly(di-n-alkylsilane)s such as poly(dimethylsilane) and poly(di-n-hexylsilane)

Comprehensive understanding of multiple resonance thermally activated delayed fluorescence through quantum chemistry calculations

Molecules that exhibit multiple resonance (MR) type thermally activated delayed fluorescence (TADF) are highly efficient electroluminescent materials with narrow emission spectra. Despite their importance in various applications, the emission mechanism is still controversial. Here, a comprehensive understanding of the mechanism for a representative MR-TADF molecule (5, 9-diphenyl-5, 9-diaza-13b-boranaphtho[3, 2, 1-de]anthracene, DABNA-1) is presented. Using the equation-of-motion coupled-cluster singles and doubles method and Fermi’s golden rule, we quantitatively reproduced all rate constants relevant to the emission mechanism; prompt and delayed fluorescence, internal conversion (IC), intersystem crossing, and reverse intersystem crossing (RISC). In addition, the photoluminescence quantum yield and its prompt and delayed contributions were quantified by calculating the population kinetics of excited states and the transient photoluminescence decay curve. The calculations also revealed that TADF occurred via a stepwise process of 1) thermally activated IC from the electronically excited lowest triplet state T₁ to the second-lowest triplet state T₂, 2) RISC from T₂ to the lowest excited singlet state S₁, and 3) fluorescence from S₁

Solid-State 13C and 1H NMR Analyses of Hydrogen Bonding and the Conformation of Poly(vinyl alcohol) (FUNDAMENTAL MATERIAL PROPERTIES-Molecular Motion Analysis)

CP/MAS 13C NMR analyses have been made for different frozen solutions of poly(vinyl alcohol) (PVA) samples with different tacticities. The CH resonance lines of the frozen PVA solutions split in different ways significantly depending on the tacticities and the solvents. These CH resonance lines are well resolved into 9 constituent lines whose chemical shifts are estimated by assuming the downfield shifts due to intramolecular hydrogen bonding and the upfield shifts induced by the g-gauche effect. Furthermore, the relative intensities of the lines for atactic PVA samples are successfully interpreted by the statistical treatment assuming the statistical formation of the intramolecular hydrogen bond and the random distribution of the trans and gauche conformations. Separate 1H CRAMPS analyses have also revealed the existence of the OH groups free from hydrogen bonding together with hydrogen-bonded OH groups in PVA films