Direct Imaging of Isolated Single-Molecule Magnets in Metal-Organic Frameworks.

Practical applications involving the magnetic bistability of single-molecule magnets (SMMs) for next-generation computer technologies require nanostructuring, organization, and protection of nanoscale materials in two- or three-dimensional networks, to enable read-and-write processes. Owing to their porous nature and structural long-range order, metal-organic frameworks (MOFs) have been proposed as hosts to facilitate these efforts. Although probing the channels of MOF composites using indirect methods is well established, the use of direct methods to elucidate fundamental structural information is still lacking. Herein we report the direct imaging of SMMs encapsulated in a mesoporous MOF matrix using high-resolution transmission electron microscopy. These images deliver, for the first time, direct and unambiguous evidence to support the adsorption of molecular guests within the porous host. Bulk magnetic measurements further support the successful nanostructuring of SMMs. The preparation of the first magnetic composite thin films of this kind furthers the development of molecular spintronics.

[1]  Dante Gatteschi,et al.  Alternating current susceptibility, high field magnetization, and millimeter band EPR evidence for a ground S = 10 state in [Mn12O12(Ch3COO)16(H2O)4].2CH3COOH.4H2O , 1991 .

[2]  A. Caneschi,et al.  Magnetic bistability in a metal-ion cluster , 1993, Nature.

[3]  L. Thomas,et al.  Macroscopic quantum tunnelling of magnetization in a single crystal of nanomagnets , 1996, Nature.

[4]  N. Dilley,et al.  The origin of the second relaxation process in the [Mn12O12(O2CR)16(H2O)4] single-molecule magnets: ‘Jahn–Teller isomerism’ in the [Mn12O12] core , 1999 .

[5]  R. Sessoli,et al.  Quantum tunneling of magnetization and related phenomena in molecular materials. , 2003, Angewandte Chemie.

[6]  J. Veciana,et al.  Advances on the nanostructuration of magnetic molecules on surfaces: the case of single-molecule magnets (SMM). , 2007, Chemical communications.

[7]  M. Dressel,et al.  Magnetism and magnetic resonance studies of single-molecule magnets in polymer matrices , 2008 .

[8]  O. Shekhah,et al.  Thin films of metal-organic frameworks. , 2009, Chemical Society reviews.

[9]  S. Moggach,et al.  Pressure-induced Jahn-Teller switching in a Mn12 nanomagnet. , 2010, Chemical communications.

[10]  P. D. Brown,et al.  Encapsulation of single-molecule magnets in carbon nanotubes. , 2011, Nature communications.

[11]  Matteo Mannini,et al.  Chemical strategies and characterization tools for the organization of single molecule magnets on surfaces. , 2011, Chemical Society Reviews.

[12]  O. Shekhah,et al.  MOF thin films: existing and future applications. , 2011, Chemical Society reviews.

[13]  Xuan Zhang,et al.  Metal-Organic Frameworks as Platforms for the Controlled Nanostructuring of Single-Molecule Magnets. , 2015, Journal of the American Chemical Society.

[14]  J. Hupp,et al.  Metal-Organic Framework Thin Films as Platforms for Atomic Layer Deposition of Cobalt Ions To Enable Electrocatalytic Water Oxidation. , 2015, ACS applied materials & interfaces.

[15]  Nicolaas A. Vermeulen,et al.  Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000 , 2015, Nature Protocols.

[16]  M. Allendorf,et al.  Thin Film Growth of nbo MOFs and their Integration with Electroacoustic Devices , 2016 .

[17]  W. Wernsdorfer,et al.  A Stable Pentagonal Bipyramidal Dy(III) Single-Ion Magnet with a Record Magnetization Reversal Barrier over 1000 K. , 2016, Journal of the American Chemical Society.

[18]  M. Pivetta,et al.  Single-Molecule Magnets: Giant Hysteresis of Single-Molecule Magnets Adsorbed on a Nonmagnetic Insulator (Adv. Mater. 26/2016). , 2016, Advanced materials.

[19]  R. Sessoli Materials science: Magnetic molecules back in the race , 2017, Nature.

[20]  R. Sessoli Nanoscience: Single-atom data storage , 2017, Nature.

[21]  Jonathan L. Brosmer,et al.  Pursuit of Record Breaking Energy Barriers: A Study of Magnetic Axiality in Diamide Ligated DyIII Single-Molecule Magnets. , 2017, Journal of the American Chemical Society.

[22]  P. Seneor,et al.  Spintronics: The molecular way. , 2017, Nature materials.

[23]  David P. Mills,et al.  Molecular magnetic hysteresis at 60 kelvin in dysprosocenium , 2017, Nature.

[24]  Bin Zheng,et al.  Unravelling surface and interfacial structures of a metal-organic framework by transmission electron microscopy. , 2017, Nature materials.

[25]  Xuan Zhang,et al.  Systematic Investigation of Controlled Nanostructuring of Mn12 Single-Molecule Magnets Templated by Metal-Organic Frameworks. , 2017, Inorganic chemistry.

[26]  C. Lutz,et al.  Reading and writing single-atom magnets , 2016, Nature.

[27]  Yan‐Zhen Zheng,et al.  Field- and temperature-dependent quantum tunnelling of the magnetisation in a large barrier single-molecule magnet , 2018, Nature Communications.

[28]  Fu-Sheng Guo,et al.  Magnetic hysteresis up to 80 kelvin in a dysprosium metallocene single-molecule magnet , 2018, Science.

[29]  J. Long,et al.  Large Anisotropy Barrier in a Tetranuclear Single-Molecule Magnet Featuring Low-Coordinate Cobalt Centers. , 2018, Journal of the American Chemical Society.

[30]  R. Sougrat,et al.  Atomic-resolution transmission electron microscopy of electron beam–sensitive crystalline materials , 2018, Science.

[31]  R. Luque,et al.  Ordered macro-microporous metal-organic framework single crystals , 2018, Science.