CO-TUTELLE THESE DE DOCTORAT DE L'UNIVERSITE DE RENNES 1 OMUE NIVERSITE RETAGNE OIRE C U B L ECOLE DOCTORALE N° 596 Matière Molécules et Matériaux Spécialité : Chimie Inorganique NIKOLAEV INSTITUTE OF INORGANIC CHEMISTRY (NIIC) Novosibirsk, Russia Par Viktoria Muravieva Briques moléculaires à clusters hétérométalliques chalcogénées {Re 6-xMoxSe8} x = 1-3 : cristallochimie, structures electroniques et propriétés redox Thèse présentée et soutenue à Novosibirsk, le 27 novembre 2019 Unité de recherche : Institut des Sciences Chimiques de Rennes – UMR CNRS 6226 Nikolaev Institute of Inorganic Chemistry, Novosibirsk Rapporteurs avant soutenance : Composition du Jury : Emmanuel CADOT Emmanuel CADOT Professeur, Université de Versailles Professeur, Université de Versailles / rapporteur Sylvie FERLAY Vladimir FEDIN Professeur, Université de Strasbourg Professeur, NIIC de Novosibirsk / examinateur Stéphane CORDIER Directeur de recherches CNRS, Université de Rennes 1 / Directeur de thèse Nikolay NAUMOV Professeur, NIIC de Novosibirsk/ Co-directeur de thèse Maxim SOKOLOV Professeur, Novosibirsk State University / examinateur Galina ROMANENKO Researcher, International Tomography Center, Novosibirsk / examinatrice Membres invités: Pierric LEMOINE Chargé de Recherches CNRS, Université de Rennes 1 1 Carmelo PRESTIPINO Chargé de Recherche CNRS, Université de Rennes 1 1 Contents Résumé détaillé de la thèse ................................................................................................ 5 The list of Acronyms ........................................................................................................ 23 The list of compounds obtained ...................................................................................... 25 1. