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Université de Fribourg

Preparation of imidazolidin-4-ones and their evaluation as hydrolytically cleavable precursors for the slow release of bioactive volatile carbonyl derivatives

Trachsel, Alain ; Buchs, Barbara ; Godin, Guillaume ; Crochet, Aurélien ; Fromm, Katharina M. ; Herrmann, Andreas

In: European Journal of Organic Chemistry, 2012, no. 14, p. 2837–2854

Imidazolidin-4-ones are suitable in practical applications as hydrolytically cleavable precursors for the controlled release of fragrant aldehydes and ketones. The corresponding profragrances were prepared by treating aliphatic carbonyl compounds with commercially available amino acid amines in the presence of a base to yield mixtures of diastereomers. The two diastereomers isolated from the...

Université de Fribourg

Synthesis and characterization of new pentacoordinate iron-based aryloxide complexes

Chérémond, Yvens ; Crochet, Aurélien ; Fromm, Katharina M.

In: European Journal of Inorganic Chemistry, 2012, p. -

Heterobimetallic lithium–iron coordination compounds are interesting targets for several reasons: they can be used as precursors for mixed metal oxides, as catalysts, for example, for ring-opening polymerization reactions or to study oxidation/reduction processes. Finally their magnetic properties are also of interest. New heterobimetallic aryloxide complexes, namely...

Université de Fribourg

Tautomerism in 1-phenylazo-4-naphthols: experimental results vs quantum-chemical predictions

Antonov, Liudmil ; Kurteva, Vanya ; Crochet, Aurélien ; Mirolo, Laurent ; Fromm, Katharina M. ; Angelova, Silvia

In: Dyes and Pigments, 2012, vol. 92, no. 1, p. 714–723

The reliability in the description of the tautomerism of 1-phenylazo-4-naphthol by using of HF and MP2 ab initio levels of theory and DFT methods with variety of pure GGA (OLYP), hybrid (B3LYP and B3PW91), long range corrected (LC-BLYP) and double-hybrid (B2PLYP and mPW2PLYP) functionals with large number of basis sets was estimated. In this evaluation three criteria were used: reproduction...

Université de Fribourg

Switching azonaphthols containing a side chain with limited flexibility. Part 1. Synthesis and tautomeric properties

Kurteva, Vanya B. ; Antonov, Liudmil ; Nedeltcheva, Daniela V. ; Crochet, Aurélien ; Fromm, Katharina M. ; Nikolova, Rositsa P. ; Shivachev, Boris L. ; Nikiforova, Maya S.

In: Dyes and Pigments, 2012, vol. 92, no. 3, p. 1266–1277

A series of azo dyes, possessing amide fragments with restricted flexibility tethered to 4-(phenyldiazenyl)naphthalen-1-ol, was obtained from 1-hydroxy-2-naphthoic acid by subsequent conversion to amides and diazo coupling. It was shown that the position of the tautomeric equilibrium in solution strongly depends on the solvent in both UV and NMR concentration scale. The compounds exist as...

Université de Fribourg

Coordination Networks of Mercury(II) Halides and Polyether Ligand

Crochet, Aurélien ; Fromm, Katharina M.

In: Zeitschrift für anorganische und allgemeine Chemie, 2011, vol. 637, no. 14-15, p. 2089–2092

New crystalline mercury halide adducts with polyetheras ligands were isolated, characterized, and identified as trans-[HgIICl₂(diox)₂]n (1) and trans-[HgIII₂(diox)]n (2). The compounds were obtained from the metal halide salts in solution of 1,4-dioxane and can be considered as “cutting-out”...

Université de Fribourg

Polymorph of dibenzo-24-crown-8 and its mercury complex

Crochet, Aurélien ; Kottelat, Emmanuel ; Fleury, Antoine ; Neuburger, Markus ; Fromm, Katharina M.

In: Zeitschrift für anorganische und allgemeine Chemie, 2011, vol. 637, no. 6, p. 672–675

Dibenzo-24-crown-8 is studied herein as a flexible ligand able to adopt different conformations, as well as for the complexation of mercury. The recrystallization of dibenzo-24-crown-8 (DB24C8) from dry THF gives a new polymorphic structure of this ligand. This new structure is described and compared to the literature compound. Additionally, coordination of this ligand to mercury iodide HgI₂ is...

Université de Fribourg

(E)-1-(4-Methoxyanthracen-1-yl)-2-phenyldiazene

Crochet, Aurélien ; Fromm, Katharina M. ; Kurteva, Vanya B. ; Antonov, Liudmil

In: Acta Crystallographica Section E, 2011, vol. 67, no. 4, p. o993

The title compound, C₂₁H₁₆N₂O, has an E-conformation about the diazene N=N bond. It is reasonably planar with the phenyl ring being inclined to the mean plane of the anthracene moiety [planar to within 0.077 (3) Å] by 6.43 (10)°. The crystal structure is stabilized by C-H..π and weak π-π interactions [centroid-centroid distances of 3.7192 (16) and 3.8382 (15) Å],...

Université de Fribourg

Polyether adducts of d-block metal compounds as starting materials for new cluster compounds

Crochet, Aurélien ; Fromm, Katharina M.

In: Zeitschrift für anorganische und allgemeine Chemie, 2010, vol. 636, no. 8, p. 1484–1496

New crystalline cobalt, nickel, zinc, and mercury halide adducts with polyethers as ligands have been isolated, characterized, and identified as [Co(μ-Cl)₂CoCl₂(glyme)₂] (glyme = 1,2-dimethoxyethane), cis-[CoI₂(H₂O)₂(glyme)₂]²⁺[CoI₄]²⁻, [NiI₂(glyme)₂], [ZnI₂(glyme)], [HgCl₂(glyme)], [CoI₂(diglyme)] (diglyme = bis(2-methoxyethyl)ether), [ZnI₂(diglyme)],...

Université de Fribourg

From alkaline earth ion aggregates via transition metal coordination polymer networks towards heterometallic single source precursors for oxidic materials

Gschwind, Fabienne ; Crochet, Aurélien ; Maudez, William ; Fromm, Katharina M.

In: CHIMIA International Journal for Chemistry, 2010, vol. 64, no. 5, p. 299-320

Heterometallic oxides are used as materials in many applications, e.g. from ferroelectrics to superconductors. Making these compounds usually requires high temperatures and long reaction times. Molecular precursors may contribute to render their processing shorter and accessible at lower temperatures, thus cheaper in energy and time. In this review article, different approaches toward oxide...

Université de Fribourg

Tautocrowns: a concept for a sensing molecule with an active side-arm

Antonov, Liudmil ; Kurteva, Vanya B. ; Simeonov, Svilen P. ; Deneva, Vera V. ; Crochet, Aurélien ; Fromm, Katharina M.

In: Tetrahedron, 2010, vol. 66, no. 24, p. 4292-4297

A new sensing molecule containing aza-15-crown-5 as a receptor and 4- (phenyldiazenyl)naphthalen-1-ol as a signal converter has been synthesized. In the free ligand, the hydrogen bonding between the tautomeric OH group and the nitrogen atom from the macrocycle fully shifts the tautomeric equilibrium towards the enol form. The complexation reverses the equilibrium as a result of the strong...