Anion-templated assembly of multinuclear copper(<scp>ii</scp>)–triazole complexes

Gopalakrishnan, Mohan; Krittametaporn, Nuttaporn; Yoshinari, Nobuto; Konno, Takumi; Sangtrirutnugul, Preeyanuch

doi:10.1039/d0nj02832k

Cited by 4 publications

(2 citation statements)

References 45 publications

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“…The closely related silicon hexafluoride dianion, SiF 6 2– , is also a molecule of interest as it has been shown to dissociate into SiF 5 – and F – . , SiF 6 2– also shares an octahedral geometry with the isoelectronic PF 6 – ion, and both have histories of use in coordination chemistry. − The microscale hydration of the SiF 6 2– ion provides an opportunity to probe the charge dependence of microhydration patterns between the doubly charged SiF 6 2– ion and the singly charged SiF 5 – ion as well as the BF 4 – and PF 6 – ions, both of whose hydration patterns have been studied previously at both the microscale − and in the bulk phase. ,, …”

Section: Introductionmentioning

confidence: 99%

Probing the Effects of Size and Charge on the Monohydration and Dihydration of SiF₅^– and SiF₆^2– via Comparisons with BF₄^– and PF₆^–

Mosely,

Tschumper

2024

J. Phys. Chem. A

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This study systematically examines the interactions of the trigonal bipyramidal silicon pentafluoride and octahedral silicon hexafluoride anions with either one or two water molecules, (SiF 5 − (H 2 O) n and SiF 6 2− (H 2 O) n , respectively, where n = 1, 2). Full geometry optimizations and subsequent harmonic vibrational frequency computations are performed using the CCSD(T) ab initio method with a triple-ζ correlation consistent basis set augmented with diffuse functions on all non-hydrogen atoms (cc-pVTZ for H and aug-cc-pVTZ for Si, O, and F; denoted as haTZ). Two monohydrate and six dihydrate minima have been identified for the SiF 5 − (H 2 O) n systems, whereas one monohydrate and five dihydrate minima have been identified for the SiF 6 2− (H 2 O) n systems. Both monohydrated anions have a minimum in which the water molecule adopts a symmetric double ionic hydrogen bond (DIHB) motif with C 2v symmetry. However, a second unique monohydrate minimum has been identified for SiF 5 − in which the water molecule adopts an asymmetric DIHB motif along the edge of the trigonal bipyramidal anion between one axial and one equatorial F atom. This C s structure is more than 2 kcal mol −1 lower in energy than the C 2v local minimum at the CCSD(T)/haTZ level of theory. While the interactions between the solvent and ionic solute are quite strong for the monohydrated anions (electronic dissociation energies of ≈12 and ≈24 kcal mol −1 for the SiF 5 − (H 2 O) 1 and SiF 6 2− (H 2 O) 1 global minima, respectively), these values are nearly perfectly doubled for the dihydrates, with the lowest-energy SiF 5 − (H 2 O) 2 and SiF 6 2− (H 2 O) 2 minima exhibiting dissociation energies of ≈24 and ≈47 kcal mol −1 , respectively. Structures that form hydrogen bonds between the solvating water molecules also exhibit the largest shifts in the harmonic OH stretching frequencies for the waters of hydration. These shifts can exceed −100 cm −1 for the SiF 5 − (H 2 O) 2 minimum and −300 cm −1 for the SiF 6 2− (H 2 O) 2 minimum relative to an isolated H 2 O molecule at the CCSD(T)/haTZ level of theory. This work also corrects the OH stretching frequency shifts for two dihydrate minima of PF 6− that were previously erroneously reported (J.

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Section: Introductionmentioning

confidence: 99%

Probing the Effects of Size and Charge on the Monohydration and Dihydration of SiF₅^– and SiF₆^2– via Comparisons with BF₄^– and PF₆^–

Mosely,

Tschumper

2024

J. Phys. Chem. A

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“…The biochemical implication of ions in human health and environment focuses on the synthetic strategy of a receptor in such a manner that the chemosensor selectively emits recognizable signals on binding with bioactive or toxic cations and anions. Polypodal Schiff bases may synthesize multinuclear metallo–macrocycle complexes, 1,2 which may act as potential magnetic materials, 3,4 homogeneous catalysts, 5 optical and electronic materials, 6,7 sensing devices, 8 etc . Schiff bases with fluorogenic components such as carbazole, 9,10 quinoline, 11,12 rhodamine, 13,14 naphthyl, 15,16 pyrenyl, 17,18 fluorenyl, 19,20 and diformyl 21,22 influence the emission energy, intensity, pattern, and the molecules might serve as sensitive detectors of ions/molecules.…”

