A series of lanthanide metal‐organic frameworks (Ln‐MOFs) are synthesized through solvothermal conditions with 1,3‐bis(4‐carboxyphenyl)imidazolium (H2L). Owing to the lanthanide contraction effect, two different types of Ln‐MOFs, namely, {[Ln(L)2(OH)]·3H2O}n (Ln:Pr, Nd, Sm) and {[Ln(L)2(COO)(H2O)2]·H2O}n (Ln: Eu, Gd, Tb, Dy, Tm, Yb, Y), and their corresponding codoped Ln‐MOFs EuxTb1‐xL are obtained. With careful adjustment of the relative concentration of the lanthanide ions and the excitation wavelength, the color of the luminescence can be systematically modulated and white light emission can be further successfully achieved. Furthermore, by virtue of the temperature‐dependent luminescent behavior, Eu0.2Tb0.8L allows for the design of a thermometer with an excellent linear response to temperature over a wide range, from 40 to 300 K. This work highlights the practical applications of Ln‐MOFs for tailoring fluorescent color and even obtaining practical white light emission, and especially for sensing temperature as luminescent thermometers in a single framework by controlling in different ways.

Iodo-BODIPY: a visible-light-driven, highly efficient and photostable metal-free organic photocatalyst3

A sandwich complex, as exemplified by ferrocene in the 1950s, usually refers to one metal center bound by two arene ligands. The subject has subsequently been extended to carbon-free aromatic ligands and multiple-metal-atom "monolayered" center, but not to an all-metal species. Here, we describe the synthesis of an unprecedented all-metal aromatic sandwich complex, [Sb3Au3Sb3](3-), which was isolated as K([2.2.2]crypt)(+) salt and identified by single-crystal X-ray diffraction. Quantum chemical calculations indicate that intramolecular electron transfers for the three metallic layers (Sb → Au donation and Sb ← Au back-donation) markedly redistribute the valence electrons from the cyclo-Sb3 ligands and Au3 interlayer to the Au-Sb bonds, which hold the complex together via σ bonding. Each cyclo-Sb3 possesses aromaticity with delocalized three-center three-electron (3c-3e) π bonds, which are essentially equivalent to a 3c-4e ππ* triplet system, following the reversed 4n Hückel rule for aromaticity in a triplet state.

A microporous Cu-MOF with optimized open metal sites and pore space was constructed based on a designed bent ligand; it exhibits high-capacity multiple gas storage under atmospheric pressure and efficient catalytic activity for chemical fixation of CO2 under mild conditions.

Triply fused cluster: edge shared of three [Rh@Sn10] subunits lead to the largest endohedral polystannide with an entirely new triply fused topology.

Stanene (Sn)-based materials have been extensively applied in industrial production and daily life, but their potential biomedical application remains largely unexplored, which is due to the absence of the appropriate and effective methods for fabricating Sn-based biomaterials. Herein, we explored a new approach combining cryogenic exfoliation and liquid-phase exfoliation to successfully manufacture two-dimensional (2D) Sn nanosheets (SnNSs). The obtained SnNSs exhibited a typical sheet-like structure with an average size of ~ 100 nm and a thickness of ~ 5.1 nm. After PEGylation, the resulting PEGylated SnNSs (SnNSs@PEG) exhibited good stability, superior biocompatibility, and excellent photothermal performance, which could serve as robust photothermal agents for multi-modal imaging (fluorescence/photoacoustic/photothermal imaging)-guided photothermal elimination of cancer. Furthermore, we also used first-principles density functional theory calculations to investigate the photothermal mechanism of SnNSs, revealing that the free electrons in upper and lower layers of SnNSs contribute to the conversion of the photo to thermal. This work not only introduces a new approach to fabricate 2D SnNSs but also establishes the SnNSs-based nanomedicines for photonic cancer theranostics. This new type of SnNSs with great potential in the field of nanomedicines may spur a wave of developing Sn-based biological materials to benefit biomedical applications.

Gas-phase clusters are deemed to be σ-aromatic when they satisfy the 4n+2 rule of aromaticity for delocalized σ electrons and fulfill other requirements known for aromatic systems. While the range of n values was shown to be quite broad when applied to short-lived clusters found in molecular-beam experiments, stability of all-metal cluster-like fragments isolated in condensed phase was previously shown to be mainly ascribed to two electrons (n=0). In this work, the applicability of this concept is extended towards solid-state compounds by demonstrating a unique example of a storable compound, which was isolated as a stable [K([2.2.2]crypt)] salt, featuring a [Au Sb ] cluster core possessing two all-metal aromatic AuSb fragments with six delocalized σ electrons each (n=1). This discovery pushes the boundaries of the original idea of Kekulé and firmly establishes the usefulness of the σ-aromaticity concept as a general idea for both small clusters and solid-state compounds.

No abstract