Mother structures related to the hexagonal and cubic close packing in Cu<sub>24</sub> clusters: solvent-influenced derivatives

Amayuelas, Eder; Fidalgo‐Marijuan, Arkaitz; Barandika, Gotzone; Bazán, Begoña; Urtiaga, M. Karmele; Arriortua, Marı́a I.

doi:10.1039/c5ce00251f

Cited by 11 publications

(8 citation statements)

References 30 publications

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“…The optimized geometry ( O h symmetry) of the high-spin Cu 24 ( m -BDC) 24 cage is in good agreement with the X-ray structure of [Cu 24 ( m -BDC) 24 (DMF) 20 (H 2 O) 4 ]·24DMF·40H 2 O . The Cu–Cu distances in the Cu 2 O 8 units are slight too short, probably due to the absence of coordinated DMF and H 2 O molecules in the calculated structure.…”

Section: Results and Discussionsupporting

confidence: 66%

“…An alternative starting geometry also considered was the lowest-energy structure from a heuristic method to locate the global minimum on the OPLS potential energy surface. 41,42 In all cases except for the (CH 4 ) 4 cluster, the lower-symmetry starting structure produced stronger binding energies ( 37 The Cu−Cu distances in the Cu 2 O 8 units are slight too short, probably due to the absence of coordinated DMF and H 2 O molecules in the calculated structure. However, the Cu−O and cross-ring Cu−Cu distances are predicted very well.…”

Section: ■ Results and Discussionmentioning

confidence: 96%

“… a Distances are in ångstroms. b Ref . Averaged distances in [Cu 24 ( m -BDC) 24 (DMF) 20 (H 2 O) 4 ]·24DMF·40H 2 O. …”

Section: Results and Discussionmentioning

confidence: 99%

“…The HKUST-1 POM has an unusually large affinity for enclosing small molecules such as H 2 , H 2 O, CO 2 , and CH 4 . ,,,, Using the notation of material scientists, HKUST-1 can hold 240 cm 3 (STP) cm –3 of methane at 35 bar (240 cm 3 of methane at STP per cm 3 of HKUST-1) . The main cavity of HKUST-1 (cavity C) is isostructural to Cu 24 ( m -BDC) 24 (Figure ), a POM (polyoxometalate) that has been synthesized and characterized. − The Cu 24 ( m -BDC) 24 cluster has 408 atoms with formula Cu 24 C 192 H 96 CO 96 which makes this POM difficult to study due to its size. Enclosed CH 4 molecules can interact with the metal sites (CUS) or interact with the triangular or square windows.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Study of Methane Storage in Cu₂₄(m-BDC)₂₄

McKee

2019

J. Phys. Chem. A

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Calculations on the Cu 24 (m-BDC) 24 (m-BDC = 1,3benzenedicarboxylate) polyoxometalate (POM) cage with 0, 12, 24, and 40 methane molecules inside were made using the M06 exchange/correlation functional. During filling of the cage with 40 CH 4 molecules, the 12 strongest binding CH 4 molecules are those to the coordination unsaturated sites (CUS) to the inwardly directed Cu(+2) centers via agostic interactions. The next 12 CH 4 molecules are less tightly bound followed by the next 16 CH 4 molecules with average binding energies of 8.27, 7.88, and 7.36 kcal/mol per CH 4 , respectively. A section of the Cu 24 (m-BDC) 24 cage was taken with the formula Cu 4 (m-BDC)(BC) 6 (BC = benezenecarboxylate) in order to estimate zero-point, thermal, and entropy corrections of the larger cage. Estimating free energies at 1 bar, the Cu 24 (m-BDC) 24 POM is predicted to lose 16, 12, and 12 CH 4 molecules at 67, 123, and 171 °C, respectively. The 40CH 4 @Cu 24 (m-BDC) 24 cage, which is isostructural to the main cavity of HKUST-1 with 40 CH 4 molecules inside, is predicted to have a loading of 224 cm 3 (STP) cm −3 at 1 bar.

