Dalton Transactions

doi: 10.1039/d4dt90035apmid: N/A

doi: 10.1039/d4dt90036gpmid: N/A

Takeyama, Tomoyuki; Shimazaki, Yuichi

doi: 10.1039/d3dt04230hpmid: 38319292

The phenoxyl radical binding copper complexes have been widely developed and their detailed geometric and electronic structures have been clarified. While many one-electron oxidized CuII–phenolate complexes have been reported previously, recent studies of the Cu–phenolate complexes proceed toward elucidation of the complexes with other oxidation states, such as the phenoxyl radical binding CuI complexes and CuIV–phenolate complexes in the formal oxidation state. This Perspective focuses on new aspects of the properties and reactivities of various Cu-phenolate and Cu–phenoxyl radical complexes with emphasis on the relationship between geometric and electronic structures.

Zheng, Kangting; Ma, Pengtao

doi: 10.1039/d3dt03999dpmid: 38295380

Since the first formation of the famous “Peacock–Weakley” anions [Ln(W5O18)2]8/9−, a steady stream of breakthroughs have been made in the chemistry of multitalented lanthanide (Ln)-based polyoxometalates (POMs) for their potentially desirable properties. In particular, LnIII ions are generally recognised as the “vitamins of the modern industry” owing to their ability to cover a wide emission range, endowing Ln-based POMs with great potential for versatile and diverse luminescence-related applications. In this frontier, we discuss the synthesis strategies and intramolecular energy transfer in Ln-based POM derivatives. Then, the progressive improvements achieved with Ln-based POMs in photoluminescence applications are highlighted, focusing mainly on luminescent and fluorescent probes. Finally, the challenges for Ln-based POM materials for photoluminescence applications are discussed.

Liu, Qianqian; Liu, Kehan; Huang, Jianfeng; Hui, Chiyuan; Li, Xiaoyi; Feng, Liangliang

doi: 10.1039/d3dt04244hpmid: 38294259

Electrocatalytic water splitting is considered to be one of the most promising technologies for large-scale sustained production of H2. Developing non-noble metal-based electrocatalytic materials with low cost, high activity and long life is the key to electrolysis of water. Transition metal sulfides (TMSs) with good electrical conductivity and a tunable electronic structure are potential candidates that are expected to replace noble metal electrocatalysts. In addition, self-supported electrodes have fast electron transfer and mass transport, resulting in enhanced kinetics and stability. In this paper, TMS self-supported electrocatalysts are taken as examples and their recent progress as hydrogen evolution reaction (HER) electrocatalysts is reviewed. The HER mechanism is first introduced. Then, based on optimizing the active sites, electrical conductivity, electronic structure and adsorption/dissociation energies of water and intermediates of the electrocatalysts, the article focuses on summarizing five modulation strategies to improve the activity and stability of TMS self-supported electrode electrocatalysts in recent years. Finally, the challenges and opportunities for the future development of TMS self-supported electrodes in the field of electrocatalytic water splitting are presented.

Imamura, Yuki; Yoshino, Haruka; Le Ouay, Benjamin; Ohtani, Ryo; Ohba, Masaaki

doi: 10.1039/d3dt03914epmid: 38347817

A novel 2D Hofmann-type framework was prepared with a bidentate co-ligand, 5,5′-dimethyl-2,2′-bipyridyl (dmbpy), which forces the curvature of the layer. X-ray diffraction analysis demonstrated that the coordination polymers, MnII(dmbpy)[MVN(CN)4] (MV = Mn (1) and Cr (2)), formed a considerably corrugated 2D cyanide-bridged network with a quasi C4v symmetric building unit, [CrVN(CN)4]2−, and trigonal prismatic coordination geometry around MnII. Compound 2 demonstrated a metamagnetic-like ordering at 14.4 K, caused by the intra- and inter-layer antiferromagnetic interactions between CrV (S = 1/2) and MnII (S = 5/2), and a weak ferromagnetic behaviour at 2 K reflecting the single-ion anisotropy of CrV and structural anisotropy.

