Nouveaux chélates [triazacyclononane-métaux de transition] (synthèse, complexation et premières applications)

Les polyazamacrocycles trouvent de nombreuses applications dans le domaine de la complexation de cations métalliques ou d'anions. Le laboratoire à longtemps étudié la fonctionnalisation des dérivés tétraazamacrocycliques et leurs propriétés de complexation. Afin d'accroître le savoir-faire du laboratoire et d'explorer de nouvelles propriétés de complexation des polyamines cycliques, nous nous sommes intéressé à transposer ce savoir à la fonctionnalisation d'un macrocycle plus petit : le tacn. Ce travail repose sur la mise au point d'une nouvelle stratégie de fonctionnalisation sélective du tacn et la synthèse de nouveaux dérivés. Les composés obtenus ont permis l'étude de leurs propriétés de complexation vis-à-vis de différents métaux de transition. Les propriétés de complexes de cuivre (II) ont été étudiées pour des applications en imagerie TEP ou en radioimmunothérapie. La détection de zinc (II) basée sur une détection IRM par de nouvelles sondes ditopiques tacn-do3a a été étudiée. La complexation de fer (II) pour des applications en transition de spin ont également permis de déterminer les propriétés de complexation de dérivés du tacn.The polyazamacrocycles have many applications in the field metal cations or anions complexation. Our laboratory studied the functionalization of tetraazamacrocyclic derivatives and their complexation properties during a long time. To enhance the expertise of our laboratory and to explore new properties of complexation of cyclic polyamines, we were interested in transpose his expertise to the functionalization of a smaller macrocycle: the tacn. This work is based on the development of a new synthetic strategy of selective functionalization of tacn and the synthesis of new derivatives. The complexation properties of this new functionalized macrocycles with different transition metals were also studied. The properties of copper (II) complexes have been studied for applications in Positron Emission Tomography (PET) imaging or radioimmunotherapy (RIT). The detection of zinc (II) based on Magnetic Resonance Imaging (MRI) detection by new ditopic probes tacn-do3a has been studied. Complexation of iron (II) for applications in spin crossover also revealed the complexation properties of the tacn derivatives.BREST-SCD-Bib. electronique (290199901) / SudocSudocFranceF

New chelates [triazacyclononane-transition metals] : synthesis, complexation and first applications

Les polyazamacrocycles trouvent de nombreuses applications dans le domaine de la complexation de cations métalliques ou d'anions. Le laboratoire à longtemps étudié la fonctionnalisation des dérivés tétraazamacrocycliques et leurs propriétés de complexation. Afin d'accroître le savoir-faire du laboratoire et d'explorer de nouvelles propriétés de complexation des polyamines cycliques, nous nous sommes intéressé à transposer ce savoir à la fonctionnalisation d'un macrocycle plus petit : le tacn. Ce travail repose sur la mise au point d'une nouvelle stratégie de fonctionnalisation sélective du tacn et la synthèse de nouveaux dérivés. Les composés obtenus ont permis l'étude de leurs propriétés de complexation vis-à-vis de différents métaux de transition. Les propriétés de complexes de cuivre (II) ont été étudiées pour des applications en imagerie TEP ou en radioimmunothérapie. La détection de zinc (II) basée sur une détection IRM par de nouvelles sondes ditopiques tacn-do3a a été étudiée. La complexation de fer (II) pour des applications en transition de spin ont également permis de déterminer les propriétés de complexation de dérivés du tacn.The polyazamacrocycles have many applications in the field metal cations or anions complexation. Our laboratory studied the functionalization of tetraazamacrocyclic derivatives and their complexation properties during a long time. To enhance the expertise of our laboratory and to explore new properties of complexation of cyclic polyamines, we were interested in transpose his expertise to the functionalization of a smaller macrocycle: the tacn. This work is based on the development of a new synthetic strategy of selective functionalization of tacn and the synthesis of new derivatives. The complexation properties of this new functionalized macrocycles with different transition metals were also studied. The properties of copper (II) complexes have been studied for applications in Positron Emission Tomography (PET) imaging or radioimmunotherapy (RIT). The detection of zinc (II) based on Magnetic Resonance Imaging (MRI) detection by new ditopic probes tacn-do3a has been studied. Complexation of iron (II) for applications in spin crossover also revealed the complexation properties of the tacn derivatives

