One-dimensional alignment of strong Lewis acid sites in a porous coordination polymer

Kajiwara, Takashi; Higuchi, Masakazu; Yuasa, Akihiro; Higashimura, Hideyuki; Kitagawa, Susumu

doi:10.1039/c3cc43384f

Cited by 39 publications

(37 citation statements)

References 46 publications

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“…Powder X‐ray diffraction (PXRD) analyses revealed similar peak patterns for both PCPs (Figure b and 2d). As expected, the patterns are also similar to that of La‐BTTc (Figure c), except that the peak positions shifted to lower diffraction angles. The framework structures were determined unambiguously by single‐crystal X‐ray diffraction analyses (Figure ; Supporting Information, Table S1) of suitable crystals that were prepared by the coordination modulation method (for details see experimental section) .…”

Section: Resultssupporting

confidence: 80%

“… PXRD patterns for a) La‐PhBTTc (simulated), b) La‐PhBTTc (observed), c) La‐BTTc (observed), d) La‐ThBTB (observed), and e) La‐ThBTB (simulated).…”

Section: Resultsmentioning

confidence: 99%

“…The framework structure of La‐BTTc exhibits one‐dimensional (1‐D) hexagonal channels, similar to La‐BTB (also known as MIL‐103(La) ; BTB=benzene‐1,3,5‐tris(4‐benzoate); Figure ) but different from it, and densely aligned La III OMSs along the channels. The strong Lewis acidity was confirmed by spectroscopic measurements and catalytic reactions …”

Section: Introductionmentioning

confidence: 82%

“…Based on this strategy, we recently reported a new PCP ( La‐BTTc ), which consists of La III cations and the thiophene‐based tritopic organic linker benzene‐1,3,5‐tris(2‐thiophene‐5‐carboxylate (BTTc; Figure ) . The introduction of the thiophene rings into the π‐conjugated organic moiety leads to a highly coplanar skeleton, which favors π‐stacking.…”

Section: Introductionmentioning

confidence: 99%

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Design and Synthesis of Porous Coordination Polymers with Expanded One‐Dimensional Channels and Strongly Lewis‐Acidic Sites

et al. 2017

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New porous coordination polymers (PCPs) consisting of La III cations and thiophene-based tritopic organic linkers, La-ThBTB and La-PhBTTc, are synthesized and structurally characterized. While these La-PCPs exhibit the same type of one-dimensional hexagonal channels, their thermal and chemical stability vary significantly with respect to each other, thus demonstrating the crucial importance of the design of the skeletal structure of the organic linker. Because of the large channel sizes and strong Lewis acidity of these La-PCPs, the catalytic activity in the Lewis-acidcatalyzed cyanosilylation of carbonyl compounds shows among the highest reported so far for PCPs.

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Section: Resultssupporting

confidence: 80%

“… PXRD patterns for a) La‐PhBTTc (simulated), b) La‐PhBTTc (observed), c) La‐BTTc (observed), d) La‐ThBTB (observed), and e) La‐ThBTB (simulated).…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 82%

Section: Introductionmentioning

confidence: 99%

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Design and Synthesis of Porous Coordination Polymers with Expanded One‐Dimensional Channels and Strongly Lewis‐Acidic Sites

et al. 2017

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“…Several reports on MOF catalysed cyanosilylation reaction have appeared in the recent past, however, MOFs with copper metal node have rarely been used as a catalyst for the same reaction . Zhu et al .…”

Section: Cyanosilylation Reactionmentioning

confidence: 99%

Metal‐Organic Frameworks as Platform for Lewis‐Acid‐Catalyzed Organic Transformations

