Solution State‐Like Reactivity of a Flexible Crystalline Werner‐Type Metal ComplexZhang, Yunya; Zheng, Xin; Saito, Yuki; Takeda, Takashi; Hoshino, Norihisa; Takahashi, Kiyonori; Nakamura, Takayoshi; Akutagawa, Tomoyuki; Noro, Shin‐ichiro
doi: 10.1002/anie.202407924pmid: 39092669
Flexible crystalline solids exhibit unique properties in response to external stimuli like heat and light. However, challenges exist in developing crystalline solids that have similar degrees of flexibility as in solution. Herein, we report the preparation of the new flexible crystalline metal complex [Cd(CF3SO3)2(4‐spy)4] (4‐spy=4‐styrylpyridine), which contains photoreactive 4‐spy ligand. Unlike traditional solids, this metal complex displays solution state‐like [2+2] photocycloaddition reactivity. Specifically, UV irradiation of the crystalline material leads to formation of the same diverse array of dimers and cis isomer that are generated by photoreaction in the solution state. In addition, the photoresponsive flexibility of the solid leads to a photosalient effect and photo‐induced formation of pores. The origin of the solution state‐like photoreactivity of the solid is related to properties of the Cd(II) cation and fluorinated CF3SO3 anion, and the multi‐orientational arrangement of the 4‐spy ligands.
Unravelling White Phosphorus: Experimental and Computational Studies Reveal the Mechanisms of P4 HydrostannylationCammarata, Jose; Westermair, Franz F.; Coburger, Peter; Duvinage, Daniel; Janssen, Marvin; Uttendorfer, Maria K.; Beckmann, Jens; Gschwind, Ruth M.; Wolf, Robert; Scott, Daniel J.
doi: 10.1002/anie.202408423pmid: 38946592
The hydrostannylation of white phosphorus (P4) allows this crucial industrial precursor to be easily transformed into useful P1 products via direct, ‘one pot’ (or even catalytic) procedures. However, a thorough mechanistic understanding of this transformation has remained elusive, hindering attempts to use this rare example of successful, direct P4 functionalization as a model for further reaction development. Here, we provide a deep and generalizable mechanistic picture for P4 hydrostannylation by combining DFT calculations with in situ 31P NMR reaction monitoring and kinetic trapping of previously unobservable reaction intermediates using bulky tin hydrides. The results offer important insights into both how this reaction proceeds and why it is successful and provide implicit guidelines for future research in the field of P4 activation.
“Anions‐in‐Colloid” Hydrated Deep Eutectic Electrolyte for High Reversible Zinc Metal AnodesCheng, Min; Li, Diantao; Cao, Junlun; Sun, Tianjiang; Sun, Qiong; Zhang, Weijia; Zha, Zhengtai; Shi, Mengyao; Zhang, Kai; Tao, Zhanliang
doi: 10.1002/anie.202410210pmid: 39023074
Zn metal as a promising anode for aqueous batteries suffers from severe zinc dendrites, anion‐related side reactions, hydrogen evolution reaction (HER) and narrow electrochemical stable window (ESW). Herein, an “anions‐in‐colloid” hydrated deep eutectic electrolyte consisting of Zn(ClO4)2 ⋅ 6H2O, β‐cyclodextrin (β‐CD), and H2O with mass ratio of 7 : 4.5 : 3 (ACDE‐3) is designed to improve the stability of zinc anode. The ACDE‐3 reconfigures the hydrogen‐bond (HB) network and regulates the solvation shell. More importantly, the hydroxyl‐rich β‐cyclodextrins (β‐CDs) in ACDE‐3 self‐assemble into micelles, in which the steric effect between adjacent β‐CDs in micelles restricts the movement of anions. This unique “anions‐in‐colloid” structure enables the eutectic system with a high Zn2+ transference number (tZn2+) of 0.84. Thus, ACDE‐3 inhibits the formation of dendrite, prevents the anion‐involved side reactions, suppresses the HER, and enlarges the ESW to 2.32 V. The Zn//Zn symmetric cell delivers a long lifespan of 900 hours at 0.5 mA cm−2, and the Zn//Cu half cells have a high average columbic efficiency (ACE) of 97.9 % at 0.5 mA cm−2 from cycle 15 to 200 with a uniform and compact zinc deposition. When matched with a poly(1,5‐naphthalenediamine) (poly(1, 5‐NAPD)) cathode, the full battery with a low negative/positive capacity (N/P) ratio of 2 can still cycle steadily for 200 cycles at a current density of 1.0 A g−1. Additionally, this electrolyte has been proven to be operative over a wide temperature range from −40 °C to 40 °C.