Nouveaux chélates [triazacyclononane-métaux de transition] : synthèse, complexation et premières applications

The polyazamacrocycles have many applications in the field metal cations or anions complexation. Our laboratory studied the functionalization of tetraazamacrocyclic derivatives and their complexation properties during a long time. To enhance the expertise of our laboratory and to explore new properties of complexation of cyclic polyamines, we were interested in transpose his expertise to the functionalization of a smaller macrocycle: the tacn. This work is based on the development of a new synthetic strategy of selective functionalization of tacn and the synthesis of new derivatives. The complexation properties of this new functionalized macrocycles with different transition metals were also studied. The properties of copper (II) complexes have been studied for applications in Positron Emission Tomography (PET) imaging or radioimmunotherapy (RIT). The detection of zinc (II) based on Magnetic Resonance Imaging (MRI) detection by new ditopic probes tacn-do3a has been studied. Complexation of iron (II) for applications in spin crossover also revealed the complexation properties of the tacn derivatives.Les polyazamacrocycles trouvent de nombreuses applications dans le domaine de la complexation de cations métalliques ou d'anions. Le laboratoire à longtemps étudié la fonctionnalisation des dérivés tétraazamacrocycliques et leurs propriétés de complexation. Afin d'accroître le savoir-faire du laboratoire et d'explorer de nouvelles propriétés de complexation des polyamines cycliques, nous nous sommes intéressé à transposer ce savoir à la fonctionnalisation d'un macrocycle plus petit : le tacn. Ce travail repose sur la mise au point d'une nouvelle stratégie de fonctionnalisation sélective du tacn et la synthèse de nouveaux dérivés. Les composés obtenus ont permis l'étude de leurs propriétés de complexation vis-à-vis de différents métaux de transition. Les propriétés de complexes de cuivre (II) ont été étudiées pour des applications en imagerie TEP ou en radioimmunothérapie. La détection de zinc (II) basée sur une détection IRM par de nouvelles sondes ditopiques tacn-do3a a été étudiée. La complexation de fer (II) pour des applications en transition de spin ont également permis de déterminer les propriétés de complexation de dérivés du tacn

Synthèse et activités antipaludiques de bis-alkylamidines N-monosubstituées, bis-alkylguanidines et de leurs bioprécurseurs de type amidoxime et O-dérivés

Des stratégies prodrogues amidoxime et oxadiazolone ont été appliquées à de nouvelles drogues bis-alkylamidines N-monosubstituées que nous avons synthétisées selon une nouvelle stratégie divergente basée sur l'utilisation de la bis-alkyloxadiazolone N-substituée comme intermédiaire de synthèse. Des dérivés N-alkylsulfonyles de bis-alkylamidoximes ont été développés dans le but d'obtenir des structures stables in vitro tout en conservant de fortes activités orales. Enfin, de nouvelles drogues bis-alkylguanidines ont été synthétisées ainsi que leurs bioprécurseurs N-hydroxyguanidines, aminooxadiazolones et iminooxadiazolidinones. Les activités antipaludiques in vitro et in vivo des composés obtenus ont été évaluéesAmidoxime and oxadiazolone prodrug strategies have been applied to new N-monosubstituted bis-alkylamidine drugs which were synthesised by a new divergent strategy based on the use of the N-substitued bis-alkyloxadiazolone as an intermediate. Bis-alkylamidoxime N-alkylsulfonyles derivatives have been developed to obtain in vitro stable structures preserving potent oral activities. Finally, new bis-alkylguanidine drugs were synthesised as well as their bioprecursors N-hydroxyguanidines, aminooxadiazolones and iminooxadiazolidinones. In vitro and in vivo antiplasmodial activities of the obtained compounds were evaluatedMONTPELLIER-BU Sciences (341722106) / SudocSudocFranceF

exo-Diastereoisomer of 10-aryl-1,4,7-triazabicyclo[5.2.1]decane as intermediary in specific derivatisation of triazacyclononane

