Uncovering the Intramolecular Emission and Tuning the Nonlinear Optical Properties of Organic Materials by Cocrystallization

The spectroscopic and photophysical properties of organic materials in the solid‐state are widely accepted as a result of their molecular packing structure and intermolecular interactions, such as J‐ and H‐aggregation, charge‐transfer (CT), excimer and exciplex. However, in this work, we show that Spe‐F₄DIB cocrystals (SFCs) surprisingly retain the energy levels of photoluminescence (PL) states of Spe crystals, despite a significantly altered molecular packing structure after cocrystallization. In comparison, Npe‐F₄DIB cocrystals (NFCs) with new spectroscopic states display different spectra and photophysical behaviors as compared with those of individual component crystals. These may be related to the molecular configuration in crystals, and we propose Spe as an “intramolecular emissive” material, thus providing a new viewpoint on light‐emitting species of organic chromophores. Moreover, the nonlinear optical (NLO) properties of Npe and Spe are firstly demonstrated and modulated by cocrystallization. The established “molecule‐packing‐property” relationship helps to rationally control the optical properties of organic materials through cocrystallization.     

Field dependence of magnetoresistance in epitaxial single-crystal La2/3Ca1/3MnO3-δ thin film

Epitaxial La_2/3Ca_1/3MnO₃ thin films were prepared on NdGaO₃(1lO) substrates by d.c. magnetron sputtering method. The measurements of magnetoresistance ρ(H) upon magnetic field at different temperatures were carried out in the field range of 0–8 T. It is found that ρ(H) obeys the following relations: when the temperature (T) is higher than the Curie temperature below and whenT is far WowT _c. It is suS8ested that the negative magnetoresistive effect is mainly due to enhancement of the magnetoconductance. Project supported by the National Natural Science Foundation of China (Grant No. 19504012) and the Chinese Academy of Sciences.     

镶嵌于NH2-MIL-125 (Ti)衍生氮掺多孔碳中的花状超细纳米TiO2作为高活性和稳定性的锂离子电池负极材料

由于具有高安全性和优异的循环稳定性,二氧化钛(TiO₂)作为负极材料被广泛地应用于锂离子电池领域。但是较差的导电性和离子传输速率限制了TiO₂的进一步应用和发展。鉴于此,我们以花状NH₂-MIL-125 (Ti)为前驱体和硬模板,成功合成出了具有花状结构的超细纳米TiO₂/多孔氮掺杂碳片(N-doped porous carbon)复合物(记为FL-TiO₂/NPC)。过程中所制备的纳米TiO₂-金属有机构架(Ti-MOF)展现出由二维褶皱多孔纳米片堆积、组装而成的花状结构。一方面,二维褶皱纳米片包含TiO₂纳米颗粒可以增大活性物质与电解液的接触面积;另一方面,氮掺杂多孔碳基体可以提高整体复合物的导电性和结构完整性。将所获得的FL-TiO₂/NPC作为负极组装成的锂半电池, 在0.5 A·g^-1、300圈后仍有384.2 mAh·g^-1以及在1 A·g^-1、500圈仍有279.1 mAh·g^-1的比容量。进一步性能测试表明,在2 A·g^-1、2000圈长循环测试后,其仍能保持256.5 mAh·g^-1的比容量和接近100%的库伦效率。该优异的电化学活性和稳定性主要起源于材料独特的花状结构。我们的合成策略为今后制备高储锂性能的金属氧化物/多孔氮掺杂碳负极提供了一种新的思路。     

Microcalorimetric in situ synthesis and the solid-state reaction enthalpy change for 1D CoII coordination polymer

Journal of Thermal Analysis and Calorimetry - One cobalt (II) coordination polymer, named as [Co(3,3′-BDA)(H2O)2]n (3,3′-H2BDA is 3,3′-dicarboxyl-2,2′-bipyridine), has been...     

An efficient synthesis of highly functionalized [5,6] aromatic spiroketals by hetero-Diels-Alder reaction

A hetero-Diels-Alder reaction of vinyl sulfoxides with o-quinone methides precursor constructs highly functionalized [5,6] aromatic spiroketal skeletons in moderate to good yields with high regioselectivity. The two functional groups (ketone and olefin) can be further subjected to many synthetic transformations.     

Stability analysis of the zero solution for two class evolution equations

By constructing some suitable Lyapunov-type functionals and applying the theory of the definite-quadratic form, we obtain the stability of the zero solution of two classes of evolution equations with delays, including reaction–diffusion equations and damped wave equations. Our criteria depend on the derivatives of delays. Consequently, when the delays are constants, these criteria are independent of the magnitudes of the delays, so the delays are harmless for the stability of the zero solution.     

