Effect of the Metal within Regioisomeric Paddle‐Wheel‐Type Metal–Organic Frameworks

Ha, Hyun‐Joon; Kim, Youngik; Kim, Dopil; Lee, Ji‐Hyun; Song, Yoodae; Kim, Su Yeon; Park, Myung Hwan; Yoon, Minyoung; Kim, Min

doi:10.1002/chem.201903210

Cited by 7 publications

(7 citation statements)

References 31 publications

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“…We seek to link the coordinatively unsaturated nodes of metallic Ni 3 (HIB) 2 monolayers by using extrinsic ligands. Three potential bridging organic linker candidates are explored: 1,4-pyrazine, DABCO (1,4-diazabicyclo[2.2.2]octane), and 4,4′-bipyridine, all of which are commonly used linkers in the MOF field. − Retrofitting these linkers results in interlayer spacing of 7 Å (pyrazine), ∼9 Å (DABCO), and ∼11 Å (bipyridine). In each case, the sheets are sufficiently far apart (per Figure b) to minimize π-stacking interactions between the covalent sheets.…”

Section: Resultsmentioning

confidence: 99%

Electronic Challenges of Retrofitting 2D Electrically Conductive MOFs to Form 3D Conductive Lattices

Lê

Mancuso

Hendon

2021

ACS Appl. Electron. Mater.

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Porous electrical conductors offer opportunities for nextgeneration energy storage solutions and electrocatalytic technologies. Metal−organic frameworks are one of the highest porosity scaffolds but typically feature low electrical conductivity due to their highly ionic metal−ligand interface. In this paper, we use computational approaches to study the inclusion of ligating pillars in a known electrically conductive framework, Ni 3 (hexaiminobenzene) 2 . We hypothesize that because Ni 3 (hexaiminobenzene) 2 is an in-plane conductor, retrofitting this material may yield a 3D-connected network with metallicity in all crystallographic directions. However, we find that while this strategy likely yields unstable connectivity for the Ni 2+ system, the use of either Cr 2+ or Fe 2+ provides a unique avenue to form 3D-connected conductors. The study further highlights the critical role of the metal d z 2 orbitals in creating conductive metal−organic frameworks.

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Section: Resultsmentioning

confidence: 99%

Electronic Challenges of Retrofitting 2D Electrically Conductive MOFs to Form 3D Conductive Lattices

Lê

Mancuso

Hendon

2021

ACS Appl. Electron. Mater.

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“…One example of a breathable MOF is [Zn 2 II (BDC) 2 (DABCO)] (BDC = 1,4-benzenedicarboxylate, DABCO = 1,4-diazabicyclo[2.2.2]octane ( 1 )), − where two-dimensional (2D) layers are formed by paddle wheels composed of divalent metal cations and are bridged by BDC linkers. The layers are pillared by DABCO to form a three-dimensional (3D) framework.…”

Section: Introductionmentioning

confidence: 99%

Long-Term Solar Energy Storage under Ambient Conditions in a MOF-Based Solid–Solid Phase-Change Material

2020

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This paper demonstrates a metal–organic framework (MOF) containing photoswitches within the pores as a hybrid solar thermal fuel (STF) and solid–solid phase-change material (ss-PCM). A series of azobenzene-loaded MOFs were synthesized with the general formula Zn2(BDC)2(DABCO)(AB) x (BDC = 1,4-benzenedicarboxylate, DABCO = 1,4-diazabicyclo[2.2.2]octane, AB = azobenzene, where x = 1.0, 0.9, 0.5, 0.3), herein named 1⊃AB1.0, 1⊃AB0.9, 1⊃AB0.5, and 1⊃AB0.3 respectively. X-ray powder diffraction, solid-state NMR, and density functional theory calculations were used to explore in detail the structural changes of the host framework that take place upon loading with the AB guest molecules. Differential scanning calorimetry measurements reveal a reversible phase change, which is absent from the evacuated framework. Upon irradiation with 365 nm light, 40% of the AB guests converted from the trans to the higher-energy cis isomeric form in 1⊃AB1.0. The energy stored within the metastable cis isomers is released upon heating and balances the endotherm associated with the phase transition. However, the exotherm associated with the phase transition is retained upon cooling, resulting in a net energy release over a full heating–cooling cycle. The maximum energy density is observed for the fully loaded composite 1⊃AB1.0, which releases 28.9 J g–1. In addition, the cis-AB guests in this composite showed negligible thermal reconversion during 4 months at ambient temperature, with an estimated energy storage half-life of 4.5 years. Further development of MOF-based STF-ss-PCMs could lead to applications for solar energy conversion and storage, and thermal management.