Yadav

Kanoo

2019

Chemistry An Asian Journal

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Metal-organicframeworks (MOFs)are highly promising Lewis acid catalysts;t hey either inherently possess Lewis acid sites (LASs) on it or the LASs can be generated through various post-synthetic methods, the later can be performed in MOFs in at rivial fashion. MOFs are suitable platform for catalysis because of its highly crystalline and porous nature.M oreover,w ith recent advancements, thermal and chemical stability is not ap roblem with many MOFs. In this Minireview, an enormousv ersatility of MOFs,i n terms of their microporosity/mesoporosity,s ize/shapes elec-tivity,c hirality,p ore size, etc.,h as been highlighted. These are advantageous for designing and performing various targeted organic transformations. Although, many organic transformations catalyzed by MOFs with LASs have been reported in the recent past. In this Minireview,w eh ave restricted ourselves to four important organic reactions:(i) cyanosilylation,( ii)Diels-Alder reaction, (iii)C ÀHa ctivation,a nd (iv) CO 2 -addition.T he discussion focuses mostly on the recentr eports (42 examples). Cyanosilylation ReactionCyanosilylation reaction which is nucleophillic addition of trimethylsilylcyanide (TMSCN) to carbonyl compounds producing cyanohydrins is av ery important organic transformation. Cyanohydrins are considered as versatile building blocks for fine chemicals, agrochemicals and pharmaceuticals, that is, a-hydroxyacids, b-hydroxyamines, a-aminonitriles, a-hydroxyketones and b-aminoalcohols. [41][42][43][44] In contrast to other toxic substancess uch as KCN, HCN and NaCN, TMSCN is ap referred reagent for cyanosilylation reactiona si ti se asy to handle, the SiÀCb ond has low dissociation energy andm ost importantly it [a] A.

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Solvent‐Dependent Delamination, Restacking, and Ferroelectric Behavior in a New Charge‐Separated Layered Compound: [NH₄][Ag₃(C₉H₅NO₄S)₂(C₁₃H₁₄N₂)₂]⋅8 H₂O

Sushrutha

Shivanna

Pal

et al. 2016

Chemistry An Asian Journal

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A new anionic coordination polymer, [NH ][Ag (C H NO S) (C H N ) ]⋅8 H O, with a two-dimensional structure, has been synthesized by a reaction between silver nitrate, 8-hydroxyquinoline-5-sulfonic acid (HQS), and 4,4'-trimethylene dipyridine (TMDP). The compound stabilizes in a noncentrosymmetric space group, and the lattice water molecules and the charge-compensating [NH ] group occupy the inter-lamellar spaces. The lattice water molecules can be fully removed and reinserted, which is accompanied by a crystalline-amorphous-crystalline transformation. This transformation resembles the collapse/delamination and restacking of the layers. To the best of our knowledge, this is the first observation of delamination and restacking in an inorganic coordination polymer that contains silver. The presence of a natural dipole (the anionic framework and cationic ammonium ions) along with the noncentrosymmetric space group gives rise to the room-temperature ferroelectric behavior of the compound. The ferroelectric behavior is also water-dependent and exhibits a ferroelectric-paraelectric transformation. The temperature-dependent dielectric measurements indicate that the ferroelectric/ paraelectric transformation occurs at 320 K. This transformation has also been investigated by using in-situ IR spectroscopy and PXRD studies. The second-harmonic generation (SHG) study indicated values that are comparable to some of the known SHG solids, such as potassium dihydrogen phosphate (KDP) and urea.

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One-dimensional alignment of strong Lewis acid sites in a porous coordination polymer

Cited by 39 publications

References 46 publications

Design and Synthesis of Porous Coordination Polymers with Expanded One‐Dimensional Channels and Strongly Lewis‐Acidic Sites

Design and Synthesis of Porous Coordination Polymers with Expanded One‐Dimensional Channels and Strongly Lewis‐Acidic Sites

Metal‐Organic Frameworks as Platform for Lewis‐Acid‐Catalyzed Organic Transformations

Solvent‐Dependent Delamination, Restacking, and Ferroelectric Behavior in a New Charge‐Separated Layered Compound: [NH₄][Ag₃(C₉H₅NO₄S)₂(C₁₃H₁₄N₂)₂]⋅8 H₂O

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One-dimensional alignment of strong Lewis acid sites in a porous coordination polymer

Cited by 39 publications

References 46 publications

Design and Synthesis of Porous Coordination Polymers with Expanded One‐Dimensional Channels and Strongly Lewis‐Acidic Sites

Design and Synthesis of Porous Coordination Polymers with Expanded One‐Dimensional Channels and Strongly Lewis‐Acidic Sites

Metal‐Organic Frameworks as Platform for Lewis‐Acid‐Catalyzed Organic Transformations

Solvent‐Dependent Delamination, Restacking, and Ferroelectric Behavior in a New Charge‐Separated Layered Compound: [NH4][Ag3(C9H5NO4S)2(C13H14N2)2]⋅8 H2O

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Solvent‐Dependent Delamination, Restacking, and Ferroelectric Behavior in a New Charge‐Separated Layered Compound: [NH₄][Ag₃(C₉H₅NO₄S)₂(C₁₃H₁₄N₂)₂]⋅8 H₂O