Solvation of Copper(II) Ion in Acetone-Water and Ethanol-Water Solutions

Friedman, Newton J.; Plane, Robert A.

doi:10.1021/ic50005a003

Cited by 34 publications

(17 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This is as expected based on the respective ligand-field strengths of the complex ligands. 20 The absorption peaks also deviate from a purely Gaussian distribution by skewing their centers towards higher energies. [5][6][7] However, there are other additional effects that are not directly attributable to ligand field theory.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Origins of optical absorption characteristics of Cu²⁺ complexes in aqueous solutions

Qiu

Wood

Ehrmann

et al. 2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

Many transition metal complexes exhibit infrared or visible optical absorption arising from d-d transitions that are the key to functionality in technological applications and biological processes. The observed spectral characteristics of the absorption spectra depend on several underlying physical parameters whose relative contributions are still not fully understood. Although conventional arguments based on ligand-field theory can be invoked to rationalize the peak absorption energy, they cannot describe the detailed features of the observed spectral profile such as the spectral width and shape, or unexpected correlations between the oscillator strength and absorption peak position. Here, we combine experimental observations with first-principles simulations to investigate origins of the absorption spectral profile in model systems of aqueous Cu(2+) ions with Cl(-), Br(-), NO2(-) and CH3CO2(-) ligands. The ligand identity and concentration, fine structure in the electronic d-orbitals of Cu(2+), complex geometry, and solvation environment are all found to play key roles in determining the spectral profile. Moreover, similar physiochemical origins of these factors lead to interesting and unexpected correlations in spectral features. The results provide important insights into the underlying mechanisms of the observed spectral features and offer a framework for advancing the ability of theoretical models to predict and interpret the behavior of such systems.

show abstract

Section: Resultsmentioning

confidence: 99%

“…Similar observations have been reported by Friedman et al for Cu 2+ complexes in acetone-water mixtures where the extinction coefficient increased as H 2 O was replaced by acetone in the solution. 20 The absorption peaks also deviate from a purely Gaussian distribution by skewing their centers towards higher energies.…”

mentioning

confidence: 99%

Origins of optical absorption characteristics of Cu²⁺ complexes in aqueous solutions

Qiu

Wood

Ehrmann

et al. 2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…Friedinan and Plane (11) have shown that such coinplexes are present in acetone solutions of copper perchlorate containing small amounts of water. Because the acetone used in the present nrorlt was not dried and because the extinction coefficient, E , = 17 I/mole c n~ is similar to that for [ C U ( O~-I~)~~C ]~+ (11), it is reasonable to assuine that this is the predoininant species in the solution and the one 'reacting \v-it11 Phen.…”

Section: Results and Discussioxmentioning

confidence: 99%

The Correlation of Absorption Spectra and Structure of Pseudo-Octahedral and Trigonal Bipyramidal Copper(ii)–1,10-Phenanthroline Complexes in Acetone Solutions

Faye¹

1966

Can. J. Chem.

View full text Add to dashboard Cite

By the use of elementary ligand field theory to interpret the absorption spectra of complexes formed in the copper(II)–1,10-phenanthrolene (Phen) system in an acetone medium, it has been shown that the mono-Phen complex is of approximately octahedral symmetry and the bis-Phen complex probably has a trigonal bipyramidal structure. At high Phen concentration, a tris-complex is formed that is probably trigonally distorted from octahedral symmetry. The results of the present work suggest that the "pentammine effect" observed in spectra of the copper(II)–ammonia complex is due to the formation of a trigonal bipyramidal complex.

show abstract

“…The observation that Mn 2+ and Zn 2+ did not cause excimer complex formation in DMSO might be due to the masking of these metal ions by a sulfoxide coordination. 16 Thus, we next tested acetone as a less nucleophilic solvent for metal ions. The test was carried out with acetone solutions of 10 equivalents metal ions (LiClO .…”

Section: Methodsmentioning

confidence: 99%

A tong-like fluorescence sensor for metal ions: perfect conformational switch of hinge sugar by pyrene stacking

et al. 2004

View full text Add to dashboard Cite

Carbohydrates are among the potential materials for molecular devices, since they are abundant natural resources. However, their rigidity has restricted their use for movable devices. Hinge sugars, 2,4-diamino-2,4-dideoxy-xylopyranosides, shed light on the use of carbohydrates as movable components, as demonstrated by the motion by which all four equatorial substituents can change to an axial orientation in synchronization with a chelation-driven 4C1-1C4 ring flip. In this study, we synthesized a tong-like metal ion sensor, 1,3-di-O-pyrenylmethylated hinge sugar (1), and its model compound, methyl 2,4-di-O-pyrenecarbonyl-xylopyranoside (2), to extend the abilities of hinge sugars as molecular components. From observations of the solvent-dependent conformational and fluorescent behavior of 2, we found that the pyrene stacking assists the 1C4 formation of xylopyranoside by 1.7 kcal mol(-1). We also found that compound 1 produced excimer fluorescence by chelation to Pt2+, Zn2+, Cd2+, Mg2+ or Mn2+, and unexpectedly by addition of acids. 1H NMR measurements ascribed this behavior to the 4C1-1C4 ring flip of hinge sugar in response to chelation or protonation at N2, and revealed rapid and perfect 1C4 formation in the case of Zn2+. These findings will extend the scope of hinge sugars as movable components.

show abstract

Solvation of Copper(II) Ion in Acetone-Water and Ethanol-Water Solutions

Cited by 34 publications

References 0 publications

Origins of optical absorption characteristics of Cu²⁺ complexes in aqueous solutions

Origins of optical absorption characteristics of Cu²⁺ complexes in aqueous solutions

The Correlation of Absorption Spectra and Structure of Pseudo-Octahedral and Trigonal Bipyramidal Copper(ii)–1,10-Phenanthroline Complexes in Acetone Solutions

A tong-like fluorescence sensor for metal ions: perfect conformational switch of hinge sugar by pyrene stacking

Contact Info

Product

Resources

About

Solvation of Copper(II) Ion in Acetone-Water and Ethanol-Water Solutions

Cited by 34 publications

References 0 publications

Origins of optical absorption characteristics of Cu2+ complexes in aqueous solutions

Origins of optical absorption characteristics of Cu2+ complexes in aqueous solutions

The Correlation of Absorption Spectra and Structure of Pseudo-Octahedral and Trigonal Bipyramidal Copper(ii)–1,10-Phenanthroline Complexes in Acetone Solutions

A tong-like fluorescence sensor for metal ions: perfect conformational switch of hinge sugar by pyrene stacking

Contact Info

Product

Resources

About

Origins of optical absorption characteristics of Cu²⁺ complexes in aqueous solutions

Origins of optical absorption characteristics of Cu²⁺ complexes in aqueous solutions