Dalton Transactions

doi: 10.1039/d3dt90187dpmid: N/A

doi: 10.1039/d3dt90188bpmid: N/A

doi: 10.1039/d3dt90189kpmid: N/A

Uemura, Takashi; Bera, Jitendra K.; Brooker, Sally; Zheng, Li-Min

doi: 10.1039/d3dt90169fpmid: 37850328

Kawawaki, Tokuhisa; Negishi, Yuichi

doi: 10.1039/d3dt02005cpmid: 37712891

Metal nanoclusters (NCs) with sizes of approximately 2 nm or less have different physical/chemical properties from those of the bulk metals owing to quantum size effects. Metal NCs, which can be size-controlled and heterometal doped at atomic accuracy, are expected to be the next generation of important materials, and new metal NCs are reported regularly. However, compared with conventional materials such as metal complexes and relatively large metal nanoparticles (>2 nm), these metal NCs are still underdeveloped in terms of evaluation and establishment of application methods. Electrochemical measurements are one of the most widely used methods for synthesis, application, and characterisation of metal NCs. This review summarizes the basic knowledge of the electrochemistry and experimental techniques, and provides examples of the reported electronic states of thiolate-protected gold NCs elucidated by electrochemical approaches. It is expected that this review will provide useful information for researchers starting to study metal NCs.

Li, Ke; Zhu, Kai-Ling; Cui, Li-Ping; Chen, Jia-Jia

doi: 10.1039/d3dt00105apmid: 36861841

Giant polyoxomolybdates are a special class of polyoxometalate clusters which can bridge the gap between small molecule clusters and large polymeric entities. Besides, giant polyoxomolybdates also show interesting applications in catalysis, biochemistry, photovoltaic and electronic devices, and other fields. Revealing the evolution route of the reducing species into the final cluster structure and also their further hierarchical self-assembly behaviour is undoubtedly fascinating, aiming to guide the design and synthesis. Herein, we reviewed the self-assembly mechanism study of giant polyoxomolybdate clusters, and the exploration of a new structure and new synthesis methodology is also summarized. Finally, we emphasize the importance of in-operando characterization in revealing the self-assembly mechanism of giant polyoxomolybdates, and especially for the further reconstruction of intermediates into the designable synthesis of new structures.

Wang, Ting; Zhang, Yushu; Wang, Zhifang; Chen, Yao; Cheng, Peng; Zhang, Zhenjie

doi: 10.1039/d3dt01684fpmid: 37461388

Covalent organic frameworks (COFs) with high specific porosity, easy functionalization, and tailored structure are an emerging class of crystalline porous polymers that have been extensively exploited as ideal materials in various fields. Among them, sp2-carbon linked COFs with high chemical stability, porous backbone, and unique π-electron conjugated architectures structure have raised widespread attention. Specifically, the porous channels of olefin-linked COFs could be packed with active sites for catalysis and guest molecules, while π–π stacking interactions and conjugation systems pave the way for electron transfer. In recent years, many efforts have been devoted to the development of sp2-carbon linked COFs for applications in catalysis, energy storage, gas adsorption, and separation. In this review, we highlight the design principles, synthesis strategies, and impactful applications of olefin-linked COFs. We are looking forward to this review to deepen the understanding of the synthesis of olefin-linked COFs and motivate the further development of these novel conjugated organic materials with distinctive physicochemical properties, as well as their applications in a variety of fields.

Zhang, Zhipeng; Ye, Huan; Cai, Fei; Sun, Yao

doi: 10.1039/d3dt01893hpmid: 37476886

Recently, metal-based drugs have attracted relentless interest in the biomedical field. However, their short excitation/emission wavelengths and unsatisfactory therapeutic efficiency limit their biological applications in vivo. Currently, the second near-infrared window (NIR-II, 1000–1700 nm) provides more accurate imaging and therapeutic options. Thus, there has been a constant focus on developing multifunctional NIR metal agents for imaging and therapy that have deeper tissue penetration. Fortunately, supramolecular coordination complexes (SCCs) formed by the coordination-driven self-assembly of NIR-II emissive ligands can address the above issues. Importantly, metal receptors with chemotherapeutic properties in SCCs can bind to luminescent ligands, thus becoming a versatile therapeutic platform for chemotherapy, imaging and phototherapy. In this context, we systematically summarize the evolution of NIR-II emissive SCCs for biomedical applications and discuss future challenges and prospects.

Liu, Minchao; Yu, Hongyue; Zhao, Tiancong; Li, Xiaomin

doi: 10.1039/d3dt01381bpmid: 37490002

With the promising advances in nanomedicine, numerous strategies have emerged for the diagnosis and treatment of diseases. Among them, enzyme-based multifunctional nanocomposites have attracted a great deal of attention in the field of catalytic biomedicine. These nanocomposites with high catalytic activity are capable of converting low/non-toxic substances into therapeutic ones, thus realizing highly efficient, site-specific therapy with minimal side effects. Enzyme-based nanocomposites for catalytic biomedicine are mainly divided into three types: (i) natural-enzyme based nanocomposites; (ii) artificial-nanozyme based nanocomposites; and (iii) nanocomposites of natural-enzymes and nanozymes. In this review, we discuss key aspects of enzyme-based catalytic biomedicine, including the construction of enzyme-based nanocomposites, their unique properties and applications in catalytic biomedicine. We also highlight the main challenges faced in this field, and provide relevant guidelines for the rational design and extensive application of enzyme-based nanocomposites from our point of view.

Peng, Yaoyao; Su, Zhifang; Jin, Meng; Zhu, Lei; Guan, Zong-Jie; Fang, Yu

doi: 10.1039/d3dt01679jpmid: 37492891

Photocatalytic organic conversion is considered an efficient, environmentally friendly, and energy-saving strategy for organic synthesis. In recent decades, the molecular cage has emerged as a creative functional material with broad applications in host–guest recognition, drug delivery, catalysis, intelligent materials and other fields. Based on the unique properties of porous molecular cage materials, they provide an ideal platform for leveraging pre-structuring in catalytic reactions and show great potential in various photocatalytic organic reactions. As a result, they have emerged as promising alternatives to conventional molecules or inorganic photocatalysts in redox processes. In this Review, the synthesis strategies based on coordination cages and organic cages, as well as their recent progress in photocatalytic organic conversion, are comprehensively summarized. Finally, we deliver the persistent challenges associated with porous molecular cage compounds that need to be overcome for further development in this field.