Covalently Bound Nitroxyl Radicals in an Organic Framework.

A series of covalent organic framework (COF) structures is synthesized that possesses a tunable density of covalently bound nitroxyl radicals within the COF pores. The highest density of organic radicals produces an electron paramagnetic resonance (EPR) signal that suggests the majority of radicals strongly interact with other radicals, whereas for smaller loadings the EPR signals indicate the radicals are primarily isolated but with restricted motion. The dielectric loss as determined from microwave absorption of the framework structures compared with an amorphous control suggests that free motion of the radicals is inhibited when more than 25% of available sites are occupied. The ability to tune the mode of radical interactions and the subsequent effect on redox, electrical, and optical characteristics in a porous framework may lead to a class of structures with properties ideal for photoelectrochemistry or energy storage.

[1]  James R. McKone,et al.  Superior Charge Storage and Power Density of a Conducting Polymer-Modified Covalent Organic Framework , 2016, ACS central science.

[2]  H. Furukawa,et al.  Seven Post-synthetic Covalent Reactions in Tandem Leading to Enzyme-like Complexity within Metal-Organic Framework Crystals. , 2016, Journal of the American Chemical Society.

[3]  J. Ding,et al.  Tunable Electrical Conductivity and Magnetic Property of the Two Dimensional Metal Organic Framework [Cu(TPyP)Cu2(O2CCH3)4]. , 2016, ACS applied materials & interfaces.

[4]  R. Banerjee,et al.  Cobalt-Modified Covalent Organic Framework as a Robust Water Oxidation Electrocatalyst , 2016 .

[5]  Johannes T. Margraf,et al.  Molecular docking sites designed for the generation of highly crystalline covalent organic frameworks , 2016 .

[6]  Zuxun Zhang,et al.  High Conductive Two-Dimensional Covalent Organic Framework for Lithium Storage with Large Capacity. , 2016, ACS applied materials & interfaces.

[7]  T. Bein,et al.  Sequential Pore Wall Modification in a Covalent Organic Framework for Application in Lactic Acid Adsorption , 2016 .

[8]  O. Yaghi,et al.  Chemistry of Covalent Organic Frameworks. , 2015, Accounts of chemical research.

[9]  D. Jiang,et al.  Stable, crystalline, porous, covalent organic frameworks as a platform for chiral organocatalysts. , 2015, Nature chemistry.

[10]  J. Long,et al.  A Dual-Ion Battery Cathode via Oxidative Insertion of Anions in a Metal-Organic Framework. , 2015, Journal of the American Chemical Society.

[11]  Travis W. Kemper,et al.  Density of States and the Role of Energetic Disorder in Charge Transport in an Organic Radical Polymer in the Solid State , 2015 .

[12]  S. Stahl,et al.  High-Potential Electrocatalytic O2 Reduction with Nitroxyl/NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis , 2015, ACS central science.

[13]  R. Krishna,et al.  Tailor-Made Pore Surface Engineering in Covalent Organic Frameworks: Systematic Functionalization for Performance Screening. , 2015, Journal of the American Chemical Society.

[14]  Barbara K. Hughes,et al.  Close Packing of Nitroxide Radicals in Stable Organic Radical Polymeric Materials. , 2015, The journal of physical chemistry letters.

[15]  S. Irle,et al.  Locking covalent organic frameworks with hydrogen bonds: general and remarkable effects on crystalline structure, physical properties, and photochemical activity. , 2015, Journal of the American Chemical Society.

[16]  D. Trauner,et al.  Extraction of Photogenerated Electrons and Holes from a Covalent Organic Framework Integrated Heterojunction , 2014, Journal of the American Chemical Society.

[17]  F. Toma,et al.  Tunable electrical conductivity in oriented thin films of tetrathiafulvalene-based covalent organic framework , 2014 .

[18]  Barbara K. Hughes,et al.  Quenching of the perylene fluorophore by stable nitroxide radical-containing macromolecules. , 2014, The journal of physical chemistry. B.

[19]  Yushan Yan,et al.  Designed synthesis of large-pore crystalline polyimide covalent organic frameworks , 2014, Nature Communications.

[20]  T. Bein,et al.  On the road towards electroactive covalent organic frameworks. , 2014, Chemical communications.

[21]  M. E. Foster,et al.  Tunable Electrical Conductivity in Metal-Organic Framework Thin-Film Devices , 2014, Science.

[22]  T. Maris,et al.  Constructing monocrystalline covalent organic networks by polymerization , 2013, Nature Chemistry.

[23]  Jose L. Mendoza-Cortes,et al.  A Covalent Organic Framework that Exceeds the DOE 2015 Volumetric Target for H2 Uptake at 298 K. , 2012, The journal of physical chemistry letters.

[24]  W. Wang,et al.  Covalent organic frameworks. , 2012, Chemical Society reviews.

[25]  Xiao Feng,et al.  Pore surface engineering in covalent organic frameworks. , 2011, Nature communications.

[26]  William R. Dichtel,et al.  A 2D covalent organic framework with 4.7-nm pores and insight into its interlayer stacking. , 2011, Journal of the American Chemical Society.

[27]  S. Irle,et al.  An n-channel two-dimensional covalent organic framework. , 2011, Journal of the American Chemical Society.

[28]  J. F. Stoddart,et al.  Covalent Organic Frameworks with High Charge Carrier Mobility , 2011 .

[29]  K. Oyaizu,et al.  Radical Polymers for Organic Electronic Devices: A Radical Departure from Conjugated Polymers? , 2009 .

[30]  Petr Novák,et al.  Synthesis of Poly(4-methacryloyloxy-TEMPO) via Group-Transfer Polymerization and Its Evaluation in Organic Radical Battery , 2007 .

[31]  F. Wudl,et al.  THERMAL AND ELECTROMAGNETIC BEHAVIOR OF DOPED POLY(3,4-ETHYLENEDIOXYTHIOPHENE) FILMS , 1997 .

[32]  René A. J. Janssen,et al.  Five generations of nitroxyl-functionalized dendrimers , 1997 .

[33]  N. Atherton,et al.  Principles of electron spin resonance , 1993 .

[34]  James R. Bolton,et al.  Electron Spin Resonance , 1986 .

[35]  C. K. Chiang,et al.  Electrical Conductivity in Doped Polyacetylene. , 1977 .