Tpy-Mn(II)-Tpy (Tpy = 2,2':6',2″-terpyridine)-Based Pentagonal Prism for Green Photodriven Oxidation.

In coordination-driven metal-organic cages, the transition metal ions are generally utilized as linkages. Employment of its unique properties with the aim of achieving specific applications still presents great challenges. Herein, we report a decametric metal-organic cage named pentagonal prism (Mn20LC10) based on Tpy-Mn(II)-Tpy connectivity (Tpy = 2,2':6',2″-terpyridine) in which Mn(II) serves as a linker and endows the resulting metal-organic cage with good photosensitivity. In the photooxidation of benzaldehyde, pentagonal prism Mn20LC10 showed a significantly increased level of 1O2 production, the fastest conversion time, good recyclability, and substrate versatility due to its greatly improved intersystem crossing ability. Notably, the abundant active sites of metal pentagonal prism Mn20LC10 enable its photooxidation under solvent-free and daylight conditions. This work provides approaches for the development of inexpensive, green, and low-cost photosensitizer systems.

[1]  Tong Zhu,et al.  Coordination-Regulated Terpyridine-Mn(II) Complexes for Photodynamic Therapy Guided by Multiphoton Fluorescence/Magnetic Resonance Imaging. , 2022, Inorganic chemistry.

[2]  Dong Yan,et al.  Rationally fabricating 3D porphrinic covalent organic frameworks with scu topology as highly efficient photocatalysts , 2022, Chem.

[3]  Ming Wang,et al.  Porphyrin-Based Multicomponent Metallacage: Host–Guest Complexation toward Photooxidation-Triggered Reversible Encapsulation and Release , 2022, JACS Au.

[4]  Q. Luo,et al.  Precise Detection and Visualization of Cyclooxygenase-2 for Golgi Imaging by a Light-Up Aggregation-Induced Emission-Based Probe , 2021, CCS Chemistry.

[5]  Sanliang Ling,et al.  Perylene Diimide-Based Multicomponent Metallacages as Photosensitizers for Visible Light-Driven Photocatalytic Oxidation Reaction , 2021, CCS Chemistry.

[6]  Hong Jiang,et al.  Endohedral functionalization of chiral metal-organic cages for encapsulating achiral dyes to induce circularly polarized luminescence , 2021, Chem.

[7]  Lixin Wu,et al.  From Mechanically Interlocked Structures to Host–Guest Chemistry Based on Twisted Dimeric Architectures by Adjusting Space Constraints , 2021, CCS Chemistry.

[8]  Linbing Sun,et al.  Breathing Metal–Organic Polyhedra Controlled by Light for Carbon Dioxide Capture and Liberation , 2021, CCS Chemistry.

[9]  L. Wojtas,et al.  Supramolecular triangular orthobicupola: Self-assembly of a giant Johnson solid J27 , 2021, Chem.

[10]  J. Sessler,et al.  Hierarchical Self-Assembly of Nanowires on the Surface by Metallo-Supramolecular Truncated Cuboctahedra. , 2021, Journal of the American Chemical Society.

[11]  Jun Yan,et al.  Molecular hexagram and octagram: Position determined 3D metallo-supermolecules and concentration-induced transformation , 2021, Chinese Chemical Letters.

[12]  Haitao Sun,et al.  Orthogonal Self-Assembly of a Two-Step Fluorescence-Resonance Energy Transfer System with Improved Photosensitization Efficiency and Photooxidation Activity. , 2020, Journal of the American Chemical Society.

[13]  Xiaopeng Li,et al.  Rotaxane-Branched Dendrimers with Enhanced Photosensitization. , 2020, Journal of the American Chemical Society.

[14]  Hao Yu,et al.  Tetraphenylethylene-Based Emissive Supramolecular Metallacages Assembled by Terpyridine Ligands , 2020 .

[15]  J. Sessler,et al.  Intra- and intermolecular self-assembly of a 20-nm-wide supramolecular hexagonal grid , 2020, Nature Chemistry.

[16]  M. Fujita,et al.  A Double-Walled Knotted Cage for Guest-Adaptive Molecular Recognition. , 2020, Journal of the American Chemical Society.

[17]  A. Stefankiewicz,et al.  Coordination cages as permanently porous ionic liquids , 2020, Nature Chemistry.

[18]  Sanliang Ling,et al.  Emissive Platinum(II) Cages with Reverse Fluorescence Resonance Energy Transfer for Multiple Sensing. , 2020, Journal of the American Chemical Society.

[19]  Liping Cao,et al.  Tetraphenylethene-Based Octacationic Cage. , 2019, Angewandte Chemie.