Electronic Configuration Tuning of Centrally Extended Non-Fullerene Acceptors Enabling Organic Solar Cells with Efficiency Approaching 19 %

In the molecular optimizations of non-fullerene acceptors (NFAs), extending the central core can tune the energy levels, reduce nonradiative energy loss, enhance the intramolecular (donor-acceptor and acceptor-acceptor) packing, facilitate the charge transport, and improve device performance. In this study, a new strategy was employed to synthesize acceptors featuring conjugation-extended electron-deficient cores. Among these, the acceptor CH-BBQ, embedded with benzobisthiadiazole, exhibited an optimal fibrillar network morphology, enhanced crystallinity, and improved charge generation/transport in blend films, leading to a power conversion efficiency of 18.94 % for CH-BBQ-based ternary organic solar cells (OSCs; 18.19 % for binary OSCs) owing to its delicate structure design and electronic configuration tuning. Both experimental and theoretical approaches were used to systematically investigate the influence of the central electron-deficient core on the properties of the acceptor and device performance. The electron-deficient core modulation paves a new pathway in the molecular engineering of NFAs, propelling relevant research forward.     

Optimized Crystal Framework by Asymmetric Core Isomerization in Selenium-Substituted Acceptor for Efficient Binary Organic Solar Cells

Both the regional isomerization and selenium-substitution of the small molecular acceptors (SMAs) play significant roles in developing efficient organic solar cells (OSCs), while their synergistic effects remain elusive. Herein, we developed three isomeric SMAs (S-CSeF, A-ISeF, and A-OSeF) via subtly manipulating the mono-selenium substituted position (central, inner, or outer) and type of heteroaromatic ring on the central core by synergistic strategies for efficient OSCs, respectively. Crystallography of asymmetric A-OSeF presents a closer intermolecular π–π stacking and more ordered 3-dimensional network packing and efficient charge-hopping pathways. With the successive out-shift of the mono-selenium substituted position, the neat films give a slightly wider band gap and gradually higher crystallinity and electron mobility. The PM1 : A-OSeF afford favourable fibrous phase separation morphology with more ordered molecular packing and efficient charge transportation compared to the other two counterparts. Consequently, the A-OSeF-based devices achieve a champion efficiency of 18.5 %, which represents the record value for the reported selenium-containing SMAs in binary OSCs. Our developed precise molecular engineering of the position and type of selenium-based heteroaromatic ring of SMAs provides a promising synergistic approach to optimizing crystal stacking and boosting top-ranked selenium-containing SMAs-based OSCs.     

A Novel 1,066 nm Nd:Gd<Subscript>0<Emphasis Type="Italic">.</Emphasis>69</Subscript>Y<Subscript>0<Emphasis Type="Italic">.</Emphasis>3</Subscript>NbO<Subscript>4</Subscript> Passively <Emphasis Type="Italic">Q</Emphasis>-Switched Pulse-Burst Laser

We demonstrate for the first time a Cr⁴⁺:YAG passively Q-switched 1066 nm pulse-burst laser under 879 nm direct pump with a novel Nd:Gd_0.69Y_0.3NbO₄ crystal. The output laser characteristics with different pump repetition rates and different Cr⁴⁺:YAG initial transmission are studied. Without the Cr⁴⁺:YAG, we obtain a maximum output energy of 2.55 mJ at an absorbed pump energy of 5.79 mJ with the highest 48% slope efficiency. The pulse-burst laser contains a maximum of 7 pulses for a Cr⁴⁺:YAG initial transmission of 55% and a pump repetition rate of 1 kHz. The single-pulse energy and narrowest pulse width reach 160 μJ and 5.5 ns at 38.2 kHz, with a peak power of 32 kW.     

复折射率光纤传输特性分析的Davidenko方法

增益或损耗对光纤的传输特性影响很大。使用Davidenko方法对复折射率光纤的传输特性进行了分析。研究了复折射率纤芯或复折射率包层阶跃光纤,通过比较发现,使用Davidenko方法得到的解与精确解符合得很好。对于芯区为复折射介质的光纤,HE11模与LP01模增益值偏差约为0.6%;对于包层区为复折射率介质的光纤,HE11模与LP01模增益值偏差约为2%。实际研究工作中,为了得到更精确的结果,应该求解全矢量的复本征方程,尤其是包层具有增益或损耗的光纤。