skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Linker Redox Mediated Control of Morphology and Properties in Semiconducting Iron‐Semiquinoid Coordination Polymers**

Journal Article · · Angewandte Chemie
ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [1]
  1. Department of Chemistry University of Chicago 5735 S Ellis Ave Chicago IL 60637 USA
  2. IRAMIS Leon Brillouin Laboratory CEA-Saclay 91191 Gif-sur-Yvette France
  3. Pritzker School of Molecular Engineering University of Chicago 5735 S Ellis Ave Chicago IL 60637 USA
  4. Department of Chemistry, Pritzker School of Molecular Engineering, James Franck Institute and Chicago Center for Theoretical Chemistry University of Chicago 5735 S Ellis Ave Chicago IL 60637 USA

Abstract The emergence of conductive 2D and less commonly 3D coordination polymers (CPs) and metal–organic frameworks (MOFs) promises novel applications in many fields. However, the synthetic parameters for these electronically complex materials are not thoroughly understood. Here we report a new 3D semiconducting CP Fe 5 (C 6 O 6 ) 3 , which is a fusion of 2D Fe‐semiquinoid materials and 3D cubic Fe x (C 6 O 6 ) y materials, by using a different initial redox‐state of the C 6 O 6 linker. The material displays high electrical conductivity (0.02 S cm −1 ), broad electronic transitions, promising thermoelectric behavior ( S 2 σ=7.0×10 −9  W m −1  K −2 ), and strong antiferromagnetic interactions at room temperature. This material illustrates how controlling the oxidation states of redox‐active components in conducting CPs/MOFs can be a “pre‐synthetic” strategy to carefully tune material topologies and properties in contrast to more commonly encountered post‐synthetic modifications.

Sponsoring Organization:
USDOE
OSTI ID:
1891566
Alternate ID(s):
OSTI ID: 1897576
Journal Information:
Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 134 Journal Issue: 45; ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (96)

