Query: High Charge Mobility in a Tetrathiafulvalene-Based Microporous Metal-Organic Framework

Candidate papers:

abstract: The tetratopic ligand tetrathiafulvalene tetrabenzoate (H4TTFTB) is used to synthesize Zn2(TTFTB) a new metal organic framework that contains columnar stacks of tetrathiafulvalene and benzoate lined infinite one dimensional channels. The new MOF remains porous upon desolvation and exhibits charge mobility commensurate with some of the best organic semiconductors, confirmed by flash photolysis time resolved microwave conductivity measurements. Zn2(TTFTB) represents the first example of a permanently porous MOF with high charge mobility and may inspire further exploration of the electronic properties of these materials.
author_names: Tarun C Narayan

Tomoyo Miyakai

Shu Seki

Mircea Dinca
title: High charge mobility in a tetrathiafulvalene based microporous metal organic framework.
venue: Journal of the American Chemical Society
year: 2012

abstract: Significance: The authors report the synthesis of a zinc(II) tetrathiafulvalene tetrabenzoate [Zn2(TTFTB) metal organic framework (MOF) with high charge mobility unlike conventional MOFs. This work shows that MOFs can be useful as electronic materials in addition to their more traditional roles as gas storage materials. Comment: The benzoate groups on the TTF ligand stack in such a way that they create a porosity that is permanent. Flash photolysis time resolved microwave conductivity (FP TRMC) was used to determine that the MOF has charge mobility comparable to organic conductors. The authors also show both powder and single crystal structures of the MOFs to complement their observation of permanent porosity. O
author_names: Timothy M Swager

Markrete Krikorian
title: Tetrathiafulvalene Based Microporous Metal Organic Framework
year: 2012

abstract: Isostructural metal organic frameworks (MOFs) M2(TTFTB) (M Mn, Co, Zn, and Cd; H4TTFTB tetrathiafulvalene tetrabenzoate) exhibit a striking correlation between their single crystal conductivities and the shortest S**S interaction defined by neighboring TTF cores, which inversely correlates with the ionic radius of the metal ions. The larger cations cause a pinching of the S**S contact, which is responsible for better orbital overlap between pz orbitals on neighboring S and C atoms. Density functional theory calculations show that these orbitals are critically involved in the valence band of these materials, such that modulation of the S**S distance has an important effect on band dispersion and, implicitly, on the conductivity. The Cd analogue, with the largest cation and shortest S**S contact, shows the largest electrical conductivity, s 2.86 0.53) x 10( 4) S/cm, which is also among the highest in microporous MOFs. These results describe the first demonstration of tunable intrinsic electrical conductivity in this class of materials and serve as a blueprint for controlling charge transport in MOFs with p stacked motifs.
author_names: Sarah S Park

Eric R Hontz

Lei Sun

Christopher H Hendon

Aron Walsh

Troy Van Voorhis

Mircea Dinca
title: Cation dependent intrinsic electrical conductivity in isostructural tetrathiafulvalene based microporous metal organic frameworks.
venue: Journal of the American Chemical Society
year: 2015

abstract: The targeted incorporation of defects into crystalline matter allows for the manipulation of many properties and has led to relevant discoveries for optimized and even novel technological applications of materials. It is therefore exciting to see that defects are now recognized to be similarly useful in tailoring properties of metal organic frameworks (MOFs) For instance, heterogeneous catalysis crucially depends on the number of active catalytic sites as well as on diffusion limitations. By the incorporation of missing linker and missing node defects into MOFs, both parameters can be accessed, improving the catalytic properties. Furthermore, the creation of defects allows for adding properties such as electronic conductivity, which are inherently absent in the parent MOFs. Herein, progress of the rapidly evolving field of the past two years is overviewed, putting a focus on properties that are altered by the incorporation and even tailoring of defects in MOFs. A brief account is also given on the emerging quantitative understanding of defects and heterogeneity in MOFs based on scale bridging computational modeling and simulations.
author_names: Stefano Dissegna

