Article
Chemistry, Multidisciplinary
Hong-Yu Lin, Le-Yong Zhou, Lin Xu
Summary: This review highlights recent advances in photocatalysis using supramolecular fluorescent metallacycles and metallacages. It discusses the utilization of metallacycles skeletons and the impact of fluorescence-resonance energy transfer on photocatalysis, as well as summarizes the use of ligands decorated with organic chromophores or redox metal sites in metallacages as photocatalysts.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Review
Multidisciplinary Sciences
Jun Zhao, Zhixuan Zhou, Guangfeng Li, Peter J. Stang, Xuzhou Yan
Summary: The coordination-driven self-assembly of metallacages has attracted significant interest due to their 3D layout and cavity-cored nature, making them particularly attractive for studying luminophores and inducing novel photophysical characters. By incorporating ligands displaying aggregation-induced emission (AIE) into metallacages, favorable photophysical properties have been achieved, leading to the development of supramolecular luminophores for diverse applications in fields such as sensing, biomedicine and catalysis.
NATIONAL SCIENCE REVIEW
(2021)
Article
Chemistry, Organic
Zhi-Yong Zeng, Xiaoli Zhao, Junhai Huang, Jing Zhu, Tongxia Jin, Lianrui Hu, Wei-Tao Dou, Lin Xu
Summary: A functionalized metallacage with anthracene groups was synthesized and analyzed using various techniques including UV/vis spectroscopy, NMR, ESI-TOF mass spectrometry, and X-ray single crystal diffraction. This metallacage showed specific fluorescence enhancement response to OH-, PO43-, and AcO- anions, which was attributed to the disassembly of the metallacage induced by these anions.
Article
Chemistry, Multidisciplinary
Hong-Yu Lin, Le-Yong Zhou, Fang Mei, Wei-Tao Dou, Lianrui Hu, Hai-Bo Yang, Lin Xu
Summary: Developing a new strategy to improve the self-assembly efficiency and construct hybrid functional materials in a confined space is the focus of this study. A highly efficient strategy for achieving the supramolecular self-assembly of metallacages in microdroplets through continuous-flow microfluidic devices was proposed. The versatility and high efficiency of this approach were demonstrated by the generation of five representative metallacages in different solvents within minutes, with nearly quantitative yields. The study also explored the supramolecular catalysis in microdroplets, showing an enhanced catalytic yield compared to the batch reactor.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Zheng Li, Weiwei Huan, Yan Wang, Ying-Wei Yang
Summary: Discrete organometallic complexes with defined structures have shown promising applications in the treatment of malignant tumors. Their advantages, including high antitumor activity, low toxicity, active targeting ability, and enhanced cellular uptake, make them suitable for clinical use. In particular, coordination-induced regulation of luminescence and photophysical properties has potential in evaluating therapeutic efficacy and enabling synergistic photodynamic or photothermal therapy. This review focuses on multimodal radiochemotherapy platforms based on self-assembled metallacycles/metallacages for cancer ablation, classifying them according to their functions. The review also discusses the demands and prospects for future development in this field.
Review
Chemistry, Multidisciplinary
Tongxia Jin, Wanding Cui, Wei-Tao Dou, Lin Xu
Summary: The integration of small organic fluorophores into supramolecular systems through coordination-driven self-assembly has attracted increasing interest. This approach allows for precise control over the number and location of fluorophores in supramolecular systems, enabling multi-channel spectral changes and tunable light emission.
SUPRAMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Kai Gao, Qian Feng, Zeyuan Zhang, Ruoqian Zhang, Yali Hou, Chaoqun Mu, Xiaopeng Li, Mingming Zhang
Summary: Emissive metallacages are used as crosslinks to prepare metallacage-cored polyurethanes, which exhibit enhanced mechanical properties, good fluorescence, self-healing, and shape memory properties. This study provides a convenient strategy to prepare metallacage-crosslinked networks and explores their applications as smart materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Materials Science, Multidisciplinary
Wei-Tao Dou, Chang-Yin Yang, Lian-Rui Hu, Bo Song, Tongxia Jin, Pei-Pei Jia, Xuelei Ji, Feng Zheng, Hai-Bo Yang, Lin Xu
Summary: Metallacages and covalent cages have been widely used in various fields, such as catalysis, separation, sensing, and biomedicine, due to their precise three-dimensional structures and tunable cavities. They can be modified in different ways to construct stimuli-responsive cages for marker detection and imaging in biological applications. They also allow the loading of imaging agents and drugs for precise disease diagnosis and treatment. This Review summarizes recent advances in metallacages and covalent cages in biological applications and presents their representative examples in imaging and therapeutics.