2D Conductive Metal–Organic Frameworks: An Emerging Platform for Electrochemical Energy Storage journal August 2020
Redox Control and High Conductivity of Nickel Bis(dithiolene) Complex π-Nanosheet: A Potential Organic Two-Dimensional Topological Insulator journal October 2014
Generalized Gradient Approximation Made Simple journal October 1996
Maximizing the Carrier Mobilities of Metal–Organic Frameworks Comprising Stacked Pentacene Units journal July 2021
Modular Chemistry: Secondary Building Units as a Basis for the Design of Highly Porous and Robust Metal−Organic Carboxylate Frameworks journal April 2001
Valence-Dependent Electrical Conductivity in a 3D Tetrahydroxyquinone-Based Metal–Organic Framework journal December 2020
Conductive two-dimensional metal–organic frameworks as multifunctional materials journal January 2018
MOF-based electronic and opto-electronic devices journal January 2014
High Thermopower in a Zn-Based 3D Semiconductive Metal–Organic Framework journal November 2020
Unraveling the Electrical and Magnetic Properties of Layered Conductive Metal‐Organic Framework With Atomic Precision journal December 2021
Electronic Devices Using Open Framework Materials journal July 2020
Is iron unique in promoting electrical conductivity in MOFs? journal January 2017
Control of Electronic Structure and Conductivity in Two-Dimensional Metal–Semiquinoid Frameworks of Titanium, Vanadium, and Chromium journal February 2018
Norm-conserving and ultrasoft pseudopotentials for first-row and transition elements journal October 1994
A Redox‐Active 2D Metal–Organic Framework for Efficient Lithium Storage with Extraordinary High Capacity journal March 2020
Tetraoxolene radical stabilization by the interaction with transition-metal ions journal June 1991
Lithium Salt of Tetrahydroxybenzoquinone: Toward the Development of a Sustainable Li-Ion Battery journal July 2009
Synthetic investigation of competing magnetic interactions in 2D metal–chloranilate radical frameworks journal January 2020
Electrically Conductive Metal–Organic Frameworks journal April 2020
Effects of Covalency on Anionic Redox Chemistry in Semiquinoid-Based Metal–Organic Frameworks journal January 2020
Structural and magnetic properties of tris(o-semiquinone) complexes of iron(III) and chromium(III) journal December 1978
Electronic Challenges of Retrofitting 2D Electrically Conductive MOFs to Form 3D Conductive Lattices journal April 2021
Unraveling the Electrical and Magnetic Properties of Layered Conductive Metal‐Organic Framework With Atomic Precision journal December 2021
Recent Advances on Anilato-Based Molecular Materials with Magnetic and/or Conducting Properties journal April 2017
Retrofitting metal-organic frameworks journal October 2019
Electric relaxation and Mn3+/Mn4+ charge transfer in Fe-doped Bi12MnO20–BiMn2O5 structural self-composite journal October 2016
Direct Evidence of Photoinduced Charge Transport Mechanism in 2D Conductive Metal Organic Frameworks journal November 2020
2D Conductive Iron-Quinoid Magnets Ordering up to T c = 105 K via Heterogenous Redox Chemistry journal March 2017
Conductive metal–organic frameworks and networks: fact or fantasy? journal January 2012
Synthetic Routes for a 2D Semiconductive Copper Hexahydroxybenzene Metal–Organic Framework journal September 2018
Demonstration of a Broadband Photodetector Based on a Two‐Dimensional Metal–Organic Framework journal January 2020
A Redox‐Active 2D Metal–Organic Framework for Efficient Lithium Storage with Extraordinary High Capacity journal January 2020
Proposed Modification of the Graphene Analogue Ni 3 (HITP) 2 To Yield a Semiconducting Material journal June 2016
Grid-Type Metal Ion Architectures: Functional Metallosupramolecular Arrays journal July 2004
Conductive 2D metal-organic framework for high-performance cathodes in aqueous rechargeable zinc batteries journal October 2019
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
Robust and conductive two-dimensional metal−organic frameworks with exceptionally high volumetric and areal capacitance journal January 2018
An updated roadmap for the integration of metal–organic frameworks with electronic devices and chemical sensors journal January 2017
Cu 3 (hexaiminotriphenylene) 2 : An Electrically Conductive 2D Metal-Organic Framework for Chemiresistive Sensing journal February 2015
Linear response approach to the calculation of the effective interaction parameters in the LDA + U method journal January 2005
Conductive MOF electrodes for stable supercapacitors with high areal capacitance journal October 2016
High-mobility band-like charge transport in a semiconducting two-dimensional metal–organic framework journal October 2018
Atomically precise single-crystal structures of electrically conducting 2D metal–organic frameworks journal November 2020
Recent development and applications of electrical conductive MOFs journal January 2021
Quantum Spin Liquid State in a Two-Dimensional Semiconductive Metal–Organic Framework journal July 2020
Metal–organic Kagome lattices M 3 (2,3,6,7,10,11-hexaiminotriphenylene) 2 (M = Ni and Cu): from semiconducting to metallic by metal substitution journal January 2015
Mixed Valency as a Strategy for Achieving Charge Delocalization in Semiconducting and Conducting Framework Materials journal November 2017
Opening Metal–Organic Frameworks Vol. 2: Inserting Longer Pillars into Pillared-Paddlewheel Structures through Solvent-Assisted Linker Exchange journal August 2013
Unusual properties of midband states in systems with off-diagonal disorder journal February 1994
Conducting Anilate-Based Mixed-Valence Fe(II)Fe(III) Coordination Polymer: Small-Polaron Hopping Model for Oxalate-Type Fe(II)Fe(III) 2D Networks journal September 2018
