Oligoether complexes of alkaline-earth metal ions. I. Structures of 2,5,8,11,14-pentaoxapentadecane (`tetraglyme`) complexed with calcium, strontium and barium thiocyanates

Wei, Y. Y.; Tinant, B.; Declercq, J. P.; Meerssche, M. Van; Dale, J.

doi:10.1107/s0108270187092965

Cited by 12 publications

(4 citation statements)

References 8 publications

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“…A fixed (and reproducible) inorganic building unit was vital to our systematic study of assembly in that it eliminated speciation diversity often seen in aqueous uranyl chemistry and coordination polymer synthesis. Further, the propensity of the inorganic tectons to form one dimensional chains, similar to those found in isothiocyanate systems containing rare earth, 65,66 alkaline earth, [67][68][69] and transition metals, 70,71 provided a reoccurring motif in 1-8, which made possible a more direct comparison of substituent effects upon crystal assembly.…”

Section: Discussionmentioning

confidence: 65%

The exploration of supramolecular interactions stemming from the [UO₂(NCS)₄(H₂O)]²⁻tecton and substituted pyridinium cations

Surbella

Cahill

2014

CrystEngComm

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The synthesis and crystal structures of eight compounds containing the anionic uranyl isothiocyanate tecton [UO 2 (NCS) 4 (H 2 O)] 2− , charge balanced by substituted pyridinium cations (4XpyH: X = Cl, Br, I, SCN, CH 3 , NH 2 , N(CH 3 ) 2 ) are reported. Hydrogen bonding interactions between coordinated water molecules and the non-coordinated sulfur atoms (O-H 2 ⋯S) of the adjoining tectons facilitate the formation of infinite 'pseudo' chains of inorganic tectons. The substituted pyridinium cations were paired with these fixed uranyl isothiocyanate tectons due to their ability to sustain multiple intermolecular interactions with the sulfur atoms of the uranyl tectons, thus promoting assembly. The variation of the substituent group bound to the organic cations allowed for the resulting non-covalent interactions to be systematically assessed in order to determine their relative effects upon packing. Additionally, respective acceptor-donor pairings as well as the relative strengths of the halogen, pseudohalogen [C-X⋯A (X = Cl, Br, I, SCN and A = O, S)] and hydrogen bonding [R-H⋯A (R = N, C and A = O, S, π)] interactions were investigated. The acceptor-donor relationships emulated hard-soft pairings and consequently increased in strength as a function of this trend.

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Section: Discussionmentioning

confidence: 65%

The exploration of supramolecular interactions stemming from the [UO₂(NCS)₄(H₂O)]²⁻tecton and substituted pyridinium cations

Surbella

Cahill

2014

CrystEngComm

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“…Nonetheless, the G4-chelated structure of Ca 2+ in the solid phase, such as [Ca(G4)](SCN) 2 ÁH 2 O, has been reported in the literature. 34 reported that solvated Ca 2+ in G1, G2, and G3 solutions also has a coordination number of eight; nonetheless, there are no refined structures of these solvated ions. 35 Due to a lack of relevant information, the Ca 2+ solvation structure in G4 solution is determined in this study by a combination of IR spectroscopy and DFT calculations.…”

Section: Ca 2+ Solvation Structurementioning

confidence: 99%

Investigation of alkali and alkaline earth solvation structures in tetraglyme solvent

Nguyen

Picard

Sergent

et al. 2021

Phys. Chem. Chem. Phys.

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“…There is a number of crystal structure determinations of complexes between a metal ion and glymes or low molecular weight poly(ethylene glycol)s where conformations are found, which could be described as different combinations of structures D1 and D2. − In the crystal structures of (PEO) 3 LiCF 3 SO 3 17 and (PEO) 3 Li[N(CF 3 SO 2 ) 2 ], the lithium ions are coordinated to three ether oxygens of the same chain and two oxygens belonging to the anions. Contrary to what was observed for the short-chain oligomers, the conformational sequences in the latter structures are not combinations of structures D1 and D2 but contain the sequence (aG + aaG + aaG - a) n .…”

Section: Introductionmentioning

confidence: 99%

Elementary Steps of Lithium Ion Transport in PEO via Quantum Mechanical Calculations

1998

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A first attempt to model lithium ion transport along a poly(ethylene oxide), PEO, chain by quantum mechanical calculations is reported here. The PEO oligomer diglyme (CH3O−(CH2CH2O)2−CH3) has been used as a model system for a PEO polymer. Different transition states have been calculated with ab initio methods for conformational changes leading to changes in coordination number for lithium from three to two in the lithium−diglyme complexes. The imaginary frequencies for the transition states and the associated intrinsic reaction coordinate paths have been calculated. Energy barriers of ∼90 kJ mol-1 are found along all the paths. The use of a bidentate structure as an intermediate between the two different tridentate structures is suggested. All structures have been optimized at the HF/6-31G** level of theory, and the total energy calculations have been performed at different levels of sophistication (HF/6-31G** and MP2/6-311+G**//HF/6-31G**). Furthermore, two equivalent transition states for the next oligomer in size, triglyme, complexed with a lithium ion have been calculated to test and show the stability of the calculations of the present model when elongating the oligomer. The results are compared with NMR data for the activation energies of conformational transformations in complexed PEO. A transport path for Li+ along a single PEO chain involving tri- to “tetra-” to tridentate coordination changes with small energy differences has been calculated.

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Oligoether complexes of alkaline-earth metal ions. I. Structures of 2,5,8,11,14-pentaoxapentadecane (`tetraglyme`) complexed with calcium, strontium and barium thiocyanates

Cited by 12 publications

References 8 publications

The exploration of supramolecular interactions stemming from the [UO₂(NCS)₄(H₂O)]²⁻tecton and substituted pyridinium cations

The exploration of supramolecular interactions stemming from the [UO₂(NCS)₄(H₂O)]²⁻tecton and substituted pyridinium cations

Investigation of alkali and alkaline earth solvation structures in tetraglyme solvent

Elementary Steps of Lithium Ion Transport in PEO via Quantum Mechanical Calculations

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Oligoether complexes of alkaline-earth metal ions. I. Structures of 2,5,8,11,14-pentaoxapentadecane (`tetraglyme`) complexed with calcium, strontium and barium thiocyanates

Cited by 12 publications

References 8 publications

The exploration of supramolecular interactions stemming from the [UO2(NCS)4(H2O)]2−tecton and substituted pyridinium cations

The exploration of supramolecular interactions stemming from the [UO2(NCS)4(H2O)]2−tecton and substituted pyridinium cations

Investigation of alkali and alkaline earth solvation structures in tetraglyme solvent

Elementary Steps of Lithium Ion Transport in PEO via Quantum Mechanical Calculations

Contact Info

Product

Resources

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The exploration of supramolecular interactions stemming from the [UO₂(NCS)₄(H₂O)]²⁻tecton and substituted pyridinium cations

The exploration of supramolecular interactions stemming from the [UO₂(NCS)₄(H₂O)]²⁻tecton and substituted pyridinium cations