Matched Electron‐Transport Materials Enabling Efficient and Stable Perovskite Quantum‐Dot‐Based Light‐Emitting DiodesWang, Jindi; Li, Mingyang; Cai, Bo; Ren, Hongdan; Fan, Wenxuan; Xu, Leimeng; Yao, Jisong; Wang, Shalong; Song, Jizhong
doi: 10.1002/anie.202410689pmid: 39072910
Light‐emitting diodes (LEDs) based on perovskite quantum dots (QDs), abbreviated as P‐QLEDs have been regarded as significantly crucial emitters for lighting and displays. Efficient and stable P‐QLEDs still lack ideal electron transport materials (ETM), which could efficiently block hole, transport electron, reduce interface non‐radiative recombination and possess high thermal stability. Here, we report 2,4,6‐Tris(3′‐(pyridine‐3‐yl) biphenyl‐3‐yl)‐1,3,5‐triazine (TmPPPyTz, 3P) with strong electron‐withdrawing moieties of pyridine and triazine to modulate the performance of P‐QLEDs. Compared with commonly used 1,3,5‐Tris(1‐phenyl‐1H‐benzimidazol‐2‐yl)benzene (TPBi), the pyridine in 3P have a strong interaction with perovskites, which can effectively suppress the interface non‐radiative recombination caused by the Pb2+ defects on the surface of QDs. In addition, 3P have deep highest occupied molecular orbital (HOMO) (enhancing hole‐blocking properties), matched lowest unoccupied molecular orbital (LUMO) and excellent electron mobility (enhancing electron transport properties), realizing the carrier balance and maximizing the exciton recombination. Furthermore, high thermal resistance of 3P obviously improves the stability of QDs under variable temperature, continuous UV illumination, and electric field excitation. Resultantly, the P‐QLEDs using the 3P as ETM achieved an outstanding performance with a champion EQE of 30.2 % and an operational lifetime T50 of 3220 hours at an initial luminance of 100 cd m−2, which is 151 % and about 11‐fold improvement compared to control devices (EQE=20 %, T50=297 hours), respectively. These results provide a new concept for constructing the efficient and stable P‐QLEDs from the perspective of selective ETM.
Scalable Production of 2D Non‐Layered Metal Oxides through Metal–Organic Gel Rapid Redox TransformationLiu, Zhiyuan; Wang, Dong; Yang, Huazeng; Feng, Liu; Xu, Xin; Si, Weimeng; Hou, Yongzhao; Wen, Guangwu; Zhang, Rui; Qiu, Jieshan
doi: 10.1002/anie.202409204pmid: 39010735
Two‐dimensional (2D) nonlayered metal compounds with porous structure show broad application prospects in electrochemistry‐related fields due to their abundant active sites, open ions/electrons diffusion channels, and faradaic reactions. However, scalable and universal synthesis of 2D porous compounds still remains challenging. Here, inspired by blowing gum, a metal‐organic gel (MOG) rapid redox transformation (MRRT) strategy is proposed for the mass production of a wide variety of 2D porous metal oxides. Adequate crosslinking degree of MOG precursor and its rapid redox with NO3− are critical for generating gas pressure from interior to exterior, thus blowing the MOG into 2D carbon nanosheets, which further act as self‐sacrifice template for formation of oxides with porous and ultrathin structure. The versatility of this strategy is demonstrated by the fabrication of 39 metal oxides, including 10 transition metal oxides, one II‐main group oxide, two III‐main group oxides, 22 perovskite oxides, four high‐entropy oxides. As an illustrative verification, the 2D transition metal oxides exhibit excellent capacitive deionization (CDI) performance. Moreover, the assembled CDI cell could act as desalting battery to supply electrical energy during electrode regeneration. This MRRT strategy offers opportunities for achieving universal synthesis of 2D porous oxides with nonlayered structures and studying their electrochemistry‐related applications.