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Section: Results and Discussionsupporting

confidence: 66%

Section: ■ Results and Discussionmentioning

confidence: 96%

“… a Distances are in ångstroms. b Ref . Averaged distances in [Cu 24 ( m -BDC) 24 (DMF) 20 (H 2 O) 4 ]·24DMF·40H 2 O. …”

Section: Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Theoretical Study of Methane Storage in Cu₂₄(m-BDC)₂₄

McKee

2019

J. Phys. Chem. A

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“…The most effective route to construct CPs is to use metal ions with mixed bridging ligands, especially with the bridging ligands containing O/N atoms [10][11][12]. In the construction of CPs, carboxylates and N-donor ligands have been widely chosen [13][14][15] as building blocks mainly due to two aspects: (i) They can exhibit rich coordination modes and (ii) they can participate in hydrogen bonding interactions by acting as donors and/or acceptors. The rational design of CPs is the control of linkage between the metal ions that allows the construction of particular structural motifs and the chemical properties of the crystalline solids [16,17].…”

Section: Introductionmentioning

confidence: 99%

The Importance of CH···X (X = O, π) Interaction of a New Mixed Ligand Cu(II) Coordination Polymer: Structure, Hirshfeld Surface and Theoretical Studies

Seth

2018

Crystals

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In this study, a new equimolar (1:1:1) mixed ligand Cu(II) polymer, [Cu(IDA)(ImP)] n (1) with iminodiacetato (IDA) and imidazo[1,2-a]-pyridine (ImP) was synthesized and characterized by single crystal X-ray diffraction analysis. X-ray crystallography reveals that compound (1) consists of polymeric zigzag chain along [010] the carboxylate carbonyl oxygen atom by two-fold symmetry screw axis. The solid-state structure is stabilized through C-H···O hydrogen bonds and C-H···π interactions that lead the molecules to generate two-dimensional supramolecular assemblies. The intricate combinations of hydrogen bonds and C-H···π interactions are fully described along with computational studies. A thorough analysis of Hirshfeld surface and fingerprint plots elegantly quantify the interactions involved within the structure. The binding energies associated with the noncovalent interactions observed in the crystal structure and the interplay between them were calculated using theoretical DFT calculations. Weak noncovalent interactions were analyzed and characterized using Bader's theory of "atoms-in-molecules" (AIM). Finally, the solid-state supramolecular assembly was characterized by the "Noncovalent Interaction" (NCI) plot index.Crystals 2018, 8, 455 2 of 15 attraction, hydrogen bonding, interactions involving π-ring [21][22][23][24]. In this respect, C-H···π [25][26][27], π-stacking [28-31], anion···π [32][33][34][35] and lone pair···π [36,37] interactions have been successfully used in building supramolecular networks [38]. A proper understanding of these forces is extremely significant, since the problem of prediction is often limited to the recognition patterns or supramolecular synthons of different functional groups. The control of the topology of crystal packing through covalent and noncovalent interactions is the main goal of crystal engineering. Therefore, proper understanding of noncovalent forces is crucial to design and predict new supramolecular entities based on mono-dimensional coordination polymers.Keeping this in mind, a new Cu(II) polymer [Cu(IDA)(ImP)] n (1) (H 2 IDA = Iminodiacetic acid and ImP = Imidazo[1-a]-pyridine]), has been synthesized (see Scheme 1) and characterized by single crystal X-ray diffraction. The title 1D polymer is stabilized through hydrogen bonds and C-H···π interaction in building 2D layered structures. The structural descriptions have been corroborated with theoretical calculations. The weak noncovalent interactions observed in the title polymer have been analyzed both energetically and using Bader's theory of "atoms in molecules" by means of Density Functional theory (DFT) calculations. Crystals 2018, 8, x FOR PEER REVIEW 2 of 15 hydrogen bonding, interactions involving π-ring [21-24]. In this respect, C-H•••π [25-27], π-stacking [28-31], anion•••π [32-35] and lone pair•••π [36,37] interactions have been successfully used in building supramolecular networks [38]. A proper understanding of these forces is extremely significant, since the problem of prediction is often limited to the...

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