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1.
Indeno[1,2‐b]fluorene‐based [2,2]cyclophanes with 4n/4n and 4n/[4n+2] π‐electron systems were prepared, and their structures were identified by X‐ray crystallography. With short π–π distances around 3.0 Å, [2.2](5,11)indeno[1,2‐b]fluorenophane and its precursor [2.2](5,11)indeno[1,2‐b]fluorene‐6,12‐dionophane exhibit remarkable transannular interactions, leading to their unusual electrochemical and photophysical properties. With the aid of femtosecond transient absorption spectroscopy, the transition from the monomeric excited state to the redshifted H‐type dimeric state was first observed, correlating to the calculated excitonic energy splitting and the steady‐state absorption spectra induced by charge‐transfer‐mediated superexchange interaction.  相似文献   
2.
Alkaline metals are an ideal negative electrode for rechargeable batteries. Forming a fluorine‐rich interphase by a fluorinated electrolyte is recognized as key to utilizing lithium metal electrodes, and the same strategy is being applied to sodium metal electrodes. However, their reversible plating/stripping reactions have yet to be achieved. Herein, we report a contrary concept of fluorine‐free electrolytes for sodium metal batteries. A sodium tetraphenylborate/monoglyme electrolyte enables reversible sodium plating/stripping at an average Coulombic efficiency of 99.85 % over 300 cycles. Importantly, the interphase is composed mainly of carbon, oxygen, and sodium elements with a negligible presence of fluorine, but it has both high stability and extremely low resistance. This work suggests a new direction for stabilizing sodium metal electrodes via fluorine‐free interphases.  相似文献   
3.
本文采用高压均质结合对辊挤压工艺对天然凹凸棒石进行棒晶解离得到了纯度较高和比表面积较大(133.7 m2/g)的纳米解离凹凸棒石. 进一步通过机械共混法分别将天然凹凸棒石和纳米解离凹凸棒石与硅橡胶生胶复合制备了天然凹凸棒石-硅橡胶和纳米解离凹凸棒石-硅橡胶材料,研究了天然凹凸棒石和纳米解离凹凸棒石对凹凸棒石/硅橡胶复合材料热氧化降解和老化性能的影响. 结果表明,天然凹凸棒石-硅橡胶和纳米解离凹凸棒石-硅橡胶在300 oC热氧老化处理0.5 h后,相比于纯硅橡胶,初始5%失重温度从385 oC提高至396∽399 oC. 系列表征结果表明,天然凹凸棒石和纳米解离凹凸棒石增强了纳米粒子与硅橡胶之间的相互作用从而抑制了纳米颗粒聚集,并且可显著提高硅橡胶侧链Si-CH3的保存率,从而提高了该复合材料的热氧化降解和老化性能. 此外,纳米解离凹凸棒石可大大抑制纳米粒子的长大;因此老化后,纳米解离凹凸棒石-硅橡胶表现出了比硅橡胶(10.6%、7.4%和5.0%)更高的拉伸强度、断裂伸长率和撕裂强度保留率(40.6%、34.9% 和30.1%).  相似文献   
4.
Both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) are crucial to water splitting, but require alternative active sites. Now, a general π‐electron‐assisted strategy to anchor single‐atom sites (M=Ir, Pt, Ru, Pd, Fe, Ni) on a heterogeneous support is reported. The M atoms can simultaneously anchor on two distinct domains of the hybrid support, four‐fold N/C atoms (M@NC), and centers of Co octahedra (M@Co), which are expected to serve as bifunctional electrocatalysts towards the HER and the OER. The Ir catalyst exhibits the best water‐splitting performance, showing a low applied potential of 1.603 V to achieve 10 mA cm?2 in 1.0 m KOH solution with cycling over 5 h. DFT calculations indicate that the Ir@Co (Ir) sites can accelerate the OER, while the Ir@NC3 sites are responsible for the enhanced HER, clarifying the unprecedented performance of this bifunctional catalyst towards full water splitting.  相似文献   
5.
Diindeno-fused dibenzo[a,h]anthracene 6 and diindeno-fused dibenzo[c,l]chrysene 9 contain the key moieties 1,4-quinodipropene (1,4-QDP) and 2,6-naphthoquinodipropene (2,6-NQDP), respectively, and they both have an open-shell singlet ground state. The latter compound exhibits a strong biradical character and interesting properties, including a low ΔET−S (2.44 kcal mol−1), a small HOMO–LUMO gap (1.06 eV), a wide photoabsorption range (250–1172 nm), and a large two-photon absorption cross-section (σ=1342±56 GM). This work verifies that 6 has a slightly larger HOMO–LUMO gap and ΔET−S than its helical isomer diindeno[2,1-f:1′,2′-j]picene (DIP), but is a much stronger two-photon absorber, verifying the important effect of geometry on the photophysical properties.  相似文献   
6.
