Low Heat of Adsorption of Ethylene Achieved by Major Solid‐State Structural Rearrangement of a Discrete Copper(I) Complex

Jayaratna, Naleen B.; Cowan, Matthew G.; Parasar, Devaborniny; Funke, Hans H.; Reibenspies, Joseph H.; Mykhailiuk, Pavel K.; Artamonov, Oleksii; Noble, Richard D.; Dias, H. V. Rasika

doi:10.1002/ange.201810460

Cited by 10 publications

(3 citation statements)

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“…[26] Non-porous small molecule adsorbents are an emerging class of materials that can overcome the traditional trade-offs between selectivity vs capacity and selectivity vs heat of adsorption. [27][28] Though these materials can be limited by their relatively low surface areas, the adsorption of small alkenes such as ethene and propene can be rapid. Recently, we reported that trinuclear copper(I) complexes { [3,5- Figure 1) and {[4-Br-3,5-(CF 3 ) 2 Pz]Cu} 3 ([CuÀ Br] 3 ) bind small olefins like ethene reversibly, both in the solid-state and in solutions, and serve as remarkably effective, selective, and energy efficient ethene/ethane separation materials.…”

Section: Introductionmentioning

confidence: 99%

“…Non‐porous small molecule adsorbents are an emerging class of materials that can overcome the traditional trade‐offs between selectivity vs capacity and selectivity vs heat of adsorption [27–28] . Though these materials can be limited by their relatively low surface areas, the adsorption of small alkenes such as ethene and propene can be rapid.…”

Section: Introductionmentioning

confidence: 99%

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Isolable 1‐Butene Copper(I) Complexes and 1‐Butene/Butane Separation Using Structurally Adaptable Copper Pyrazolates

et al. 2020

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Non-porous small molecule adsorbents such as {[3,5-(CF 3) 2 Pz] Cu} 3 (where Pz = pyrazolate) are an emerging class of materials that display attractive features for etheneÀ ethane separation. This work examines the chemistry of fluorinated copper(I) pyrazolates {[3,5-(CF 3) 2 Pz]Cu} 3 and {[4-Br-3,5-(CF 3) 2 Pz]Cu} 3 with much larger 1-butene in both solution and solid state, and reports the isolation of rare 1-butene complexes of copper(I), {[3,5-(CF 3) 2 Pz]Cu(H 2 C=CHC 2 H 5)} 2 and {[4-Br-3,5-(CF 3) 2 Pz] Cu(H 2 C=CHC 2 H 5)} 2 and their structural, spectroscopic, and computational data. The copperÀ butene adduct formation in solution involves olefin-induced structural transformation of trinuclear copper(I) pyrazolates to dinuclear mixed-ligand systems. Remarkably, larger 1-butene is able to penetrate the dense solid material and to coordinate with copper(I) ions at high molar occupancy. A comparison to analogous ethene and propene complexes of copper(I) is also provided.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Isolable 1‐Butene Copper(I) Complexes and 1‐Butene/Butane Separation Using Structurally Adaptable Copper Pyrazolates

et al. 2020

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“…[6][7][8][9][10][11][12][13][14][15][16][17] Beyond that, ordered materials constructed from CTCs are being pursued in very recent years for their controllable skeletons and excellent optical/catalytic performances. [18][19][20][21][22][23][24][25] The clusters herein are formed by sandwiching a foreign closed-shell metal cation between two gold(I) CTC molecules, resulting in an [Au 3 ]…M + …[Au 3 ] chemical formula for the resulting heptanuclear cluster. [6,[26][27][28][29][30][31][32] Since they were discovered in 1998, [28] few reports on structure determinations and luminescence properties only cover the central metal cations of Ag + and Tl + .…”

Section: Introductionmentioning

confidence: 99%

Soft Metal Cations Trigger Sandwich‐Cluster Luminescence of a New Au(I)‐Vinylimidazolate Cyclic Trinuclear Complex

et al. 2022

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Dedicated to Professor Rinaldo Poli on the occasion of his 65th birthday, with admiration and with many congratulations for all his scientific achievementsThe formation of heterobimetallic complexes from parent cyclic trinuclear complexes (CTCs) of gold(I) has become straightforward in recent years with this team and others showing that the strategy leads to strengthened AuÀ M' bonding and optoelectronic properties. A new gold(I)-vinylimidazolate CTC, 1, was prepared and the formation of highly emissive sandwich adducts with the soft metal cations Cu + , Ag + , and Tl + , 2-4, respectively, was investigated. Compound 1 does not exhibit peculiar emissive properties at room or cryogenic temperatures as the adducts do. Its unit cell packing displays an unprecedented collection of repeating units for CTCs. While the intermolecular Au…Au distances are versatile (3.470, 3.673, and 4.045 Å), they connect only single Au centres from adjacent CTCs and form extended circular networks. Hirshfeld surface analyses mapped the new CTC contours underlining the possible cooperative effects of not only metallophilic interactions but also CÀ H…π and hydrogen bonding in the packing of 1 (as opposed to the dominance of the former in most other reported CTCs). DFT calculations validate the formation of sandwich-like structures for compounds 2-4 with averaged AuÀ M distances of 2.665 Å, 2.802 Å, and 3.036 Å, respectively, close by to experimental crystal data obtained for similar sandwich compounds.

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Overcoming Fundamental Limitations in Adsorbent Design: Alkene Adsorption by Non‐porous Copper(I) Complexes

et al. 2020

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Purifying alkenes from alkanes requires cryogenic distillation. This consumes energy equivalent to countries of ca. 5 million people. Replacing distillation with adsorption processes would significantly increase energy efficiency. Trade‐offs between kinetics, selectivity, capacity, and heat of adsorption have prevented production of an optimal adsorbent. We report adsorbents that overcome these trade‐offs. [Cu‐Br]3 and [Cu‐H]3 are air‐stable trinuclear complexes that undergo reversible solid‐state inter‐molecular rearrangements to produce dinuclear [Cu‐Br⋅(alkene)]2 and [Cu‐H⋅(alkene)]2. The reversible solid‐state rearrangement, confirmed in situ using powder X‐ray diffraction, allows adsorbent design trade‐offs to be overcome, coupling low heat of adsorption (−10 to −17 kJ mol−1alkene), high alkene:alkane selectivity (47; 29), and uptake capacity (>2.5 molalkene mol−1Cu3). Most remarkably, [Cu‐H]3 displays fast uptake and regenerates capacity within 10 minutes.

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Low Heat of Adsorption of Ethylene Achieved by Major Solid‐State Structural Rearrangement of a Discrete Copper(I) Complex

Cited by 10 publications

References 40 publications

Isolable 1‐Butene Copper(I) Complexes and 1‐Butene/Butane Separation Using Structurally Adaptable Copper Pyrazolates

Isolable 1‐Butene Copper(I) Complexes and 1‐Butene/Butane Separation Using Structurally Adaptable Copper Pyrazolates

Soft Metal Cations Trigger Sandwich‐Cluster Luminescence of a New Au(I)‐Vinylimidazolate Cyclic Trinuclear Complex

Overcoming Fundamental Limitations in Adsorbent Design: Alkene Adsorption by Non‐porous Copper(I) Complexes

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