Konstantin Epp

Werner R Heinz

Gregor Kieslich

Roland A Fischer
title: Defective Metal Organic Frameworks.
venue: Advanced materials
year: 2018

abstract: The reaction of MnCl2 with 2,5 disulfhydrylbenzene 1,4 dicarboxylic acid (H4DSBDC) in which the phenol groups in 2,5 dihydroxybenzene 1,4 dicarboxylic acid (H4DOBDC) have been replaced by thiophenol units, led to the isolation of Mn2(DSBDC) a thiolated analogue of the M2(DOBDC) series of metal organic frameworks (MOFs) The sulfur atoms participate in infinite one dimensional Mn S chains, and Mn2(DSBDC) shows a high surface area and high charge mobility similar to that found in some of the most common organic semiconductors. The synthetic approach to Mn2(DSBDC) and its excellent electronic properties provide a blueprint for a potentially rich area of exploration in microporous conductive MOFs with low dimensional charge transport pathways.
author_names: Lei Sun

Tomoyo Miyakai

Shu Seki

Mircea Dinca
title: Mn2(2,5 disulfhydrylbenzene 1,4 dicarboxylate) a microporous metal organic framework with infinite Mn S chains and high intrinsic charge mobility.
venue: Journal of the American Chemical Society
year: 2013

abstract: Metal organic frameworks (MOFs) allow compositional and structural diversity beyond conventional solid state materials. Continued interest in the field is justified by potential applications of exceptional breadth, ranging from gas storage and separation, which takes advantage of the inherent pores and their volume, to electronic applications, which requires precise control of electronic structure. In this Outlook we present some of the pertinent challenges that MOFs face in their conventional implementations, as well as opportunities in less traditional areas. Here the aim is to discuss select design concepts and future research goals that emphasize nuances relevant to this class of materials as a whole. Particular emphasis is placed on synthetic aspects, as they influence the potential for MOFs in gas separation, electrical conductivity, and catalytic applications.
author_names: Christopher H Hendon

Adam J Rieth

Maciej D Korzynski

Mircea Dinca
title: Grand Challenges and Future Opportunities for Metal Organic Frameworks
venue: ACS central science
year: 2017

abstract: The burgeoning field of metal organic frameworks (MOFs) has been marked by numerous key advances over the past two decades. An emerging theme is the incorporation of radical species which may be ligated as an integral structural component of, or simply appended to, the material, or else merely a guest within it. Radical incorporation has been shown to endow MOFs with a plethora of unique and fascinating magnetic, electronic and optical properties, paving the way towards their application as spin probes, and in magnetic/electronic devices, chemical sensing and molecular recognition. In view of the rapid growth of the literature in the area, this review highlights progress over the past three years (since 2011) and seeks to uncover promising ideas that will underscore future advancements at both the fundamental and applied levels.
author_names: Thomas B Faust

Deanna M D'Alessandro
title: Radicals in metal organic frameworks
year: 2014

abstract: Metal organic frameworks (MOFs) are considered as very promising candidates to build electrodes for electrochemical energy storage devices such as lithium ion batteries, fuel cells and supercapacitors, due to their diverse structure, adjustable aperture, large specific surface area and abundant active sites. Supercapacitor has been widely investigated in the past decades. Of critical importance in these devices is the electrode active materials, and this application has been intensively studied with the development of novel nanomaterials. In this review we summarize recent reports on MOFs as electrode materials for supercapacitors. Specifically, the synthesis of MOF materials for supercapacitor electrodes and their performance in electrochemical energy storage are discussed. We aim to include supercapacitor electrode materials related to MOFs, such as carbon, metal and composite materials. It is proposed that MOFs play an important role in the development of a new generation of supercapacitor electrode materials. Finally, we discuss the current challenges in the field of supercapacitors, with a view towards how to address these challenges with the future development of MOFs and their derivatives.Zhai Yao Jin Shu You Ji Gu Jia Cai Liao Ju You Jie Gou Duo Yang Kong Jing Ke Diao Bi Biao Mian Ji Da Ji Hua Xue Fan Ying Huo Xing Wei Dian Feng Fu Deng You Dian Yin Ci You Wang Cheng Wei Yan Fan Ying Yong Yu Dian Hua Xue Chu Neng Qi Jian De Dian Ji Cai Liao Ru Li Chi Zi Dian Chi Ran Liao Dian Chi Ji Chao Ji Dian Rong Qi Deng Jin Shi Nian Lai Jin Shu You Ji Gu Jia Cai Liao Ji Qi Yan Sheng Wu Cai Liao Yin Qi Liao Yan Fan De Yan Jiu Yu Ying Yong Tong Shi Jin Shu You Ji Gu Jia Cai Liao Ji Qi Yan Sheng De Na Mi Cai Liao Zuo Wei Dian Hua Xue Chu Neng Qi Jian Zhong De Guan Jian Dian Ji Ye Shou Dao Liao Yan Fan De Yan Jiu Ben Wen Zhu Yao Zong Shu Liao Jin Qi Jin Shu You Ji Gu Jia Cai Liao Ji Qi Yan Sheng Wu Zai Chao Ji Dian Rong Qi Zhong De Yan Jiu Jin Zhan Tao Lun Liao Jin Shu You Ji Gu Jia Cai Liao Zhi Bei Chao Ji Dian Rong Qi Dian Ji Cai Liao De Fang Fa Ji Qi Zai Dian Hua Xue Chu Neng Ling Yu Ti Xian Chu De You Yi Xing Neng Ji Te Shu Xing Zhi Tong Shi Ye Zong Jie Liao Jin Qi Jin Shu You Ji Gu Jia Cai Liao De Yan Sheng Wu Ru Tan Cai Liao Jin Shu Cai Liao Ji Fu He Wu Zai Chao Ji Dian Rong Qi Zhong De Yan Jiu Jin Zhan Jie Guo Shuo Ming Jin Shu You Ji Gu Jia Cai Liao Zai Fa Zhan Xin Yi Dai Chao Ji Dian Rong Qi Dian Ji Cai Liao Ling Yu Ju You Zhong Yao De Zuo Yong Zui Hou Tao Lun Liao Jin Shu You Ji Gu Jia Cai Liao Ji Qi Yan Sheng Wu Mu Qian Zai Chao Ji Dian Rong Qi Ling Yu Cun Zai De Wen Ti Yi Ji Wei Lai Ke Neng De Fa Zhan Fang Xiang
author_names: Yujie Zhao

