Dalton Transactions

doi: 10.1039/d3dt90212apmid: N/A

doi: 10.1039/d3dt90213gpmid: N/A

doi: 10.1039/d3dt90214epmid: N/A

Luo, Zhiying; Sheng, Yu; Jiang, Chenyi; Pan, Ying; Wang, Xiaoxiong; Nezamzadeh-Ejhieh, Ali; Ouyang, Jie; Lu, Chengyu; Liu, Jianqiang

doi: 10.1039/d3dt02543hpmid: 37953742

Metal–organic frameworks (MOFs) have been broadly applied in biomedical and other fields. MOFs have high porosity, a large comparative area, and good biostability and have attracted significant attention, especially in cancer therapies. This paper presents the latest applications of MOFs in chemodynamic therapy (CDT), sonodynamic therapy (SDT), photodynamic therapy (PDT), photothermal therapy (PTT), immunotherapy (IT), and combination therapy for breast cancer. A combination therapy is the combination of two different treatment modalities, such as CDT and PDT combination therapy, and is considered more effective than separate therapies. Herein, we have also discussed the advantages and disadvantages of combination therapy in the treatment of breast cancer. This paper aims to illustrate the potential of MOFs in new cancer therapeutic approaches, discuss their potential advantages, and provide some reflections on the latest research results.

Patra, Rajesh; Mondal, Sumit; Sarma, Debajit

doi: 10.1039/d3dt02884dpmid: 37961841

Metal–organic frameworks (MOFs) are unique hybrid porous materials formed by combining metal ions or clusters with organic ligands. Thiol and thioether-based MOFs belong to a specific category of MOFs where one or many thiols or thioether groups are present in organic linkers. Depending on the linkers, thiol-thioether MOFs can be divided into three categories: (i) MOFs where both thiol or thioether groups are part of the carboxylic acid ligands, (ii) MOFs where only thiol or thioether groups are present in the organic linker, and (iii) MOFs where both thiol or thioether groups are part of azolate-containing linkers. MOFs containing thiol-thioether-based acid ligands are synthesized through two primary approaches; one is by utilizing thiol and thioether-based carboxylic acid ligands where the bonding pattern of ligands with metal ions plays a vital role in MOF formation (HSAB principle). MOFs synthesized by this approach can be structurally differentiated into two categories: structures without common structural motifs and structures with common structural motifs (related to UiO-66, UiO-67, UiO-68, MIL-53, NU-1100, etc.). The second approach to synthesize thiol and thioether-based MOFs is indirect methods, where thiol or thioether functionality is introduced in MOFs by techniques like post-synthetic modifications (PSM), post-synthetic exchange (PSE) and by forming composite materials. Generally, MOFs containing only thiol-thioether-based ligands are synthesized by interfacial assisted synthesis, forming two-dimensional sheet frameworks, and show significantly high conductivity. A limited study has been done on MOFs containing thiol-thioether-based azolate ligands where both nitrogen- and sulfur-containing functionality are present in the MOF frameworks. These materials exhibit intriguing properties stemming from the interplay between metal centres, organic ligands, and sulfur functionality. As a result, they offer great potential for multifaceted applications, ranging from catalysis, sensing, and conductivity, to adsorption. This perspective is organised through an introduction, schematic representations, and tabular data of the reported thiol and thioether MOFs and concluded with future directions.

Hossack, Christopher; Cahill, Christopher; Besson, Claire

doi: 10.1039/d3dt02737fpmid: 37943084

Since their discovery in 1966, scorpionate ligands have been utilized to make coordination compounds for a variety of applications such as: studying organometallic reactions, biomimetic complexes, light-emitting materials and single-ion magnets. The recent development of a solvent-free pyrazole substitution chemistry has yielded the quantitative synthesis of asymmetrically functionalized all-pyrazole heteroscorpionate ligands. In this frontier article, we highlight the utility of all-pyrazole heteroscorpionates, specifically, nitro-trispyrazolylborates, in f-element chemistry. They offer great versatility in coordinating ability, donor strength, steric bulk and even optical charge transfer properties, all of which can be used to tune the properties of resultant complexes with metal ions. We show how they can impart structural diversity, sensitize Ln3+ luminescence and engender magnetic anisotropy and slow magnetic relaxation in the ion they coordinate. Additionally, we comment on the future of functionalized trispyrazolyl scorpionates, which includes enabling post-synthetic modifications of f-element complexes and becoming a platform to study the electronic properties of low oxidation state actinides.