International audienceReaction of triazacyclononane (tacn) and aromatic aldehydes leads to aminal adducts, which exhibit onlythe exoconfiguration. In these aminal compounds, secondary amine function possesses a higher re-activity towards electrophilic reactants than the two nitrogen atoms linked to aminal carbon, giving riseto the specific derivatisation of tacn by different functionalised groups. Study of this behaviour alsopermits the access to a ditopic tacn-cyclam bicyclic polyamine

Spin Cross-Over (SCO) Complex Based on Unsymmetrical Functionalized Triazacyclononane Ligand: Structural Characterization and Magnetic Properties

The unsymmetrical ligand 1-(2-aminophenyl)-4,7-bis(pyridin-2-ylmethyl)-1,4,7-triazacyclononane (L6) has been prepared and characterized by NMR spectroscopy. The L6 ligand is based on the triazamacrocycle (tacn) ring that is functionalized by two flexible 2-pyridylmethyl and one rigid 2-aminophenyl groups. Reaction of this ligand with Fe(ClO4)2·xH2O led to the complex [Fe(L6)](ClO4)2 (1), which was characterized as the first Fe(II) complex based on the unsymmetrical N-functionalized tacn ligand. The crystal structure revealed a discrete monomeric [FeL6]2+ entity in which the unsymmetrical N-functionalized triazacyclononane molecule (L6) acts as hexadentate ligand. As observed in the few parent examples that are based on the symmetrical N-functionalized tacn ligands, the triazacyclononane ring is facially coordinated and the N-donor atoms of the three functional groups (two pyridine and one aniline groups) are disposed in the same side of the tacn ring, leading to a distorted FeN6 environment. The magnetic studies of 1 revealed the presence of an incomplete spin crossover (SCO) transition above 425 K, whose progress would be prevented by a very exothermic thermal decomposition at ca. 472 K, as shown by thermogravimetric and DSC measurements

Synthesis of an unsymmetrical N-functionalized triazacyclononane ligand and its Cu(II) complex

International audienceThe unsymmetrical 1,4-bis(2-aminophenyl)-7-(pyridin-2-ylmethyl)-1,4,7-triazacyclononane ligand (L3) has been prepared and characterized by NMR spectroscopy. The L3 ligand is based on the triazamacrocycle ring bearing one flexible 2-pyridylmethyl linked to the macrocycle group via the methyl group, and two rigid 2-aminophenyl pendant donor groups linked to the macrocycle via the aromatic carbon atoms. Reaction of this ligand with Cu(ClO4)(2)center dot 6H(2)O afforded the corresponding complex [Cu(L3)](ClO4)(2)center dot H2O (4) which was structurally characterized both in solid state and in solution. The crystal structure of 4 consists of a discrete monomeric [Cu(L3)](2+) in which the Cu(II) ion is six coordinated with three nitrogen atoms of the macrocycle ring, two of the aminophenyle and one of the pyridine appended functions. The triazacyclonane macrocycle ring is facially coordinated and the N-donor atoms of the three pendant groups (two aniline and one pyridine groups), are disposed in the same side of the basal macrocyclic ring, leading to a distorted and elongated CuN4N2 octahedron. UV-Vis spectroscopy of complex 4 in acetonitrile displays a d-d transition band at lambda = 673 nm. The voltammetric studies show that the [Cu(L3)](2+) cation can be reduced quasi-reversibly and oxidized irreversibly, both process being monoelectronic. (C) 2014 Elsevier B.V. All rights reserved