Jinzhang Liu

Michael R Horn

Nunzio Motta

Mingjun Hu

Yan Li
title: Recent advancements in metal organic framework based electrodes for supercapacitors
venue: Science China Materials
year: 2018

abstract: A three dimensional network solid composed of Fe(III) centers and paramagnetic semiquinoid linkers, (NBu4)2Fe(III)2(dhbq)3 (dhbq(2 /3 2,5 dioxidobenzoquinone/1,2 dioxido 4,5 semiquinone) is shown to exhibit a conductivity of 0.16 0.01 S/cm at 298 K, one of the highest values yet observed for a metal organic framework (MOF) The origin of this electronic conductivity is determined to be ligand mixed valency, which is characterized using a suite of spectroscopic techniques, slow scan cyclic voltammetry, and variable temperature conductivity and magnetic susceptibility measurements. Importantly, UV vis NIR diffuse reflectance measurements reveal the first observation of Robin Day Class II/III mixed valency in a MOF. Pursuit of stoichiometric control over the ligand redox states resulted in synthesis of the reduced framework material Na0.9(NBu4)1.8Fe(III)2(dhbq)3. Differences in electronic conductivity and magnetic ordering temperature between the two compounds are investigated and correlated to the relative ratio of the two different ligand redox states. Overall, the transition metal semiquinoid system is established as a particularly promising scaffold for achieving tunable long range electronic communication in MOFs.
author_names: Lucy E Darago

Michael L Aubrey

Chung-Jui Yu

Miguel I Gonzalez

Jeffrey R Long
title: Electronic Conductivity, Ferrimagnetic Ordering, and Reductive Insertion Mediated by Organic Mixed Valence in a Ferric Semiquinoid Metal Organic Framework.
venue: Journal of the American Chemical Society
year: 2015

abstract: The development of metal organic frameworks (MOFs) as microporous electronic conductors is an exciting research frontier that has the potential to revolutionize a wide range of technologically and industrially relevant fields, from catalysis to solid state sensing and energy storage devices, among others. After nearly two decades of intense research on MOFs, examples of intrinsically conducting MOFs remain relatively scarce; however, enormous strides have recently been made. This article briefly reviews the current status of the field, with a focus on experimental milestones that have shed light on crucial structure property relationships that underpin future progress. Central to our discussion are a series of design considerations, including redox matching, donor acceptor interactions, mixed valency, and p interactions. Transformational opportunities exist at both fundamental and applied levels, from improved measurement techniques and theoretical understanding of conduction mechanisms to device engineering. Taken together, these developments will herald a new era in advanced functional materials.
author_names: Chanel F Leong

Pavel M Usov

Deanna M D'Alessandro
title: Intrinsically conducting metal organic frameworks
year: 2016