ACS MATERIALS LETTERS
(2023)
Review
Polymer Science
Ruoqian Zhang, Rongrong Li, Feihe Huang, Mingming Zhang
Summary: This review summarizes the progress of metallacycle/metallacage-cored supramolecular networks, focusing on the structures connected by covalent or non-covalent interactions. The detailed descriptions of the structures, properties, functions, and applications of such networks are provided to showcase the exciting achievements in this emerging field. The review also highlights the remaining challenges and perspectives to attract more scientists to contribute to this promising area.
PROGRESS IN POLYMER SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Yuhang Liu, Zhewen Guo, Yuchen Guo, Guangfeng Li, Shengbing Yang, Xuzhou Yan, Yi Shen, Jinbing Wang
Summary: A selective formation of a barrel-shaped or a ball-shaped fluorescent metallacage was achieved by controlling the shape and stoichiometry of the building blocks. The ball-shaped metallacage exhibited stronger and blue-shifted fluorescence compared to the barrel-shaped one in dilute solutions, while a reversal of fluorescence intensities was observed in the aggregation process. This work demonstrates the impact of subtle geometrical factors on the photophysical properties of supramolecular coordination complexes.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Meng-Ying Zhou, Jin Tong, Hong-Lin Lu, Xia-Yan Wang, Shu-Yan Yu
Summary: Hierarchical self-assembly of novel supramolecular networks using pyrene-based metallacapsules and metallacages was achieved through pi center dot center dot center dot pi interactions and metal-coordination-driven approach. These metal-organic structures, constructed from diamide- and triamide-based multi-pyrazolyl ligands and dipalladium(II,II) corners, were extended into 2-D supramolecular networks by pi center dot center dot center dot pi packing and other weak intermolecular interactions.
INORGANIC CHEMISTRY COMMUNICATIONS
(2022)
Article
Multidisciplinary Sciences
Dong-Xu Cui, Yun Geng, Jun-Ning Kou, Guo-Gang Shan, Chun-Yi Sun, Kun-Hao Zhang, Xin-Long Wang, Zhong-Min Su
Summary: The study presents the synthesis of stable chiral porous organic cages and their chiral self-sorting properties. The authors designed and synthesized axially chiral porous aromatic cages with high stability. The experimental results reveal the controlled chiral self-sorting of these cages in different solvents.
NATURE COMMUNICATIONS
(2022)
Article
Multidisciplinary Sciences
Xiaoping Wang, Mao Quan, Huan Yao, Xin-Yu Pang, Hua Ke, Wei Jiang
Summary: The authors report a pair of water-soluble naphthotubes with a pH-responsive cavity for switchable bifunctional recognition in water. These hosts have a switchable cavity and can be used for the construction of smart self-assembly systems and water-soluble molecular machines.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Andrew. T. Turley, Magnus W. D. Hanson-Heine, Stephen. P. Argent, Yaoyang Hu, Thomas. A. Jones, Michael Fay, Simon Woodward
Summary: Large S-8-corona[n]arene macrocycles with alternating aryl and 1,4-C6F4 subunits were successfully synthesized on large scales using new high acceleration SNAr substitution protocols. The size and functionality of the macrocycles can be adjusted by selecting the appropriate precursor and catalyst. Furthermore, the inclusion of solvent controls the conformation and fluorine-fluorine interactions of the macrocycles, leading to spontaneous self-assembly into honeycomb-like lattices.