The Dimeric Pyramidal Cu 2 O 6 (H 2 O) 2 Unit - A Structural Invariant of a Homologous Series of Copper-Layered Phosphonates

International audienceTwo new layered copper hybrid materials, namely, the copper thiophene-2,5-diphosphonate [Cu2(H2O)2(O3P–C4H2S–PO3)] (Pnma; a = 7.525 Å, b = 18.292 Å, c = 7.520 Å) and the copper 3-fluorophenylphosphonate Cu(H2O)PO3–C6H4F (P21/c; a = 14.305 Å, b = 7.550 Å, c = 7.479 Å, β = 92.32°), have been synthesized. These compounds belong to the large homologous Cu(H2O)PO3R/[Cu2(H2O)2(O3P–R–PO3)] series, the structure of which is dictated by the presence of isolated dimeric pyramidal Cu2O6(H2O)2 units. The role of the Cu/H2O molar ratio of 1 in the stabilization of such a structure is discussed in connection with the Jahn–Teller effect of the copper cation. The study of the magnetic behavior of polycrystalline samples of the two compounds has revealed antiferromagnetic coupling between the copper ions. The interactions within the dimeric unit were estimated by the Bleaney–Bowers law with the spin Hamiltonian H = –JSCu1SCu2 + gβHS: J = –6.27 cm–1 for [Cu(H2O)PO3]2C4H2S, and J = –6.07 cm–1 for Cu(H2O)PO3–C6H4F

Lanthanide Complexes with Heteroditopic Ligands as Fluorescent Zinc Sensors

International audienceWe report the synthesis of two ligands containing a DO3A unit (H3DO3A = 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid) linked to a triazacyclononane (TACN) moiety by a 2,6-dimethylpyridine spacer designed to form stable Ln3+ complexes in solution that respond to the presence of Zn2+ ions. The Eu3+ and Gd3+ complexes have been characterized by using a combination of experimental and theoretical techniques that include absorption and emission electronic spectroscopy, NMR spectroscopy, 1H relaxometry, and DFT calculations. The Ln3+ ions are eight-coordinated by the ligand, which binds to the metal ion through the seven donor atoms of the DO3A unit and the nitrogen atom of the pyridyl linker. Luminescence lifetime measurements recorded from solutions of the Eu3+ complexes in H2O and D2O and relaxometric measurements point to the absence of inner-sphere water molecules. The addition of Zn2+ causes important changes in the absorption spectra of the complexes that evidence the formation of both 1:1 and 2:1 (Ln3+/Zn2+) complex species. However, the emission lifetimes of the Eu3+ complexes and relaxivity experience weak changes, thus indicating that Zn2+ addition does not significantly affect the number of coordinated water molecules. The Gd3+ complexes show a weak emission band at 325 nm, the intensity of which dramatically increases in the presence of Zn2+. However, the “turn-on” behaviour induced by Zn2+ is not observed for other metal cations such as Ca2+, Mg2+ or Cu2+. DFT calculations indicate that a photoinduced electron-transfer (PET) process is responsible for the quenching of the luminescence in the absence of Zn2+

Manganese Fluorene Phosphonates: Formation of Isolated Chains

International audience9,9-dimethylfluorenyl-2-phosphonic acid 1 was reacted with manganese nitrate tetrahydrate to produce under hydrothermal conditions the crystalline manganese phosphonate Mn(H2O)2[O2(OH)PC15H13]2·2H2O which crystallize in the P21/c space group. This compound is a rare example of Mn-phosphonate material featuring isolated chains. The interactions between these chains containing the 9,9-dimethylfluorenyl moieties, result from Van der Waals interactions involving the fluorene ligands and C···H–C hydrogen bonds as revealed by Hirshfeld Surfaces. This material features antiferromagnetic exchange interactions as revealed by the magnetic susceptibility as a function of the temperature