Structure, Spectroscopy, and Bonding within the Znq+–Imidazolen (q = 0, 1, 2; n = 1–4) Clusters and Implications for Zeolitic Imidazolate Frameworks and Zn–Enzymes

Boussouf, Karim; Khairat, Tarek; Prakash, M.; Komiha, N.; Chambaud, Gilberte; Hochlaf, M.

doi:10.1021/acs.jpca.5b09500

Cited by 15 publications

(12 citation statements)

References 67 publications

(105 reference statements)

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“…For neutral [Zn 0 Im], two modes of interaction between Zn 0 and Im were found: model I (MI), dominated by partial covalent character between Zn and N, in which Zn 0 is attached to the non‐protonated nitrogen atom of Im, and model II (MII) corresponding to the π‐stacking interaction between Im and Zn 0 . For [Zn + Im] and [Zn 2+ Im], only covalent σ‐type coplanar structures were identified …”

Section: Resultsmentioning

confidence: 99%

“…For [Zn + Im] and [Zn 2 + Im],o nly covalent s-type coplanar structures were identified. [22,23] The optimized geometries of CO 2 @[Zn q + Im] (q = 0, 1, 2) complexes are shown in Figures 1-3. For neutralc omplexes, we found two types of clusters:C O 2 @[Zn 0 Im] MI and CO 2 @[Zn 0 Im] MII.…”

Section: Resultsmentioning

confidence: 99%

“…Based on previous reports dealing with metal-ligand complexes and CO 2 adsorption at Zn organozinc compounds, [22,23,[29][30][31][32][33][34][35][36] the geometries of CO 2 @[Zn q + Im] (q = 0, 1, 2) complexes were optimized using PBE, PBE0, M05-2X and M11D FTs[ with the 6-311 ++G(d,p) basis set] and MP2. [37,38] These methods provide reliable properties for such complexes, as we established recently for Zn q + -Im complexes (see Ref.…”

Section: Computationaldetailsmentioning

confidence: 99%

“…The origins of such slight discrepancies were widely discussed in our benchmark studies of [Zn q + Im n ]( q = 0, 1, 2; n = 1-4) relateds pecies. [22,23] In the following, we quote the M05-2X + D3/6-311 ++G(d,p) BEs.…”

Section: Bindingenergiesmentioning

confidence: 99%

“…For [Zn q + Im n ]( q = 0, 1, 2; n = 1-4) clusters, we showed recently that the nature of the bondingb etween Zn and Im moieties depends strongly on the chargea nd on the number of Im ligands linked to Zn q + . [22,23] At present, we consider CO 2 @[Zn q + Im] (q = 0, 1, 2) clusters as prototype modelsfor CO 2 interacting with ZIFs and Zn-containing enzymes. Apriori, we expect to have somec lusters in which Zn and CO 2 interact directly,r esulting in the formationo faZnÀOb ond.…”

Section: Introductionmentioning

confidence: 99%

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Ab Initio and DFT Studies on CO₂ Interacting with Zn^q+–Imidazole (q=0, 1, 2) Complexes: Prediction of Charge Transfer through σ‐ or π‐Type Models

et al. 2016

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Using first-principles methodologies, the equilibrium structures and the relative stability of CO2 @[Zn(q+) Im] (where q=0, 1, 2; Im=imidazole) complexes are studied to understand the nature of the interactions between the CO2 and Zn(q+) -imidazole entities. These complexes are considered as prototype models mimicking the interactions of CO2 with these subunits of zeolitic imidazolate frameworks or Zn enzymes. These computations are performed using both ab initio calculations and density functional theory. Dispersion effects accounting for long-range interactions are considered. Solvent (water) effects were also considered using a polarizable continuum model approach. Natural bond orbital, charge, frontier orbital and vibrational analyses clearly reveal the occurrence of charge transfer through covalent and noncovalent interactions. Moreover, it is found that CO2 can adsorb through more favorable π-type stacking as well as σ-type hydrogen-bonding interactions. The inter-monomer interaction potentials show a significant anisotropy that might induce CO2 orientation and site-selectivity effects in porous materials and in active sites of Zn enzymes. Hence, this study provides valuable information about how CO2 adsorption takes place at the microscopic level within zeolitic imidazolate frameworks and biomolecules. These findings might help in understanding the role of such complexes in chemistry, biology and material science for further development of new materials and industrial applications.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Computationaldetailsmentioning

confidence: 99%

Section: Bindingenergiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Ab Initio and DFT Studies on CO₂ Interacting with Zn^q+–Imidazole (q=0, 1, 2) Complexes: Prediction of Charge Transfer through σ‐ or π‐Type Models