Briand, Glen G.

doi: 10.1039/d3dt03100dpmid: 37994106

Anionic redox-active ligands such as o-amidophenolates, catecholates, dithiolenes, 1,2-benzendithiolates, 2-amidobenzenethiolates, reduced α-diimines, ferrocenyl and porphyrinates are capable of reversible oxidation and thus have the ability to act as sources of electrons for metal centres. These and other non-innocent ligands have been employed in coordination complexes of base transition metals to influence their redox chemistry and afford compounds with useful catalytic, optical, magnetic and conducting properties. Despite the focus in contemporary main group chemistry on designing reactive compounds with potential catalytic activity, comparatively few studies exploring the chemistry of main group metal complexes incorporating redox-active ligands have been reported. This article highlights relevant chemical reactivity and electrochemical studies that probe the oxidation/reduction of main group metal compounds possessing redox-active ligands and comments on the prospects for this relatively untapped avenue of research.

Xia, Jun; Si, Jincheng; Zhou, Kang; Xia, Hai-Lun; Zhang, Jian; Xu, Yingqian; Wang, Lei; Liu, Xiao-Yuan

doi: 10.1039/d3dt03348apmid: 37997636

Herein, three tritopic carboxylic acids were used to construct three Zr-MOFs, HIAM-4033, HIAM-4034, and HIAM-4035, to investigate the effect of carboxyl position on the MOF structures. The results showed that HIAM-4033 and HIAM-4034 possess (3,9)-c models with different underlying nets, whereas HIAM-4035 exhibits the same underlying net as UiO-68. Nanosized HIAM-4033 exhibits excellent sensitivity and selectivity for detecting aromatic acids, such as benzoic acid and 2-fluorobenzoic acid, compared with aliphatic acids and inorganic acids. This study offers new insights into achieving an organic linker directed structure evolution of Zr-MOFs, which might facilitate the discovery of unprecedented underlying nets.

Chen, Xi-Meng; Yu, Xing-Chao; Chi, Jing-Xian; Jing, Yi; Wang, Hongju; Zhang, Na; Zhang, Chen; Ge, Yi-Wen; Chen, Xuenian

doi: 10.1039/d3dt03403hpmid: 37999641

An efficient method for the synthesis of M2B10H14 (M = Na and K) has been developed. The two possible formation mechanisms of the B10H142− anion are proposed, in which the NH2BH3− anion acts as a proton abstractor and a hydride donor. Furthermore, the B10H13− and B10H15− intermediates were detected.

Li, Yao; Guan, Guangguang; Yan, Liang; Zhang, Kaiyin; Xiang, Jun

doi: 10.1039/d3dt03215apmid: 37986578

An Fe2P nanoparticle (Fe2P NP)-decorated carbon nanofiber (represented as Fe2P@CNF) composite was in situ prepared by electrospinning and subsequent high-temperature treatment. Benefitting from the synergy effect between Fe2P NPs and CNFs, as well as improved interface polarization and impedance matching, the Fe2P@CNF composite exhibits excellent microwave absorption performance relative to pure CNFs, in which the Fe2P@CNF composite with a fill loading of only 10 wt% possesses a minimum reflection loss (RL) of −49.2 dB at 3.0 mm and a maximum effective absorption bandwidth of 6.0 GHz at 2.2 mm. Therefore, this work provides a promising approach for the design and synthesis of an Fe2P@CNF composite with high-performance microwave absorption.