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Magnetic ordering through itinerant ferromagnetism in a metal–organic framework journal April 2021
Molecular Retrofitting Adapts a Metal–Organic Framework to Extreme Pressure journal June 2017
Electrically Conductive Coordination Polymers for Electronic and Optoelectronic Device Applications journal February 2021
Spin state switching in iron coordination compounds journal January 2013
XPS Fe 2p peaks from iron tris(β-diketonates): Electronic effect of the β-diketonato ligand journal November 2016
Ab initio molecular dynamics for open-shell transition metals journal November 1993
A semiconducting gyroidal metal-sulfur framework for chemiresistive sensing journal January 2017
Two-dimensional conjugated metal–organic frameworks (2D c -MOFs): chemistry and function for MOFtronics journal January 2021
Nanorods of a novel highly conductive 2D metal–organic framework based on perthiolated coronene for thermoelectric conversion journal January 2020
Single Crystals of Electrically Conductive Two-Dimensional Metal–Organic Frameworks: Structural and Electrical Transport Properties journal December 2019
Interpenetration control in metal–organic frameworks for functional applications journal August 2013
Paramagnetic Conducting Metal–Organic Frameworks with Three‐Dimensional Structure journal September 2020
2D Conductive Metal‐Organic Frameworks: An Emerging Platform for Electrochemical Energy Storage journal May 2020
Cu 3 (hexaiminotriphenylene) 2 : An Electrically Conductive 2D Metal-Organic Framework for Chemiresistive Sensing journal February 2015
A Microporous and Naturally Nanostructured Thermoelectric Metal-Organic Framework with Ultralow Thermal Conductivity journal September 2017
Metal–Organic Framework Magnets journal February 2020
2D Semiconducting Metal–Organic Framework Thin Films for Organic Spin Valves journal November 2019
A Ferric Semiquinoid Single-Chain Magnet via Thermally-Switchable Metal–Ligand Electron Transfer journal May 2018
Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials journal February 2008
Towards Conducting Metal-Organic Frameworks journal January 2011
Formation enthalpies by mixing GGA and GGA + U calculations journal July 2011
Elektrisch leitfähige poröse Metall-organische Gerüstverbindungen journal January 2016
Electron delocalization and charge mobility as a function of reduction in a metal–organic framework journal June 2018
Effects of Mixed Valency in an Fe-Based Framework: Coexistence of Slow Magnetic Relaxation, Semiconductivity, and Redox Activity journal March 2020
Tuning the thermoelectric performance of π–d conjugated nickel coordination polymers through metal–ligand frontier molecular orbital alignment journal January 2018
From 2D to 3D: Postsynthetic Pillar Insertion in Electrically Conductive MOF journal February 2022
Electronic Conductivity, Ferrimagnetic Ordering, and Reductive Insertion Mediated by Organic Mixed-Valence in a Ferric Semiquinoid Metal–Organic Framework journal December 2015
Electroactive Organic Building Blocks for the Chemical Design of Functional Porous Frameworks (MOFs and COFs) in Electronics journal June 2020
Metal-to-Semiconductor Transition in Two-Dimensional Metal–Organic Frameworks: An Ab Initio Dynamics Perspective journal May 2021
Magnetically ordered molecule-based materials journal January 2011
Coordination Programming of Two-Dimensional Metal Complex Frameworks journal March 2016
Microscopic coexistence of antiferromagnetic and spin-glass states journal June 2013
Signature of Metallic Behavior in the Metal–Organic Frameworks M 3 (hexaiminobenzene) 2 (M = Ni, Cu) journal September 2017
New Route to the Mixed Valence Semiquinone-Catecholate Based Mononuclear Fe III and Catecholate Based Dinuclear Mn III Complexes:  First Experimental Evidence of Valence Tautomerism in an Iron Complex journal September 2004
Coordination polymers for n-type thermoelectric applications journal January 2020
Efficient and tunable one-dimensional charge transport in layered lanthanide metal–organic frameworks journal November 2019
AC Susceptibility Studies of Phase Transitions and Magnetic Relaxation: Conventional, Molecular and Low-Dimensional Magnets journal December 2013
New Porous Crystals of Extended Metal-Catecholates journal August 2012
Redox-active ligands: Recent advances towards their incorporation into coordination polymers and metal-organic frameworks journal July 2021
HLE17: An Efficient Way To Predict Band Gaps of Complex Materials journal June 2019
Electrically Conductive Porous Metal-Organic Frameworks journal January 2016
Paramagnetic Conducting Metal–Organic Frameworks with Three‐Dimensional Structure journal September 2020
Spin-glass behavior in a three-dimensional antiferromagnet ordered phase: Magnetic structure of Co 2 ( OH ) ( PO 4 ) journal September 2002
2D Semiconducting Metal–Organic Framework Thin Films for Organic Spin Valves journal November 2019
Density Functional Theory in Transition-Metal Chemistry: A Self-Consistent Hubbard U Approach journal September 2006

Similar Records

Linker Redox Mediated Control of Morphology and Properties in Semiconducting Iron‐Semiquinoid Coordination Polymers**
Journal Article · Fri Oct 07 00:00:00 EDT 2022 · Angewandte Chemie (International Edition) · OSTI ID:1891566

Electronic Conductivity, Ferrimagnetic Ordering, and Reductive Insertion Mediated by Organic Mixed-Valence in a Ferric Semiquinoid Metal–Organic Framework
Journal Article · Tue Nov 17 00:00:00 EST 2015 · Journal of the American Chemical Society · OSTI ID:1891566

Synthetic Routes for a 2D Semiconductive Copper Hexahydroxybenzene Metal–Organic Framework
Journal Article · Mon Sep 03 00:00:00 EDT 2018 · Journal of the American Chemical Society · OSTI ID:1891566

Related Subjects