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“…In the previous study focusing on the flexibility control of MOFs with functional group regioisomerism, − the possibility of porosity control of MOFs with a combination of ligands was raised. Electron-rich, dimethoxy functionalization was selected, and Zn-based DMOFs were studied as the main MOF system, as it showed significant flexibility changes based on the regioisomerism . Two main ligands, namely, BDC-2,3-(OMe) 2 and BDC-2,5-(OMe) 2 , were prepared by following previously reported procedures through methylation of dihydroxy ligands (Scheme S1).…”

Section: Resultsmentioning

confidence: 99%

“…It is not appropriate to use quantum chemistry to investigate entire MOF particles with a nearly infinite 3D matrix-like structure. As discussed previously, rationally truncated cluster model structures can instead be used to generally understand and describe the electronic and geometric features of entire MOFs. The cluster model has been widely used to investigate MOF properties such as spin property, hydrogen gas adsorption, and photophysical properties .…”

Section: Resultsmentioning

confidence: 99%

“…The general shape of the optimized models includes two square pyramids with Zn 2+ placed at the center. Deviation from an octahedral-like structure for a zinc central atom has also been reported previously, and a similar geometric distortion was observed for the two model structures studied herein. In the optimized model structures, the ortho -functionalized BDC-2,3-(OMe) 2 ligands have two methoxy groups placed at the same side causing severe steric hindrance, resulting in methoxy groups perpendicular to a benzene ring on BDC.…”

Section: Resultsmentioning

confidence: 99%

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Experimental, Structural, and Computational Investigation of Mixed Metal–Organic Frameworks from Regioisomeric Ligands for Porosity Control

Kim

et al. 2020

Crystal Growth & Design

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Porosity control and structural analysis of metal–organic frameworks (MOFs) can be achieved using regioisomeric ligand mixtures. While ortho-dimethoxy-functionalized MOFs yielded highly porous structures and para-dimethoxy-functionalized MOFs displayed almost nonporous properties in their N2 isotherms after evacuation, regioisomeric ligand-mixed MOFs showed variable N2 uptake amount and surface area depending on the ligand-mixing ratio. The quantity of N2 absorbed was tuned between 20 and 300 cm3/g by adjusting the ligand-mixing ratio. Both experimental analysis and computational modeling were performed to understand the porosity differences between ortho- and para-dimethoxy-functionalized MOFs. Detailed structural analysis using X-ray crystallographic data revealed significant differences in the coordination environments of DMOF-[2,3-(OMe)2] and DMOF-[2,5-(OMe)2] (DMOF = dabco MOF, dabco = 1,4-diazabicyclo[2.2.0]octane). The coordination bond between Zn2+ and carboxylate in the ortho-functionalized DMOF-[2,3-(OMe)2] was more rigid than that in the para-functionalized DMOF-[2,5-(OMe)2]. Quantum-chemical simulation also showed differences in the coordination environments of Zn secondary building unit surrounded by methoxy-functionalized ligands and pillar ligands. In addition, the binding energy differences between Zn2+ and regioisomeric ligands (ortho- and para-dimethoxy-functionalized benzene-1,4-dicarboxylates) explained the rigidity and porosity changes of the mixed MOFs upon evacuation and perfectly matched with experimental N2 adsorption and X-ray crystallography data.

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Effect of the Metal within Regioisomeric Paddle‐Wheel‐Type Metal–Organic Frameworks

Cited by 7 publications

References 31 publications

Electronic Challenges of Retrofitting 2D Electrically Conductive MOFs to Form 3D Conductive Lattices

Electronic Challenges of Retrofitting 2D Electrically Conductive MOFs to Form 3D Conductive Lattices

Long-Term Solar Energy Storage under Ambient Conditions in a MOF-Based Solid–Solid Phase-Change Material

Experimental, Structural, and Computational Investigation of Mixed Metal–Organic Frameworks from Regioisomeric Ligands for Porosity Control

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