Review
Chemistry, Multidisciplinary
Hong-Yu Lin, Yu-Te Wang, Xueliang Shi, Hai-Bo Yang, Lin Xu
Summary: Two-dimensional metallacycles and three-dimensional metallacages constructed by coordination-driven self-assembly have garnered significant attention due to their unique structures, properties, and efficient synthesis. The introduction of switching into supramolecular chemistry systems allows for reversible features triggered by different stimuli, resulting in novel switchable metallacycles and metallacages. These structures exhibit versatile properties, respond to artificial signals, and hold promise for applications in various fields such as drug delivery, data processing, pollutant removal, and smart functional materials.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Matthew R. Crawley, Daoyang Zhang, Amanda N. Oldacre, Christine M. Beavers, Alan E. Friedman, Timothy R. Cook
Summary: This study focused on assembling eight cofacial porphyrin prisms using MTPyP and functionalized ruthenium-based molecular clips, demonstrating significant improvement in catalytic rate constant k(s) and selectivity for the 4e(-)/4H* reduction of O-2 to H2O. The role of steric bulk of the clip in the structural dynamics of these prisms, which modulates the ORR reactivity with respect to selectivity and kinetics, was highlighted.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Vincent J. Pastore, Meghan G. Sullivan, Javid Rzayev, Timothy R. Cook
Summary: A series of new polymer-inorganic composites have been synthesized using a postsynthetic ligand exchange strategy from poly(amic acid) and various M-MOF-74 frameworks. This method has shown versatility in exchanging ligands with several additional metal ions and frameworks containing 2,5-dihydroxyterephthalate ligands, expanding the application of polymer-ligand exchange hybridization.
JOURNAL OF COORDINATION CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Gregory E. Sokolow, Matthew R. Crawley, Daniel R. Morphet, Didar Asik, Joseph A. Spernyak, A. J. Robert McGray, Timothy R. Cook, Janet R. Morrow
Summary: A metal-organic polyhedron with four paramagnetic Fe(III) centers was studied as an MRI probe and showed significant enhancement in solution. In vivo studies demonstrated strong contrast enhancement and accumulation of the polyhedron.
INORGANIC CHEMISTRY
(2022)
Article
Engineering, Chemical
Taliehsadat Alebrahim, Alisa Chakraborty, Leiqing Hu, Shalin Patil, Shiwang Cheng, Durga Acharya, Cara M. Doherty, Anita J. Hill, Timothy R. Cook, Haiqing Lin
Summary: Model systems are developed to investigate the effect of polyether-metal ion interactions on gas separation characteristics. Increasing the salt content generally decreases gas diffusivity and permeability, but low loadings of certain salts can increase gas permeability without affecting selectivity.
JOURNAL OF MEMBRANE SCIENCE
(2022)
Article
Chemistry, Inorganic & Nuclear
Daoyang Zhang, Matthew R. Crawley, Amanda N. Oldacre, Lea J. Kyle, Samantha N. MacMillan, Timothy R. Cook
Summary: Cofacial porphyrin catalysts synthesized via coordination-driven self-assembly were evaluated for their activity in the Oxygen Reduction Reaction (ORR). It was found that the structures of the catalysts, formed by different coordination patterns, showed significant differences in selectivity and reactivity. This study highlights the potential of coordination-driven self-assembly for tuning dinuclear catalysts.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Lauren E. Rosch, Matthew R. Crawley, Ryan M. O'Donnell, Thomas N. Rohrabaugh, Trenton R. Ensley, Thomas A. Sobiech, Timothy R. Cook
Summary: Despite 40 years of research on photophysical properties, significant gaps remain in understanding chalcogenopyrylium polymethine dyes. This study fills in these gaps through experiments on a family of dyes, revealing that structural and electronic changes can affect the photophysics of these dyes. The excited states of these dyes have short lifetimes with rapid relaxation processes, and they do not exhibit any triplet transient processes. Additionally, rotation of the pyran ring about the methine backbone is a critical factor that distinguishes the dynamics of these dyes from more rigid analogues.
