Syntheses, molecular structures, electrochemical behavior, theoretical study, and antitumor activities of organotin(IV) complexes containing 1-(4-chlorophenyl)-1-cyclopentanecarboxylato ligands

The organotin(IV) compounds [Me2Sn(L)(2)] (1), [Et(2)sn(L)(2)] (2), [(Bu2Sn)-Bu-n(L)(2)] (3), [(n)Oct(2)Sn(L)(2)] (4), [Ph2Sn(L)(2)] (5), and [PhOSnL](6) (6) have been synthesized from the reactions of 1-(4-chlorophenyl)-1-cyclopentanecarboxylic acid (HL) with the corresponding diorganotin(IV) oxide or dichloride. They were characterized by IR and multinuclear NMR spectroscopies, elemental analysis, cyclic voltammetry, and, for 2, 3, 4 and 6, single crystal X-ray diffraction analysis. While 1-5 are mononuclear diorganotin (IV) compounds, the X-ray diffraction of 6 discloses a hexameric drumlike structure with a prismatic Sn6O6 core. All these complexes undergo irreversible reductions and were screened for their in vitro antitumor activities toward HL-60, BGC-823, Bel-7402, and KB human cancer cell lines. Within the mononuclear compounds, the most active ones (3, 5) are easiest to reduce (least cathodic reduction potentials), while the least active ones (1, 4) are the most difficult to reduce. Structural rearrangements (i.e., Sn-O bond cleavages and trans-to-cis isomerization) induced by reduction, which eventually can favor the bioactivity, are disclosed by theoretical/electrochemical studies

Dopant-Free Donor (D)–p–D–p–D Conjugated Hole- Transport Materials for Efficient and Stable Perovskite Solar Cells

Three novel hole-transporting materials (HTMs) using the 4-methoxytriphenylamine (MeOTPA) core were designed and synthesized. The energy levels of the HTMs were tuned to match the perovskite energy levels by introducing symmetrical electron-donating groups linked with olefinic bonds as the bridge. The methylammonium lead triiodide (MAPbI(3)) perovskite solar cells based on the new HTM Z34 (see main text for structure) exhibited a remarkable overall power conversion efficiency (PCE) of 16.1% without any dopants or additives, which is comparable to 16.7% obtained by a p-doped 2,2,7,7-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9-spirobifluorene (spiro-OMeTAD)-based device fabricated under the same conditions. Importantly, the devices based on the three new HTMs show relatively improved stability compared to devices based on spiro-OMeTAD when aged under ambient air containing 30% relative humidity in the dark

Prompt-to-afterglow transition of optical emission in a long gamma-ray burst consistent with a fireball

Long gamma-ray bursts (GRBs), which signify the end-life collapsing of very massive stars, are produced by extremely relativistic jets colliding into circumstellar medium. Huge energy is released both in the first few seconds, namely the internal dissipation phase that powers prompt emissions, and in the subsequent self-similar jet-deceleration phase that produces afterglows observed in broad-band electromagnetic spectrum. However, prompt optical emissions of GRBs have been rarely detected, seriously limiting our understanding of the transition between the two phases. Here we report detection of prompt optical emissions from a gamma-ray burst (i.e. GRB 201223A) using a dedicated telescope array with a high temporal resolution and a wide time coverage. The early phase coincident with prompt {\gamma}-ray emissions show a luminosity in great excess with respect to the extrapolation of {\gamma}-rays, while the later luminosity bump is consistent with onset of the afterglow. The clearly detected transition allows us to differentiate physical processes contributing to early optical emissions and to diagnose the composition of the jetComment: Authors' version of article published in Nature Astronomy, see their website for official versio

Over 20% PCE perovskite solar cells with superior stability achieved by novel and low-cost hole-transporting materials

The exploration of alternative low-cost molecular hole-transporting materials (HTMs) for both highly efficient and stable perovskite solar cells (PSCs) is a relatively new research area. Two novel HTMs using the thiophene core were designed and synthesized (Z25 and Z26). The perovskite solar cells based on Z26 exhibited a remarkable overall power conversion efficiency (PCE) of 20.1%, which is comparable to 20.6% obtained with spiroOMeTAD. Importantly, the devices based-on Z26 show better stability compared to devices based on Z25 and spiroOMeTAD when aged under ambient air of 30% or 85% relative humidity in the dark and under continuous full sun illumination at maximum power point tracking respectively. The presented results demonstrate a simple strategy by introducing double bonds to design hole-transporting materials for highly efficient and stable perovskite solar cells with low cost, which is important for commercial application

