An Electrically Switchable Metal-Organic Framework

Fernández, Carlos A.; Martin, Paul C.; Schaef, T.; Bowden, Mark E.; Thallapally, Praveen K.; Dang, Liem X.; Xu, Wu; Chen, Xilin; McGrail, B. Peter

doi:10.1038/srep06114

Cited by 73 publications

(68 citation statements)

References 37 publications

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“…Cu:TCNQ can grow into two phases. [22] The above discussion shows that electric field can act as a tool to alter the structure and electrical properties in Cu:TCNQ. While, in the lower conductivity Phase-II the metal coordination is more tetrahedral.…”

Section: Introductionmentioning

confidence: 91%

Low temperature transport of a charge transfer complex nanowire grown with an electric field from the vapour phase

Basori

Raychaudhuri

2015

RSC Adv.

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Suspended Cu:TCNQ (Cu-tetracyanoquinodimethane) nanowires have been grown laterally from vapour phase connecting two electrodes (∼ 1.0µm gap) with and without the presence of external electric field applied between the electrodes during growth. Temperature and bias dependent conductance of these bridged nanowires have been investigated down to 40 K. It has been found that when the nanowire is grown in an electric field, its conductance gets enhanced significantly. The nanowires show a strong non-linear conductance beyond a threshold bias along with a linear conductance at low bias. Below 100 K, the bias dependent non-linear conductance with a threshold, can be fitted to modified Zener tunneling model for charge density wave transport in both types of nanowires, raising the possibility of onset of charge density wave type transport in the Cu:TCNQ nanowires. It has been proposed that the enhancement of the conductance in Cu:TCNQ nanowires when the growth is performed in the presence of electric field occurs due to better charge transfer as well as more ordered arrangements of TCNQ stacks during growth which is enabled by strongly anisotropic polarizability of the TCNQ moiety. This also modifies the parameters related to the non-linear conductance including the threshold value.

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Section: Introductionmentioning

confidence: 91%

Low temperature transport of a charge transfer complex nanowire grown with an electric field from the vapour phase

Basori

Raychaudhuri

2015

RSC Adv.

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“…An electric field has good controllability, but the structural switching of MOFs induced by an electric field is very rare . The electric field has emerged in recent years as a new stimulating source that can induce RPT of MOFs.…”

Section: Different External Stimulimentioning

confidence: 99%

Reversible Phase Transition of Porous Coordination Polymers

Fan

Cheng

Zheng

et al. 2020

Chemistry A European J

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Porous coordination polymers or metal–organic frameworks with reversible phase‐transition behavior possess some attractive properties, and can respond to external stimuli, including physical and chemical stimuli, in a dynamic fashion. Their phase transitions can be triggered by adsorption/desorption of guest molecules, temperature changes, high pressure, light irradiation, and electric fields; these mainly include two types of transitions: crystal–amorphous and crystal–crystal transitions. These types of porous coordination polymers have received much attention because of their interesting properties and potential applications. Herein, reversible phase transition porous coordination polymers are summarized and classified based on different stimuli sources. Corresponding typical examples are then introduced. Finally, examples of their applications in gas separation, chemical sensors, guest molecule encapsulation, and energy storage are also presented.

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“…Fernandez et al reported the switchable Cu(TCNQ) MOF, which can be reversibly transformed between a high-resistance state and a conducting state by the application of an external potential. 24 These works have demonstrated the potential of MOFs for incorporation into future electronic devices. MOFs could provide superior functionalities to devices based on traditional inorganic materials, due to their extraordinarily tuneable and adaptable chemical structures and porosities, which provides a vast design palette for the tuning of MOF electronic properties.…”

Section: Introductionmentioning

confidence: 96%

Unusually Large Band Gap Changes in Breathing Metal–Organic Framework Materials

Ling

Slater

2015

J. Phys. Chem. C

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Many of the potential applications for metal organic frameworks (MOFs) focus on exploiting their porosity for molecular storage, release and separation where the functional behaviour is controlled by a subtle balance of host-guest interactions. Typically the host structure is relatively unperturbed by the presence of guests, however, a subset of metal organic frameworks exhibit dramatic phase change behaviour triggered by the adsorption of guests or other stimuli, for which the MIL-53 material is an archetype. In this work, we use density functional approaches to examine the electronic structure changes associated with changes of phase and density and find the associated change in band gaps can be larger than 1 eV for known MIL-53 type materials and hypothecated structures. Moreover, we show that internal pressure (via guest molecules) and external pressure can exert a major influence on the band gap size and gap states. The large response in electronic properties to breathing transitions in MOFs could be exploitable in future applications in resistive switching, phase change memory, piezoresistor, gas sensor, and thermochromic materials.structure of non-conducting MOFs, although the more widespread parlance of band gap terminology is still de facto and we will refer to both band gaps and HOMO-LUMO nomenclature in this work.The MOF literature is dominated by synthesis and characterisation reports of new materials and input from theory typically focuses on rationalising observation through classical simulations of host-guest interactions. Nevertheless, there are an increasing number of electronic studies of MOFs which date back more than decade: early work of Dovesi reported a high-level ab initio study of the electronic properties of MOF-5, 10 through tight-binding calculations, Kuc et al. found the band gaps of a series of Zn-based isoreticular MOFs (IRMOFs) are determined by the carbon sp 2 states of the organic linkers and longer linkers yield smaller band gaps. 9 In a recent density functional theory (DFT) study by Pham et al., halogen functionalization of the organic linkers of IRMOFs was found to modify the band gaps and also affect the absolute positions of the valence band maxima. 11 The nature of the metal centres also affects electronic properties; using DFT, Fuentes-Cabrera et al. studied IRMOF1 with different metal centres, including Be, Mg, Ca, Zn and Cd, and found all these materials possess similar band gaps but distinct conduction band splitting, and that the metallicity can be influenced by selective metal doping. 12 Tunable electronic properties of IRMOFs have been verified in different experiments. For example, in a recent UV/Vis spectroscopy experiment by Gascon et al., it was reported the band gaps of IRMOFs are conditioned by the organic linkers of IRMOFs, and that 1,4-or 2,6-naphthalenedicarboxylic acid organic linkers yielded the smallest band gaps (~ 3.3 eV) . 13 In another experiment by Lin et al., it was shown that the band gaps of Zn-based MOFs can be tuned by changing the cluster size...

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An Electrically Switchable Metal-Organic Framework

Cited by 73 publications

References 37 publications

Low temperature transport of a charge transfer complex nanowire grown with an electric field from the vapour phase

Low temperature transport of a charge transfer complex nanowire grown with an electric field from the vapour phase

Reversible Phase Transition of Porous Coordination Polymers

Unusually Large Band Gap Changes in Breathing Metal–Organic Framework Materials

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