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Open-Shell Coordination Compounds Based on Cyanide and Scorpionate Ligands Delphine Garnier

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Open-Shell Coordination Compounds Based on Cyanide and Scorpionate Ligands Delphine Garnier Open-shell Coordination Compounds based on Cyanide and Scorpionate Ligands Delphine Garnier To cite this version: Delphine Garnier. Open-shell Coordination Compounds based on Cyanide and Scorpionate Ligands. Material chemistry. Université Pierre et Marie Curie - Paris VI; Karlsruher Institut für Technologie, 2015. English. NNT : 2015PA066296. tel-01560790 HAL Id: tel-01560790 https://tel.archives-ouvertes.fr/tel-01560790 Submitted on 12 Jul 2017 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Université Pierre et Marie Curie Karlsruhe Institute of Technology ED 406 Institut Parisien de Chimie Moleculaire (IPCM) – UMR 8232 Equipe ERMMES Open-shell Coordination Compounds based on Cyanide and Scorpionate Ligands Par Delphine Garnier Thèse de doctorat de Chimie Moléculaire Dirigée par Prof. Dr. Frank Breher et Prof. Dr. Rodrigue Lescouëzec Présentée et soutenue publiquement le 10/07/15 Devant un jury composé de : Prof. Dr. Frank Breher Prof. Dr. Rodrigue Lescouëzec Dr. Cyril Ollivier Prof. Dr. Rolf Schuster Prof. Dr. Jan Paradies This work was produced between October 2011 and June 2015 at the Institute of Inorganic Chemistry of Karlsruhe Institute of Technology (KIT, Karlsruhe, Germany) under the supervision of Prof. Dr. Frank Breher and at the Institut Parisien de Chimie Moléculaire (IPCM) – UMR 8232 – ERMMES work group (University Pierre and Marie Curie, Paris, France) under the supervision of Prof. Dr. Rodrigue Lescouëzec. 4 « Pourquoi faire simple quand on peut faire compliqué ? » Proverbe Shadok À Mamie, à Mimie et à Jo À mes parents À Joël 5 6 Table of content 1 INTRODUCTION ....................................................................................................................... 9 2 OVERALL AIMS ........................................................................................................................ 23 3 MONONUCLEAR IRON(II) AND IRON(III) BUILDING BLOCKS ........................................................ 25 3.1 TRICYANIDO IRON (II) AND IRON (III) COMPLEXES OF SCORPIONATE LIGAND L ..................................................... 26 3.1.1 Syntheses of tricyanido iron complexes ..................................................................................... 26 3.1.2 Structural analyses ...................................................................................................................... 33 3.1.3 Fourier Transform InfraRed spectroscopy ................................................................................. 44 3.1.4 Cyclic voltammetry ...................................................................................................................... 50 3.1.5 EPR spectroscopy and magnetic measurements....................................................................... 53 3.1.6 MAS-NMR spectroscopy.............................................................................................................. 58 III - - 4 MOLECULAR SQUARES BASED ON THE [FE (TP*)(CN)3] ([7] ) BUILDING BLOCK ......................... 101 4.1.1 Syntheses ................................................................................................................................... 102 4.1.2 Structural analyses .................................................................................................................... 104 4.1.3 Fourier Transform InfraRed spectroscopy ............................................................................... 107 4.1.4 SQUID magnetometry ............................................................................................................... 109 5 POLYMETALLIC CYANIDE-BRIDGED TRANSITION METAL COMPLEXES USING THE [FE(TPM*)(CN)3] (8) BUILDING BLOCK ...................................................................................................................... 119 5.1 CYANIDE-BRIDGED COORDINATION POLYMERS .............................................................................................. 119 5.1.1 Syntheses ................................................................................................................................... 120 5.1.2 Structural analyses .................................................................................................................... 122 5.1.3 Fourier Transform InfraRed spectroscopy ............................................................................... 126 5.1.4 SQUID magnetometry ............................................................................................................... 128 5.2 CYANIDE-BRIDGED TETRANUCLEAR MOLECULAR COMPLEXES ........................................................................... 131 5.2.1 Syntheses ................................................................................................................................... 131 5.2.2 Structural analyses .................................................................................................................... 133 5.2.3 Fourier Transform InfraRed spectroscopy ............................................................................... 139 5.2.4 SQUID magnetometry ............................................................................................................... 141 - - 6 CYANIDE-BRIDGED MOLECULAR MULTIMETALLIC COMPLEXES USING THE [FE(TP)(CN)3] ([1] ) BUILDING BLOCK ........................................................................................................................... 143 6.1 MOLECULAR SQUARES............................................................................................................................... 145 6.1.1 Syntheses ................................................................................................................................... 145 6.1.2 Structural analyses .................................................................................................................... 147 7 6.1.3 Fourier Transform InfraRed spectroscopy ................................................................................154 6.1.4 SQUID magnetometry ...............................................................................................................158 6.2 CYANIDE-BASED HEXANUCLEAR COMPLEXES ..................................................................................................160 6.2.1 Syntheses ....................................................................................................................................160 6.2.2 Structural analyses.....................................................................................................................160 6.2.3 Fourier Transform InfraRed spectroscopy ................................................................................165 6.2.4 Magnetic properties ..................................................................................................................168 6.3 CYANIDE-BASED MOLECULAR OCTANUCLEAR COMPLEXES................................................................................170 6.3.1 Syntheses ....................................................................................................................................171 6.3.2 Structural analyses.....................................................................................................................174 6.3.3 EDX spectroscopy .......................................................................................................................181 6.3.4 NMR spectroscopy .....................................................................................................................181 6.3.5 Fourier Transform InfraRed spectroscopy ................................................................................187 6.3.6 Electrochemistry ........................................................................................................................190 6.3.7 UV-visible Spectroscopy.............................................................................................................194 6.3.8 SQUID magnetometry ...............................................................................................................195 7 CONCLUSIONS AND OUTLOOK............................................................................................... 203 8 ZUSAMMENFASSUNG UND AUSBLICK .................................................................................... 209 9 CONCLUSION ET PERSPECTIVES ............................................................................................. 215 10 EXPERIMENTAL SECTION ....................................................................................................... 231 10.1 REAGENTS AND SOLVENTS .....................................................................................................................231 10.2 ANALYTIC AND SPECTROSCOPIC METHODS ...............................................................................................232 10.3 SYNTHESES OF BUILDING BLOCKS ............................................................................................................238
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