Topology-dependent emissive properties of zirconium-based porphyrin MOFs

Deria, Pravas; Yu, Jierui; Balaraman, Rajesh P.; Mashni, Jamil A.; White, S.

doi:10.1039/c6cc07343c

Cited by 78 publications

(95 citation statements)

References 29 publications

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“…Single crystal X-ray diffraction analysis reveals that compound 2 crystallizes in monoclinic crystal system (space group C2/m ). The structure consists of 8-connected Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (COO) 8 SBUs that are propagated by 4-connected abtc 4− linkers along three dimensions, forming a framework with a rare 4,8-c scu topology 31 , 40 42 , 43 . The connectivity of the SBU is reduced to 8 from 12 in compound 1 as a result of four out of twelve carboxylate groups being replaced by terminal H 2 O/OH − .…”

Section: Resultsmentioning

confidence: 99%

Topologically guided tuning of Zr-MOF pore structures for highly selective separation of C6 alkane isomers

et al. 2018

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As an alternative technology to energy intensive distillations, adsorptive separation by porous solids offers lower energy cost and higher efficiency. Herein we report a topology-directed design and synthesis of a series of Zr-based metal-organic frameworks with optimized pore structure for efficient separation of C6 alkane isomers, a critical step in the petroleum refining process to produce gasoline with high octane rating. Zr6O4(OH)4(bptc)3 adsorbs a large amount of n-hexane but excluding branched isomers. The n-hexane uptake is ~70% higher than that of a benchmark adsorbent, zeolite-5A. A derivative structure, Zr6O4(OH)8(H2O)4(abtc)2, is capable of discriminating all three C6 isomers and yielding a high separation factor for 3-methylpentane over 2,3-dimethylbutane. This property is critical for producing gasoline with further improved quality. Multicomponent breakthrough experiments provide a quantitative measure of the capability of these materials for separation of C6 alkane isomers. A detailed structural analysis reveals the unique topology, connectivity and relationship of these compounds.

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Section: Resultsmentioning

confidence: 99%

Topologically guided tuning of Zr-MOF pore structures for highly selective separation of C6 alkane isomers

et al. 2018

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“…Ligand‐flexibility in UiO‐MOFs can also be induced by guest inclusion, leading to changes in fluorescence emission spectra, with potential for use of these materials as sensors . The intrinsic fluorescence of Zr‐MOFs has also been demonstrated to be useful in pH sensing, while changes in ligand conformation in tetraphenylethylene‐ and porphyrin‐linked Zr MOFs have been shown to result in differences in their steady‐state emission spectra, although there is no in situ X‐ray diffraction data to provide structural mechanisms for such changes on uptake of guest molecules.…”

Section: Figurementioning

confidence: 99%

Correlating Pressure‐Induced Emission Modulation with Linker Rotation in a Photoluminescent MOF

et al. 2020

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Conformational changes of linker units in metal‐organic frameworks (MOFs) are often responsible for gate‐opening phenomena in selective gas adsorption and stimuli‐responsive optical and electrical sensing behaviour. Herein, we show that pressure‐induced bathochromic shifts in both fluorescence emission and UV/Vis absorption spectra of a two‐fold interpenetrated Hf MOF, linked by 1,4‐phenylene‐bis(4‐ethynylbenzoate) ligands (Hf‐peb), are induced by rotation of the central phenyl ring of the linker, from a coplanar arrangement to a twisted, previously unseen conformer. Single‐crystal X‐ray diffraction, alongside in situ fluorescence and UV/Vis absorption spectroscopies, measured up to 2.1 GPa in a diamond anvil cell on single crystals, are in excellent agreement, correlating linker rotation with modulation of emission. Topologically isolating the 1,4‐phenylene‐bis(4‐ethynylbenzoate) units within a MOF facilitates concurrent structural and spectroscopic studies in the absence of intermolecular perturbation, allowing characterisation of the luminescence properties of a high‐energy, twisted conformation of the previously well‐studied chromophore. We expect the unique environment provided by network solids, and the capability of combining crystallographic and spectroscopic analysis, will greatly enhance understanding of luminescent molecules and lead to the development of novel sensors and adsorbents.

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“…Zirconium (Zr)-based MOFs are known for their unusual structural suitability for photo-driven catalytic reaction, in which Zr(IV)-carboxylate coordination bonds enable the synthesis of MOFs with high surface area, better electronic structure, and reaction environment flexibility. Furthermore, the vulnerability of Zr-based MOFs to the functionalization of different moieties via many synthesis methods is an exemplification of their superiority [134,135]. Accordingly, Zr-based MOFs draw much attention in the exploration in photocatalyst input.…”

Section: Zr-based Mofsmentioning

confidence: 99%

Recent Innovation of Metal-Organic Frameworks for Carbon Dioxide Photocatalytic Reduction

2019

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The accumulation of carbon dioxide (CO2) pollutants in the atmosphere begets global warming, forcing us to face tangible catastrophes worldwide. Environmental affability, affordability, and efficient CO2 metamorphotic capacity are critical factors for photocatalysts; metal-organic frameworks (MOFs) are one of the best candidates. MOFs, as hybrid organic ligand and inorganic nodal metal with tailorable morphological texture and adaptable electronic structure, are contemporary artificial photocatalysts. The semiconducting nature and porous topology of MOFs, respectively, assists with photogenerated multi-exciton injection and adsorption of substrate proximate to void cavities, thereby converting CO2. The vitality of the employment of MOFs in CO2 photolytic reaction has emerged from the fact that they are not only an inherently eco-friendly weapon for pollutant extermination, but also a potential tool for alleviating foreseeable fuel crises. The excellent synergistic interaction between the central metal and organic linker allows decisive implementation for the design, integration, and application of the catalytic bundle. In this review, we presented recent MOF headway focusing on reports of the last three years, exhaustively categorized based on central metal-type, and novel discussion, from material preparation to photocatalytic, simulated performance recordings of respective as-synthesized materials. The selective CO2 reduction capacities into syngas or formate of standalone or composite MOFs with definite photocatalytic reaction conditions was considered and compared.

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Topology-dependent emissive properties of zirconium-based porphyrin MOFs

Cited by 78 publications

References 29 publications

Topologically guided tuning of Zr-MOF pore structures for highly selective separation of C6 alkane isomers

Topologically guided tuning of Zr-MOF pore structures for highly selective separation of C6 alkane isomers

Correlating Pressure‐Induced Emission Modulation with Linker Rotation in a Photoluminescent MOF

Recent Innovation of Metal-Organic Frameworks for Carbon Dioxide Photocatalytic Reduction

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