A reproducible formation of strongly bent crystals was accomplished by structurally restraining macrocyclic π-conjugated molecules. The model π-units consist of two 9,10-bis(2-thienylethynyl)anthracenes with a strong propensity for stacking, which are connected in a macrocyclic fashion via two alkylene linkers. The correlation between the crystalline morphology and the macrocyclic structures restrained by a variety of flexible alkylene linker combinations was systematically studied. Bent crystals were obtained only with specific alkylene linkers of appropriate chain length. The alkylene linkers can adopt different conformations in the crystal packing, so as to fill voids within the macrocycle. The ability to form several similar molecular structures with different alkylene conformations gives rise to contaminations of different crystalline phases within a single crystal, and it is these phase contaminations which are responsible for the bending of the crystals.  相似文献   
7.
Trace quantities of hydrogen‐bonding impurities in otherwise highly purified and dried glassy hydrocarbon matrices at 77 K can modify the relative triplet state energy levels, and hence the photophysical properties of two aromatic ketones, xanthone and chromone, to the extent that the intrinsic spectroscopic properties are obscured. The intrinsic spectroscopic properties of each are revealed in multicrystalline n‐alkane Shpol'skii matrices, and also can be observed in rigorously purified and dried hydrocarbon glasses at 77 K. The extreme sensitivity to stoichiometric, and even substoichiometric quantities of hydrogen‐bonding impurities arises from the near‐degeneracy of the two lowest‐lying triplet states, and the sensitive nature of the n→π* blueshift phenomena to specific hydrogen‐bonding interactions.  相似文献   
8.
Herein, we introduce the cyclic 8π-electron (C8π) molecule N,N′-diaryl-dihydrodibenzo[a,c]phenazine ( DPAC ) as a dual-functional donor to establish a series of new donor–linker–acceptor (D–L–A) dyads DLA1 – DLA5 . The excited-state bent-to-planar dynamics of DPAC regulate the energy gap of the donor, while the acceptors A1 – A5 are endowed with different energy gaps and HOMO/LUMO levels. As a result, the rate and efficiency of the excited-state electron transfer vs. energy transfer can be finely harnessed, which is verified via steady-state spectroscopy and time-resolved emission measurements. This comprehensive approach demonstrates, for the first time, the manifold of excited-state properties governed by bifunctional donor-based D–L–A dyads, including bent-to-planar, photoinduced electron transfer (PET) from excited donor to acceptor (oxidative-PET), fluorescence resonance energy transfer (FRET), bent-to-planar followed by electron transfer (PFET), and PET from donor to excited acceptor (reductive-PET).  相似文献   
9.
This paper describes the effect of solvent-induced synthetic routes of aluminium pendant oxazoline-amido-phenolate complexes. Treatment of ligand precursor L with AlMe3 in a 1:1 ratio in diethyl ether yielded the four-coordinated complex (LAlMe)2. Reaction of ligand precursor L with AlMe3 in a 1:2 ratio in hexane generated the four-coordinated complex L(AlMe2)2. A novel transformation mode occurred from L(AlMe2)2 to (LAlMe)2 when using diethyl ether or tetrahydrofuran as solvent. A density functional theory computational study also supports a plausible mechanism. All results were supported by spectroscopic data and in agreement with single-crystal X-ray diffraction structural analysis.  相似文献   
10.
Titanium-based polyanions have been intensively investigated for sodium-ion batteries owing to their superior structural stability and thermal safety. However, their low working potential hindered further applications. Now, a cation and anion dual doping strategy is used to boost the redox potential of Ti-based cathodes of Na3Ti0.5V0.5(PO3)3N as a new cathode material for sodium ion batteries. Both the Ti3+/Ti4+ and V3+/V4+ redox couples are reversibly accessed, leading to two distinctive voltage platforms at ca. 3.3 V and ca. 3.8 V, respectively. The remarkably improved cycling stability (86.3 %, 3000 cycles) can be ascribed to the near-zero volume strain in this unusual cubic symmetry, which has been demonstrated by in situ synchrotron-based X-ray diffraction. First-principles calculations reveal its well-interconnected 3D Na diffusion pathways with low energy barriers, and the two-sodium-extracted intermediate NaTi0.5V0.5(PO3)3N is also a stable phase according to formation energy calculations.  相似文献   
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