[20]  Yiliang Wang,et al.  A self-assembled Ru–Pt metallacage as a lysosome-targeting photosensitizer for 2-photon photodynamic therapy , 2019, Proceedings of the National Academy of Sciences.

[21]  Shunfang Li,et al.  Porphyrinic Silver Cluster Assembled Material for Simultaneous Capture and Photocatalysis of Mustard-Gas Simulant. , 2019, Journal of the American Chemical Society.

[22]  E. Peris,et al.  Photocatalytic Properties of a Palladium Metallosquare with Encapsulated Fullerenes via Singlet Oxygen Generation. , 2019, Inorganic chemistry.

[23]  Xiaopeng Li,et al.  Light-Controlled Generation of Singlet Oxygen within a Discrete Dual-Stage Metallacycle for Cancer Therapy. , 2019, Journal of the American Chemical Society.

[24]  F. Rizzuto,et al.  Strategies for binding multiple guests in metal–organic cages , 2019, Nature Reviews Chemistry.

[25]  Deqing Zhang,et al.  A Cross-linked Conjugated Polymer Photosensitizer Enables Efficient Sunlight-Induced Photooxidation. , 2019, Angewandte Chemie.

[26]  B. Liu,et al.  Polymerization-Enhanced Two-Photon Photosensitization for Precise Photodynamic Therapy. , 2019, ACS nano.

[27]  Kenry,et al.  Polymerization-Enhanced Photosensitization , 2018, Chem.

[28]  J. Nitschke,et al.  Directed Phase Transfer of an FeII4L4 Cage and Encapsulated Cargo. , 2017, Journal of the American Chemical Society.

[29]  Shuhong Yu,et al.  Singlet Oxygen-Engaged Selective Photo-Oxidation over Pt Nanocrystals/Porphyrinic MOF: The Roles of Photothermal Effect and Pt Electronic State. , 2017, Journal of the American Chemical Society.

[30]  Takashi Kumasaka,et al.  Self-assembly of tetravalent Goldberg polyhedra from 144 small components , 2016, Nature.

[31]  Yoshihiro Ueda,et al.  Self-Assembly of M30L60 Icosidodecahedron , 2016 .

[32]  K. Landfester,et al.  Photocatalytic Selective Bromination of Electron-Rich Aromatic Compounds Using Microporous Organic Polymers with Visible Light , 2016 .

[33]  J. Reek,et al.  Self-assembled nanospheres with multiple endohedral binding sites pre-organize catalysts and substrates for highly efficient reactions , 2016, Nature Chemistry.

[34]  H. Tan,et al.  Hierarchical Self-Assembly of Discrete Organoplatinum(II) Metallacycles with Polysaccharide via Electrostatic Interactions and Their Application for Heparin Detection. , 2015, Journal of the American Chemical Society.

[35]  Wei Huang,et al.  Stabilizing triplet excited states for ultralong organic phosphorescence. , 2015, Nature materials.

[36]  P. Srivastava,et al.  Manganese terpyridine artificial metalloenzymes for benzylic oxygenation and olefin epoxidation. , 2014, Tetrahedron.

[37]  Qisheng Zhang,et al.  Luminous butterflies: efficient exciton harvesting by benzophenone derivatives for full-color delayed fluorescence OLEDs. , 2014, Angewandte Chemie.

[38]  Stephen Z. D. Cheng,et al.  Construction of a highly symmetric nanosphere via a one-pot reaction of a tristerpyridine ligand with Ru(II). , 2014, Journal of the American Chemical Society.

[39]  C. Adachi,et al.  Highly efficient organic light-emitting diodes from delayed fluorescence , 2012, Nature.

[40]  Peter J Stang,et al.  Supramolecular coordination: self-assembly of finite two- and three-dimensional ensembles. , 2011, Chemical reviews.

[41]  Xiaopeng Li,et al.  Design, synthesis, and traveling wave ion mobility mass spectrometry characterization of iron(II)- and ruthenium(II)-terpyridine metallomacrocycles. , 2011, Journal of the American Chemical Society.

[42]  J. Leprêtre,et al.  Mononuclear Mn(III) and Mn(IV) bis-terpyridine complexes: electrochemical formation and spectroscopic characterizations. , 2009, Inorganic chemistry.

[43]  Clyde W. Cady,et al.  Ultrafast Photooxidation of Mn(II)−Terpyridine Complexes Covalently Attached to TiO2 Nanoparticles , 2007 .

[44]  I. Lancellotti,et al.  Anion binding to mitochondrial cytochromes c studied through electrochemistry. Effects of the neutralization of surface charges on the redox potential. , 1996, European journal of biochemistry.

[45]  W. V. Shaw,et al.  Solving the structure of human H ferritin by genetically engineering intermolecular crystal contacts , 1991, Nature.