Computational Prediction of Metal Organic Frameworks Suitable for Molecular Infiltration as a Route to Development of Conductive Materials

Nie, Xiaowa; Kulkarni, Ambarish; Sholl, David S.

doi:10.1021/acs.jpclett.5b00298

Cited by 41 publications

(44 citation statements)

References 36 publications

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“…Indeed, computational studies have recently identified 45 additional MOFs that should become conductive upon TCNQ infiltration. [60] Because the through-bond charge transport strategy is amenable to reticular synthesis,r igorous inspection of existing MOFs may yield additional examples that could become conductive with minimal modification, as was the case for MOF-74.…”

Section: Angewandte Chemiementioning

confidence: 99%

Electrically Conductive Porous Metal–Organic Frameworks

2016

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Owing to their outstanding structural, chemical, and functional diversity, metal-organic frameworks (MOFs) have attracted considerable attention over the last two decades in a variety of energy-related applications. Notably missing among these, until recently, were applications that required good charge transport coexisting with porosity and high surface area. Although most MOFs are electrical insulators, several materials in this class have recently demonstrated excellent electrical conductivity and high charge mobility. Herein we review the synthetic and electronic design strategies that have been employed thus far for producing frameworks with permanent porosity and long-range charge transport properties. In addition, key experiments that have been employed to demonstrate electrical transport, as well as selected applications for this subclass of MOFs, will be discussed.

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Section: Angewandte Chemiementioning

confidence: 99%

Electrically Conductive Porous Metal–Organic Frameworks

2016

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“…Gradually, it is becoming more generally accepted that MOFs are often different from classical inorganic semiconductors and should be considered as periodic arrays of self-assembled molecules that retain their individual, characteristic, discrete molecular absorption modes. There is now a general consensus that the highest occupied molecular orbital -lowest unoccupied molecular orbital (HOMO-LUMO) or the highest occupied crystal orbitallowest unoccupied crystal orbital (HOCO-LUCO) terminology is more appropriate to describe the electronic In the quest for the development of MOFs for electronic applications and devices, much effort has been focussed upon making conductive MOFs, [18][19][20][21][22][23] either intrinsic conductors, [22][23] or through adsorption of small molecules inside pores that leads to conductive channels within the structure. 18 2 ] featuring one-dimensional channels that showed, a 10 4 increase in conductivity to 1x10 -4 S/cm, upon exposure to I 2 vapor.…”

Section: Introductionmentioning

confidence: 99%

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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“…(8)(9)(10)(11) A common feature of computational efforts to predict properties of MOFs is the assumption that MOFs can be modeled as defect-free materials represented by crystal structures determined experimentally. There has been little work to date to understand how defects in MOFs may affect the predictions of calculations of this kind.…”

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confidence: 99%

Defects in Metal–Organic Frameworks: Challenge or Opportunity?

Sholl

Lively

2015

J. Phys. Chem. Lett.

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305

279

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Metal–organic framework (MOF) materials are nanoporous materials whose crystalline character has made them attractive targets for synthesis of new materials and potential use in a diverse set of applications. The vast majority of studies of MOFs envision these materials as having ideal crystal structures. This Perspective gives an overview of the current understanding of defects in MOFs. Compared to related materials such as zeolites, the ability to detect and control defects in MOFs is nascent. Nevertheless, it is likely that defects will play a vital role in a number of contexts where MOFs are of widespread interest, so advancing our understanding of these structural features will be important in coming years. Potential origins of point defects, plane defects, and surface defects are discussed. The difficulty of defect detection in metal–organic frameworks is discussed and useful paths for future work are provided.

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Computational Prediction of Metal Organic Frameworks Suitable for Molecular Infiltration as a Route to Development of Conductive Materials

Cited by 41 publications

References 36 publications

Electrically Conductive Porous Metal–Organic Frameworks

Electrically Conductive Porous Metal–Organic Frameworks

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

Defects in Metal–Organic Frameworks: Challenge or Opportunity?

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