“Nanoscale Lattice Fence” in a Metal–Organic Framework: Interplay between Hinged Topology and Highly Anisotropic Thermal Response

DeVries, Lucas D.; Barron, Paul M.; Hurley, Evan P.; Hu, Chunhua; Choe, Wonyoung

doi:10.1021/ja2032822

Cited by 141 publications

(102 citation statements)

References 26 publications

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“…Powder X-ray diffraction (PXRD) showed that 1 can retain framework integrity even after being heated at 673 K for 2 h (Supplementary Fig. S4), which is much higher than those for other organic and organic-inorganic hybrid solids showing large thermal expansion properties [4][5][6][7][8][9][10][11][12][13][14][15]21,22 . Gas sorption measurements showed that 1 cannot adsorb N 2 or O 2 at 77 K up to P/P 0 E1 but adsorb considerable CO 2 at 195 K, with an apparent Langmuir surface area of 188 m 2 g À 1 .…”

Section: Resultsmentioning

confidence: 99%

“…For example, a few flexible PCPs showed much larger thermal expansion than common solids because the open coordination frameworks are relatively flexible [4][5][6][7][8][9][10][11][12][13][14][15] . Whereas small positive thermal expansion (PTE, 0oao20 Â 10 À 6 K À 1 , a and b V for axial and volumetric thermal expansion coefficients, respectively) is an intrinsic property of common solids 16 , negative (NTE, ao0 K À 1 ) [17][18][19][20] , very large (|a|4100 Â 10 À 6 K À 1 ), tunable and other special thermal expansion behaviours are extremely rare and have received considerable theoretical and practical interest [21][22][23][24] , which may be rationally realized by PCPs.…”

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confidence: 99%

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Direct visualization of a guest-triggered crystal deformation based on a flexible ultramicroporous framework

et al. 2013

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Host-guest composites may exhibit abnormal and/or controllable physical properties that are unavailable for traditional solids. However, it is still very difficult to control or visualize the occupancy and motion of the guest. Here we report a flexible ultramicroporous coordination polymer showing exceptional guest-responsive thermal-expansion properties. The vacant crystal exhibits constant and huge thermal expansion over a wide temperature range not only in vacuum but also in air, as its ultramicroporous channel excludes air adsorption even at 77 K. More interestingly, as demonstrated by single-crystal X-ray crystallography, molecular dynamic simulations and solid-state nuclear magnetic resonance, it selectively responds to the molecular rearrangement of N,N-dimethylformamide, leading to conformation reversion of the flexible ligand, which transfers these actions to deform the whole crystal lattice. These results illustrate that combination of ultramicroporous channel and flexible pore surface could be an effective strategy for the utilization of external physical and chemical stimuli.

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Section: Resultsmentioning

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Direct visualization of a guest-triggered crystal deformation based on a flexible ultramicroporous framework

et al. 2013

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“…For a Electronic addresses: dearweili@gmail.com and shenke738@gmail.com b W. Li instance, some MOFs have been reported to exhibit negative linear compressibility (NLC) [42][43][44] and massive positive or negative thermal expansion (PTE and NTE). [45][46][47][48] Considering that MOF research is mainly dominated by synthetic chemists, a general introduction to the intrinsic links between chemistry and mechanics is of particular interest, as it will bridge the gap between chemistry and mechanical engineering. In this mini-review, we will discuss the mechanical properties of MOFs from the viewpoint of structure and chemical bonding by presenting a number of prototypical examples to demonstrate the strong connection between chemistry and mechanical behavior.…”

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confidence: 99%

Research Update: Mechanical properties of metal-organic frameworks – Influence of structure and chemical bonding

Henke

Cheetham

2014

APL Materials

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“…Considering that this interaction is independent of the porphyrin unit, they believe this technique can be applied to various other porphyrin structures in order to construct MOFs with thermoresponsive behavior. 87 Demel et al created both a two-dimensional intercalated layer polymer and a MOF using tetra(4-sulfonatophenyl)porphyrin (TSPP) and a lanthanide-based octahedral oxometalate cluster (Fig. 34).…”

Section: Lee Et Al Produced a Mof By Mixing The Mn(iii) Derivative Omentioning

confidence: 99%

“…Proposed representation of lattice fence structure and expansion (right). 87 Liu et al used cucurbit [8]uril (CB8) and a tetranaphthylsubstituted porphyrin to create a self-assembled hyperbranched polymer. The structures were probed with 1 H NMR spectroscopy, electron paramagnetic resonance and isothermal titration calorimetry.…”

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confidence: 99%

Porphyrin polymers and organic frameworks

Day

Wamser

Walter

2015

Polymer International

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The versatility of porphyrins as optoelectronic or catalytic units makes them attractive elements for inclusion in functional materials. Polymers that include porphyrins have been created with a wide variety of structures and used in a wide range of applications. This review covers recent developments in the synthesis, characterization and applications of polymeric materials in which porphyrins are key components of the repeat units, including the rapidly growing area of metal-organic frameworks and related covalent organic frameworks. © 2015 Society of Chemical Industry Keywords: review; porphyrin; metal-organic framework; covalent organic framework PORPHYRINS AS FUNCTIONAL BUILDING BLOCKSThe porphyrin ring and its many structural relatives are common functional units in both natural and synthetic systems (Fig. 1). Porphyrins have a variety of properties that allow them to be useful in applications, especially their broad-ranging optoelectronic and catalytic capabilities. Furthermore, these properties are readily modulated by incorporation of various metals inside the ring or by substituent effects at various locations around the ring. In many cases, nature provides guidance for specific structure-function correlations and applications -the so-called biomimetic approaches. In nature, porphyrin (heme) units are typically embedded in a biological matrix that controls the environment of and access to the porphyrin. In synthetic systems, porphyrins in polymeric matrices have been developed in similar fashion to help control the specific application.In this review, we briefly cite previous reviews and summarize recent results regarding the synthesis, structure, properties and applications of polymeric porphyrins. We only include polymers that contain multiple porphyrin units as an integral part of the polymer, as opposed to polymeric matrices that are simply used to encapsulate individual porphyrin units. We also cover the rapidly growing field of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), where they specifically include porphyrins as a key component of the framework. Structures related to porphyrins (phthalocyanines, corroles, chlorins, etc.) and porphyrin dimers are not covered, but some porphyrin oligomers are discussed; reviews on many of these are available in the comprehensive series Handbook of Porphyrin Science.

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“Nanoscale Lattice Fence” in a Metal–Organic Framework: Interplay between Hinged Topology and Highly Anisotropic Thermal Response

Cited by 141 publications

References 26 publications

Direct visualization of a guest-triggered crystal deformation based on a flexible ultramicroporous framework

Direct visualization of a guest-triggered crystal deformation based on a flexible ultramicroporous framework

Research Update: Mechanical properties of metal-organic frameworks – Influence of structure and chemical bonding

Porphyrin polymers and organic frameworks

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