Section: Introductionmentioning

confidence: 99%

Idiosyncatic recognition of Zn²⁺ and CN⁻ using pyrazolyl-hydroxy-coumarin scaffold and live cell imaging: depiction of luminescent Zn(ii)-metallocryptand

et al. 2022

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Where Fluoride Is Present, Hexafluorosilicate Might Be Encountered: Supramolecular Binding of the SiF₆^2– Anion by Nanojars

Al Isawi,

Zeller,

Mezei

2024

ACS Omega

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While the fact that HF etches glass is rather common chemical knowledge, the reaction of fluoride ions in an organic solvent with glassware under alkaline conditions has not yet been documented. It becomes apparent that, in general, whenever any fluorine-containing material is handled in silicon-based glassware, the possible presence of SiF 6 2− should be considered regardless of the pH of the reaction medium. Subsequent to the initial, inadvertent synthesis by the reaction of CuF 2 with laboratory glassware, hexafluorosilicate-entrapping supramolecular assemblies (nanojars) of the formula [SiF 6 ⊂{cis-Cu II (μ−OH)(μ-pz)} n ] 2− (Cu n SiF 6 ; n = 28, 30, 32, 34) were rationally prepared by the reaction of Cu 2+ with pyrazole (Hpz) in the presence of a base and SiF 6 2− ions or by combining Cu n CO 3 with H 2 SiF 6 or HF. This work demonstrates that nanojars are excellent anion-binding agents not only for trigonal planar/pyramidal or tetrahedral anions but also for larger, octahedral anions, which are bound exclusively by charge-assisted hydrogen bonds. The SiF 6 2− anion guest is preferentially bound by a larger Cu 32 host, whereas CO 3 2− favors a smaller Cu 27 nanojar. The Cu n SiF 6 mixture was characterized by electrospray ionization mass spectrometry as well as variable-temperature, paramagnetic 1 H and 19 F NMR spectroscopy in solution, complemented by single-crystal X-ray diffraction studies in the solid state, which reveal the unprecedented structure of a Cu 8+14+10 nanojar (where Cu 8 , Cu 10 , and Cu 14 are the component Cu x metallamacrocycles of the Cu 32 nanojar).

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Anion-templated assembly of multinuclear copper(ii)–triazole complexes

Cited by 4 publications

References 45 publications

Probing the Effects of Size and Charge on the Monohydration and Dihydration of SiF₅^– and SiF₆^2– via Comparisons with BF₄^– and PF₆^–

Probing the Effects of Size and Charge on the Monohydration and Dihydration of SiF₅^– and SiF₆^2– via Comparisons with BF₄^– and PF₆^–

Idiosyncatic recognition of Zn²⁺ and CN⁻ using pyrazolyl-hydroxy-coumarin scaffold and live cell imaging: depiction of luminescent Zn(ii)-metallocryptand

Where Fluoride Is Present, Hexafluorosilicate Might Be Encountered: Supramolecular Binding of the SiF₆^2– Anion by Nanojars

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Anion-templated assembly of multinuclear copper(ii)–triazole complexes

Cited by 4 publications

References 45 publications

Probing the Effects of Size and Charge on the Monohydration and Dihydration of SiF5– and SiF62– via Comparisons with BF4– and PF6–

Probing the Effects of Size and Charge on the Monohydration and Dihydration of SiF5– and SiF62– via Comparisons with BF4– and PF6–

Idiosyncatic recognition of Zn2+ and CN− using pyrazolyl-hydroxy-coumarin scaffold and live cell imaging: depiction of luminescent Zn(ii)-metallocryptand

Where Fluoride Is Present, Hexafluorosilicate Might Be Encountered: Supramolecular Binding of the SiF62– Anion by Nanojars

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Probing the Effects of Size and Charge on the Monohydration and Dihydration of SiF₅^– and SiF₆^2– via Comparisons with BF₄^– and PF₆^–

Probing the Effects of Size and Charge on the Monohydration and Dihydration of SiF₅^– and SiF₆^2– via Comparisons with BF₄^– and PF₆^–

Idiosyncatic recognition of Zn²⁺ and CN⁻ using pyrazolyl-hydroxy-coumarin scaffold and live cell imaging: depiction of luminescent Zn(ii)-metallocryptand

Where Fluoride Is Present, Hexafluorosilicate Might Be Encountered: Supramolecular Binding of the SiF₆^2– Anion by Nanojars