Article
Engineering, Environmental
Ronghao Yang, Yan Zhou, Hedong Bian, Gang Cheng, Yuzhen Zhang, Chi-Ming Che, Timothy R. Cook, Yunjun Shen
Summary: The use of ligands with pendant closo-monocarborane clusters can neutralize the positive charge of luminescent complexes and enhance photophysical properties. In this study, four Pt(II) complexes with a monoanionic closo-monocarborane were synthesized and characterized. These complexes exhibit interesting photophysical behaviors, with complex 1a showing a high photoluminescent quantum yield and achieving a relatively high external quantum efficiency in OLED devices.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Yunjun Shen, Xiangjun Kong, Fengjie Yang, He-Dong Bian, Gang Cheng, Timothy R. Cook, Yuzhen Zhang
Summary: This study presents a novel platinum triplet emitter that emits blue light in both solid-state and solution states. The complex 4a exhibits the highest luminous efficiency when dispersed in a PMMA matrix. A deep-blue OLED containing 4a as the light-emitting dopant demonstrates blue photoluminescence and a maximum external quantum efficiency of 6.2%.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Meghan G. Sullivan, Gregory E. Sokolow, Eric T. Jensen, Matthew R. Crawley, Samantha N. MacMillan, Timothy R. Cook
Summary: The chemistry of zirconium-based metal-organic polyhedra (ZrMOPs) is often limited by their poor solubilities. We explored a new method for ZrMOP functionalization via node-modification, and found that it could influence solubility.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Heshali K. Welgama, Matthew R. . Crawley, James R. . McKone, Timothy R. . Cook
Summary: Prussian blue and its analogues have potential for electrochemical energy storage, but their use in flow-type devices is limited due to the lack of redox responsiveness in colloidal suspensions. Our study investigated the redox chemistry of amine functionalization of Prussian blue and its Cu analogue. The results highlight the importance of developing materials with redox activity and stability for practical applications.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Matthew R. Crawley, Daoyang Zhang, Timothy R. Cook
Summary: This work reports the synthesis of a hexa-porphyrin cube, which can catalyze the electrochemical reduction of molecular oxygen to hydrogen peroxide. By exploiting post-synthetic modification and structural control through coordination-driven self-assembly, the efficient generation of hydrogen peroxide is achieved.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Physical
Vincent J. Pastore, Meghan G. Sullivan, Heshali K. Welgama, Matthew R. Crawley, Alan E. Friedman, Clayton Rumsey, Martin Trebbin, Javid Rzayev, Timothy R. Cook
Summary: One way to modify metal-organic polyhedra (MOPs) is by adding functional groups to the organic bridging ligands. This allows for coupling reactions to enhance the architecture. In this study, a reactive norbornene-based MOP was formed through a one-pot tandem coordination-driven self-assembly/Diels-Alder reaction. Further modification of the MOPs was achieved through thiol-ene click chemistry, resulting in the formation of functionalized MOPs or polymer/MOP hybrid composites.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Physical
Mamta Dagar, Molly Corr, Timothy R. Cook, James R. McKone, Ellen M. Matson
Summary: We investigate the impact of solvent on the rates of electron transfer in heterometallic charge carriers and find that a 1:4 v/v mixture of propylene carbonate and acetonitrile can significantly increase the rate of electron transfer for one electron oxidation compared to pure acetonitrile. Additionally, the one electron reduction process also shows a two-fold increase in rate in the mixture. This behavior is attributed to solvent-solvent interactions that deviate from ideal solution behavior. The results highlight the importance of solvent in improving electron transfer kinetics and provide a way to systematically tune solvent composition for faster charge transfer.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Inorganic & Nuclear
Daoyang Zhang, Matthew R. R. Crawley, Ming Fang, Lea J. J. Kyle, Timothy R. R. Cook
Summary: We report the electrocatalytic Oxygen Reduction Reaction on a rigid Co(ii) porphyrin prism scaffold bridged by Ag(i) ions. The reactivity of this scaffold differs significantly from previous prism catalysts in that its selectivity is similar to that of monomer yet it displays sluggish kinetics, which is responsible for these differences.
DALTON TRANSACTIONS
(2022)
Review
Chemistry, Multidisciplinary
Jiong Zhou, Lang Rao, Guocan Yu, Timothy R. Cook, Xiaoyuan Chen, Feihe Huang
Summary: Nanotheranostics is the next generation of personalized medicine aiming to improve cancer patients' survival rate and quality of life. Supramolecular cancer nanotheranostics have advantages in early diagnosis and personalized therapy with promising potential in clinical applications.
CHEMICAL SOCIETY REVIEWS
(2021)