AMS measurement of 53Mn and its initial application at CIAE

The determination of cosmogenic 53Mn in terrestrial archives has important applications, such as burial ages, exposure age and erosion rates. Accelerator mass spectrometry (AMS) is the most sensitive technique to detect minute amounts of 53Mn. 53Mn measurements were developed at the China Institute of Atomic nergy (CIAE) using the DE-Q3D equipped AMS system. This approach was recently optimized with the goal to reach the sensitivity required for AMS measurements of 53Mn in deep-sea ferromanganese crust (DSFC) samples. Based on these improvements of sample preparation, current beam transmission and so on, 53Mn in two samples of DSFC was measured by AMS. The ratios of 53Mn/Mn corresponding to an age of 3.77 ± 0.42 and 13.73 ± 2.74 Ma by 129I dating method are (5.01 ± 2.15) 10 13 and (1.90 ± 0.96) 10 13. The ratios are close to the experimental reference values, deduced from the previous research. The experimental progress, performances and results are presented in this contribution.This work was mainly supported by the National Natural Science Foundations of China (NSFC), under Grant No. 11075221, and a partly supported by the National Natural Science Foundation of China under Grant Nos. 10705054, 41073044 and 11265005

Lick Observatory Supernova Search Follow-Up Program: Photometry Data Release of 93 Type Ia Supernovae

We present BVRI and unfiltered light curves of 93 Type Ia supernovae (SNe Ia) from the Lick Observatory Supernova Search (LOSS) follow-up program conducted between 2005 and 2018. Our sample consists of 78 spectroscopically normal SNe Ia, with the remainder divided between distinct subclasses (three SN 1991bg-like, three SN 1991T-like, four SNe Iax, two peculiar, and three super-Chandrasekhar events), and has a median redshift of 0.0192. The SNe in our sample have a median coverage of 16 photometric epochs at a cadence of 5.4 days, and the median first observed epoch is ~4.6 days before maximum B-band light. We describe how the SNe in our sample are discovered, observed, and processed, and we compare the results from our newly developed automated photometry pipeline to those from the previous processing pipeline used by LOSS. After investigating potential biases, we derive a final systematic uncertainty of 0.03 mag in BVRI for our dataset. We perform an analysis of our light curves with particular focus on using template fitting to measure the parameters that are useful in standardising SNe Ia as distance indicators. All of the data are available to the community, and we encourage future studies to incorporate our light curves in their analyses.Comment: 29 pages, 13 figures, accepted for publication in MNRA

Polymorph-induced photosensitivity change in titanylphthalocyanine revealed by the charge transfer integral

The crystal form of semiconductor materials is keenly correlated with the photosensitivity of optoelectronic devices. Thus, understanding the crystal form-dependent photosensitivity mechanism is critical. In this work, the microemulsion phase transfer method was adopted to prepare α- and β-titanylphthalocyanine (TiOPc NPs) with an average diameter of 35 nm. The photosensitivity (E1/2) of α-TiOPc NPs was 2.73 times better than that of β-TiOPc NPs, which was characterized by photoconductors under the same measurement conditions. DFT was performed to explain the relationship between crystal form and photosensitivity by systematically calculating the charge transfer integrals for all possible dimers in the two different crystal forms. The hole and electron reorganization energies of TiOPc were respectively calculated to be 53.5 and 271.5 meV, revealing TiOPc to be a typical p-type semiconductor. The calculated total hole transfer mobility (μ+) ratio (2.83) of α- to β-TiOPc was almost identical to the experimental E1/2 ratio (2.73) and the calculated photogeneration quantum efficiency (ηe-h) ratio (2.23). In addition, the optimum hole transfer routes in the crystal of α- and β-TiOPc were all along with the [1 0 0] crystal orientation, which was determined by the calculated μ+. A high charge transfer mobility leads to a high photosensitive TiOPc crystal. Consequently, these results indicate that the selected theoretical calculation method is reasonable for indirectly explaining the relationship between crystal form and photosensitivity. The TiOPc molecular solid-state arrangements, namely, the crystal forms of TiOPc, have a strong influence on the charge transport behavior, which in turn, affects its photosensitivity

Butterfly‐like Tetraazaacenequinodimethane Derivatives: Synthesis, Structure and Halochromic Properties

Two novel molecules TAP and TAH with pronounced reversible halochromic properties have been synthesized and fully characterized. Their butterfly-like structures have been confirmed through single-crystal X-ray diffraction. Their UV-Vis absorption after protonation dramatically red-shifted with naked-eye-visible color change in a very dilute concentration of 10-5 M. Note that the original color of the solution can be recovered after the neutralization with a base.Ministry of Education (MOE)Q.Z. acknowledges financial support from AcRF Tier 1 (RG 111/17,RG 2/17, RG 114/16,RG 113/18)and Tier 2 (MOE2017-T2-1-021and MOE 2018-T2-1-070),Singapore.X.L. thank the support from the National Natural Science Foundation of China(21676188) and the Science and Technology Plan Project of Tianjin(19ZXNCGX00020).J.Z. acknowledges financial support from Na-tional Natural Science Foundation of China, Grant Nos. 21773016.QZ also thanks the support from State Key Laboratory of Supramolecular Structure and Materials, Jilin University (sklssm2020041

Mixed Cations Enabled Combined Bulk and Interfacial Passivation for Efficient and Stable Perovskite Solar Cells

Highlights A mixed GAI and MAI (MGM) treatment modulating the bulk and interfacial defects simultaneously is reported. The devices’ performance is enhanced to ~24.5% in 0.12 cm2 and ~18.7% in 64 cm2 with improved stability. The MGM treatment can be applied to a wide range of perovskite compositions