Li, Siyuan; Jiang, Wenchao; Sui, Qi; Gao, Yujie; Jiang, Yi

doi: 10.1039/d3dt03496hpmid: 38348674

We achieve a successful transition of Co4O4 molecules from a homogeneous to a heterogeneous system by modifying the functional groups at their termini. The resulting cocatalyst, denoted as Co4O4-poly, not only preserved the catalytic sites of Co4O4 molecules but also exhibited outstanding performance in catalyzing water oxidation.

Orlova, Anastasia V.; Shmychkov, Nazar V.; Vlasova, Kseniia Yu.; Iakimova, Tamara M.; Lepnev, Leonid S.; Eliseev, Andrei A.; Utochnikova, Valentina V.

doi: 10.1039/d3dt04298gpmid: 38349065

Two new ytterbium coordination compounds Yb(HPTC)(H2O)2 (Yb1) and Yb(HPTC)(Phen) (Yb2) were obtained using 10-carboxyperylene-3,4,9-tricarboxylate ion (HPTC3−) as a sensitizer. Both coordination compounds exhibited intense NIR-II luminescence upon excitation in the visible range and formed stable suspensions with nanoparticles of 50–70 nm in size in an aqueous solution of sodium alginate. Both complexes demonstrated non-toxicity up to at least 25 mg L−1 in two cell cultures: cancer cells MCF7 and embryonic cells HEK293T – making them suitable for bioimaging. For both complexes, the accumulation in cells was directly measured and it was shown that the accumulation of Yb2 was the same for both cell types (0.51–0.52 πg per cell), while Yb1 demonstrated selective accumulation in cancer cells (0.04 πg per cell for HEK293T and 7.00 πg per cell for MCF7). Thus, Yb1 can also be proposed as a selective vis-excited NIR emitting bioprobe.

Lei, Yuan; Zhang, Zhenyu; Lin, Zhan; Bhattacharjee, Samiran; Chen, Chao

doi: 10.1039/d3dt03895epmid: 38369874

The construction of functional interlayers for separator modification in Li–S batteries has been proven to be a feasible and effective strategy to alleviate the shuttle effect. However, several challenging issues in interlayer design and fabrication, including the tedious material preparation process and high weight loading of the interlayer on the pristine separator, jeopardize the battery energy density. In this work, a nitrogen-abundant nanoporous carbon/graphene (NC/G) composite was synthesized by a facile method and fabricated into a lightweight membrane, which was investigated as a multifunctional interlayer in a Li–S battery. The abundant nitrogen sites and nanoporous structure of NC/G can effectively anchor and trap polysulfides; graphene (G) can create an excellent conductive network in NC/G. These attributes of NC/G are able to efficiently boost the sulfur redox reaction kinetics and significantly suppress the shuttle effect, leading to superb battery performance. More importantly, the low density of NC/G was conducive to reducing the load on the separator, thus reducing the decline in battery energy density, which is promising for practical applications. Even at an ultra-low loading of NC/G on the pristine separator (0.08 mg cm−2), the battery showed a competitive electrochemical performance compared with many reported materials. We believe this work provides a strategic guidance for the future fabrication of promising functional interlayers for practical Li–S battery applications.

Babula, Dawid J.; Charman, Rex S. C.; Hobson, Josie A.; Mahon, Mary F.; Liptrot, David J.

doi: 10.1039/d4dt00334apmid: 38372037

Liquid assisted ball milling of [NHC]HBr (NHC = N-heterocyclic carbene) salts with copper(i) chloride, and a range of alkali metal complexes was shown to efficiently produce (NHC)CuX (NHC = normal or RE-NHC, X = halide, alkoxide, amide, alkyl, aryl; RE-NHC = ring-expanded NHC).