Formation and mid-FT-IR investigation of short (C2–C5) straight chain tetrazinc μ4-oxo-hexa-μ-carboxylates

Berkesi, Ottó; Dreveni, I.; Andor, J.A.; Goggin, P. L.

doi:10.1016/s0020-1693(00)86823-1

Cited by 20 publications

(9 citation statements)

References 13 publications

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“…1D). The IR spectrum of ZnPa under these conditions also showed the Zn 4 O band at 530 cm −1 , although it was broader and weaker than reported for oxo complexes of short-chain zinc carboxylates, both pure and in solution ( 23 , 27 ).…”

Section: Resultsmentioning

confidence: 48%

“…1E) can form in the presence of water when the side chains of the carboxylate ligands are either bulky or disordered. Examples include the crystal structure of zinc 2,2-dimethylpropanoate ( 26 ) or the structure of zinc butanoate dissolved in water-containing CCl 4 ( 27 ). However, under water-free conditions, these zinc salts exist in a linear coordination polymer structure (referred to as “chain complex,” shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

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2D-IR spectroscopy for oil paint conservation: Elucidating the water-sensitive structure of zinc carboxylate clusters in ionomers

et al. 2019

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The molecular structure around metal ions in polymer materials has puzzled researchers for decades. This question has acquired new relevance with the discovery that aged oil paint binders can adopt an ionomer structure when metal ions leached from pigments bind to carboxylate groups on the polymerized oil network. The characteristics of the metal-polymer structure are expected to have important consequences for the rate of oil paint degradation reactions such as metal soap formation and oil hydrolysis. Here, we use two-dimensional infrared (2D-IR) spectroscopy to demonstrate that zinc carboxylates formed in paint films containing zinc white pigment adopt either a coordination chain– or an oxo-type cluster structure. Moreover, it was found that the presence of water governs the relative concentration of these two types of zinc carboxylate coordination. The results pave the way for a molecular approach to paintings conservation and the application of 2D-IR spectroscopy to the study of polymer structure.

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Section: Resultsmentioning

confidence: 48%

Section: Resultsmentioning

confidence: 99%

2D-IR spectroscopy for oil paint conservation: Elucidating the water-sensitive structure of zinc carboxylate clusters in ionomers

et al. 2019

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“…The tetranuclear complex 3 was isolated as a white powder (16.8 g, 86 %) by recrystallisation of the solid from hot heptane and subsequent removal of solvent under reduced pressure. 1 …”

Section: Instrumentationmentioning

confidence: 99%

“…The tetrahedral [Zn 4 O] 6+ core is a common motif in zinc coordination chemistry with examples among the zinc carboxylates, [1,2] carbamates [3][4][5][6] and phosphates. [7,8] In the carboxylato and carbamato series, this core is extended by bridging oxygen atoms into a framework reminiscent of wurtzite-type ZnO.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Isomerisation Reactions of Tetranuclear and Octanuclear (Carbamato)zinc Complexes

et al. 2008

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A new series of (diisopropylcarbamato)(oxido)zinc complexes were obtained by innovative synthetic approaches. (2) were synthesised by an identical reaction procedure involving protolysis of ZnEt 2 with iPr 2 NH/ CO 2 and followed by stoichiometric hydrolysis. Recrystallisation of the reaction product from nitrile solvents yielded the tetrazinc complex 1. Conversely, recrystallisation from alkane solvents yielded crystals of the octazinc complex 2. The two structural isomers were readily interconverted simply by recrystallisation from the appropriate solvent. Both complexes were structurally characterised by X-ray crystallogra-

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“…However, its presence caused no harm; moreover, it was a prerequisite of complex formation. [5][6][7] The accumulated experimental results allowed us to propose a novel mechanism for the formation of the complex having three steps: (i) in the first step occurring in the solid-state, Zn(RCOO) 2 , a planar polymeric structure is formed, (ii) the polymeric structure remains but transforms to a chain during dissolution, and, finally, (iii) the polymeric structure is in equilibrium with Zn 4 O(RCOO) 6 . Water shifts the equilibrium toward complex formation, and the lack of interaction between the carboxylate chains also favors the formation of the complex.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Spectroscopic and Computational Characterization of Zn₄O(Alicyclic or Aromatic Carboxylate)₆ Complexes as Potential MOF Precursors

et al. 2010

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Potential metal-organic-framework precursors, Zn(4)O complexes with various alicyclic or aromatic carboxylate ligands, were prepared, in many cases quantitatively, from ZnO and the relevant carboxylic acids in the presence of trace amounts of water. The complexes obtained were characterized with various classical (titration) and instrumental (IR and NMR spectroscopies) methods and molecular modeling (PM3 and PM6 semiempirical quantum chemical methods and HF/6-31G** ab initio calculations). Structural peculiarities reflected in the success or failure in the synthesis could be rationalized with the combination of IR and NMR spectroscopies and molecular modeling.

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Formation and mid-FT-IR investigation of short (C2–C5) straight chain tetrazinc μ4-oxo-hexa-μ-carboxylates

Cited by 20 publications

References 13 publications

2D-IR spectroscopy for oil paint conservation: Elucidating the water-sensitive structure of zinc carboxylate clusters in ionomers

2D-IR spectroscopy for oil paint conservation: Elucidating the water-sensitive structure of zinc carboxylate clusters in ionomers

Synthesis and Isomerisation Reactions of Tetranuclear and Octanuclear (Carbamato)zinc Complexes

Synthesis and Spectroscopic and Computational Characterization of Zn₄O(Alicyclic or Aromatic Carboxylate)₆ Complexes as Potential MOF Precursors

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Formation and mid-FT-IR investigation of short (C2–C5) straight chain tetrazinc μ4-oxo-hexa-μ-carboxylates

Cited by 20 publications

References 13 publications

2D-IR spectroscopy for oil paint conservation: Elucidating the water-sensitive structure of zinc carboxylate clusters in ionomers

2D-IR spectroscopy for oil paint conservation: Elucidating the water-sensitive structure of zinc carboxylate clusters in ionomers

Synthesis and Isomerisation Reactions of Tetranuclear and Octanuclear (Carbamato)zinc Complexes

Synthesis and Spectroscopic and Computational Characterization of Zn4O(Alicyclic or Aromatic Carboxylate)6 Complexes as Potential MOF Precursors

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Synthesis and Spectroscopic and Computational Characterization of Zn₄O(Alicyclic or Aromatic Carboxylate)₆ Complexes as Potential MOF Precursors