Ionization equilibria of cobalt(II) chloride in N,N-dimethylformamide

Grzybkowski, Wacław; Pilarczyk, Michał

doi:10.1039/f19868201703

Cited by 11 publications

(19 citation statements)

References 1 publication

(1 reference statement)

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“…Following the metal exchange process, each [Co(DMF) 6 ] 2+ complex counterion in 2a can be replaced with two equivalents of Et 4 N + by soaking crystals of 2a in a solution of (Et 4 N)Cl in DMF (see the SI for details). This process gave a blue supernatant within 1 min, arising from the formation of [CoCl 4 ] 2– ions, and the product (Et 4 N) 2 [Co 2 L 3 ] ( 4a ) via a SC-SC process. The structure of 4a remains in the space group P 3̅1 m , with a unit cell parameter a that is nearly identical to that of 2a (see Table ).…”

Section: Results and Discussionsupporting

confidence: 77%

Harnessing Structural Dynamics in a 2D Manganese–Benzoquinoid Framework To Dramatically Accelerate Metal Transport in Diffusion-Limited Metal Exchange Reactions

Liu

DeGayner

et al. 2018

J. Am. Chem. Soc.

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Postsynthetic metal exchange represents a powerful synthetic method to generate metal-organic frameworks (MOFs) that are not accessible through direct synthesis, yet it is often hampered by slow reaction kinetics and incomplete exchange. While studies of metal exchange reactions have primarily focused on the transmetalation process, transport of exogenous metal ions into the framework structure represents a critical yet underexplored process. Here, we employ X-ray crystallography, electron microscopy, and energy dispersive X-ray spectroscopy to comprehensively examine the transport of Co and Zn ions during postsynthetic metal exchange reactions within the 2D manganese-benzoquinoid framework (EtN)[MnL] (HL = 3,6-dichloro-2,5-dihydroxy-1,4-benzoquinone). These studies reveal that exogenous metal ions diffuse primarily through the 1D channel along the crystallographic c axis, and this transport represents the rate-determining step. In addition, the Mn framework exhibits reversible dynamic structure behavior, contracting upon desolvation and then rapidly restoring its original structure and full volume upon resolvation. When conducting metal exchange reactions using a partially desolvated sample, these structural dynamics lead to acceleration of metal transport by up to 2000-fold, improve product purity, and give exchange of a larger fraction of metal sites. Finally, upon performing metal exchange using full-solvated crystals, an intermediate product can be isolated that constitutes a unique example of a 2D material with a gradient vertical heterostructure.

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Section: Results and Discussionsupporting

confidence: 77%

Harnessing Structural Dynamics in a 2D Manganese–Benzoquinoid Framework To Dramatically Accelerate Metal Transport in Diffusion-Limited Metal Exchange Reactions

Liu

DeGayner

et al. 2018

J. Am. Chem. Soc.

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“…Indeed, plotting the Co/Zn ratio against the Gutmann donor numbers revealed a convincing correlation, as shown in Figure S5 (Supporting Information). Unfortunately, because solvated CoCl 2 is known to exist in equilibrium between various four‐ and six‐coordinate species,29 extending our DFT analysis to this system is problematic and led to inferior correlations, as shown in Figure S6 and S7 (Supporting Information). Nevertheless, our experimental evidence indicates that solvents that solvate Zn 2+ better enable faster exchange of Co 2+ into the MFU‐4 l lattice.…”

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confidence: 99%

Solvent‐Dependent Cation Exchange in Metal–Organic Frameworks

Brozek

Bellarosa

Soejima

et al. 2014

Chemistry A European J

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“…The inset of Figure (b) shows the saturation point of NO–Co(II) complexation, based on which about a 1.2:1 binding stoichiometry of Co(II) to the NO ligand was estimated. The CoCl 2 solution in DMF showed absorption bands at 609 and 674 nm, typical of pseudotetrahedral complexes of Co(II), and the wavelength of these bands did not change during the titration of 2DSP‐PBBI. This result indicates that ligand exchange between the NO and Cl − /DMF occurred while maintaining the pseudotetrahedral geometry in the CoCl 2 solution .…”

Section: Resultsmentioning

confidence: 99%

Polybenzobisimidazole‐derived two‐dimensional supramolecular polymer

Seo

Carpenter

Gaugler

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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We report a novel crystalline supramolecular polybenzobisimidazole (SP-PBBI) capable of providing a twodimensional polymer (2DSP-PBBI) by liquid-phase exfoliation. A regular arrangement of rigid rod-like polybenzobisimidazole (PBBI) chains is achieved by interchain hydrogen bonding. Titration of 2DSP-PBBI with cobalt chloride (CoCl 2 ) using UV-Vis spectroscopy demonstrates the presence of bidentate NO ligands on the PBBI backbone and NO-Co(II) complexation. Imaging analysis using atomic force microscopy (AFM) reveals the planar surface morphology of exfoliated 2DSP-PBBI sheets with lateral dimensions of <1 lm and thickness of <30 nm. The size of the polymer crystal growth is tuned by employing condensation/ precipitation polymerization under nonisothermal conditions.

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Ionization equilibria of cobalt(II) chloride in N,N-dimethylformamide

Cited by 11 publications

References 1 publication

Harnessing Structural Dynamics in a 2D Manganese–Benzoquinoid Framework To Dramatically Accelerate Metal Transport in Diffusion-Limited Metal Exchange Reactions

Harnessing Structural Dynamics in a 2D Manganese–Benzoquinoid Framework To Dramatically Accelerate Metal Transport in Diffusion-Limited Metal Exchange Reactions

Solvent‐Dependent Cation Exchange in Metal–Organic Frameworks

Polybenzobisimidazole‐derived two‐dimensional supramolecular polymer

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