et al. 2016

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Recent Advances in the Synthesis, Characterization and Application of Zn⁺‐containing Heterogeneous Catalysts

et al. 2016

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Monovalent Zn+ (3d104s1) systems possess a special electronic structure that can be exploited in heterogeneous catalysis and photocatalysis, though it remains challenge to synthesize Zn+‐containing materials. By careful design, Zn+‐related species can be synthesized in zeolite and layered double hydroxide systems, which in turn exhibit excellent catalytic potential in methane, CO and CO2 activation. Furthermore, by utilizing advanced characterization tools, including electron spin resonance, X‐ray absorption fine structure and density functional theory calculations, the formation mechanism of the Zn+ species and their structure‐performance relationships can be understood. Such advanced characterization tools guide the rational design of high‐performance Zn+‐containing catalysts for efficient energy conversion.

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A combined experimental and theoretical study on p‐sulfonatocalix[4]arene encapsulated 7‐methoxycoumarin

Ashwin

Baby

Prakash

et al. 2017

J of Physical Organic Chem

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Host‐guest interactions are essential in chemistry, biology, medicine and environmental science. In this combined experimental and theoretical contribution, the encapsulation of 7‐methoxycoumarin (herniarin, 7MC) with p‐sulfonatocalix[4]arene (p‐SC4) is studied using absorption and fluorescence spectroscopy, cyclic voltammetry and computational approaches. The 1:1 stoichiometry is confirmed using Job's plot. Our results show that the keto group of 7MC is the main source for electrochemical conversion of this complex. The excited state 7MC radiative decay is studied using time‐correlated single photon counting technique. The computed UV‐Vis absorption spectra for this complex at gas phase and solvent are online with the experimental spectra. Moreover, we determined the binding energy and the binding constant of the 7MC‐p‐SC4 complex. Density functional theory computations revealed that stabilization of the complex formed by p‐SC4 and 7MC is due to weak noncovalent and dispersive types of interactions. A comparison with encapsulation of amino acids by p‐SC4 is also conducted. Finally, we show that the flexibility of p‐SC4 and the weak nature of its interaction with 7MC are on the origin of the reversibility of encapsulation, which is mandatory for applications such as drug delivery.

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Structure, Spectroscopy, and Bonding within the Zn^q+–Imidazole_n (q = 0, 1, 2; n = 1–4) Clusters and Implications for Zeolitic Imidazolate Frameworks and Zn–Enzymes

Cited by 15 publications

References 67 publications

Ab Initio and DFT Studies on CO₂ Interacting with Zn^q+–Imidazole (q=0, 1, 2) Complexes: Prediction of Charge Transfer through σ‐ or π‐Type Models

Ab Initio and DFT Studies on CO₂ Interacting with Zn^q+–Imidazole (q=0, 1, 2) Complexes: Prediction of Charge Transfer through σ‐ or π‐Type Models

Recent Advances in the Synthesis, Characterization and Application of Zn⁺‐containing Heterogeneous Catalysts

A combined experimental and theoretical study on p‐sulfonatocalix[4]arene encapsulated 7‐methoxycoumarin

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Structure, Spectroscopy, and Bonding within the Znq+–Imidazolen (q = 0, 1, 2; n = 1–4) Clusters and Implications for Zeolitic Imidazolate Frameworks and Zn–Enzymes

Cited by 15 publications

References 67 publications

Ab Initio and DFT Studies on CO2 Interacting with Znq+–Imidazole (q=0, 1, 2) Complexes: Prediction of Charge Transfer through σ‐ or π‐Type Models

Ab Initio and DFT Studies on CO2 Interacting with Znq+–Imidazole (q=0, 1, 2) Complexes: Prediction of Charge Transfer through σ‐ or π‐Type Models

Recent Advances in the Synthesis, Characterization and Application of Zn+‐containing Heterogeneous Catalysts

A combined experimental and theoretical study on p‐sulfonatocalix[4]arene encapsulated 7‐methoxycoumarin

Contact Info

Product

Resources

About

Structure, Spectroscopy, and Bonding within the Zn^q+–Imidazole_n (q = 0, 1, 2; n = 1–4) Clusters and Implications for Zeolitic Imidazolate Frameworks and Zn–Enzymes

Ab Initio and DFT Studies on CO₂ Interacting with Zn^q+–Imidazole (q=0, 1, 2) Complexes: Prediction of Charge Transfer through σ‐ or π‐Type Models

Ab Initio and DFT Studies on CO₂ Interacting with Zn^q+–Imidazole (q=0, 1, 2) Complexes: Prediction of Charge Transfer through σ‐ or π‐Type Models

Recent Advances in the Synthesis, Characterization and Application of Zn⁺‐containing Heterogeneous Catalysts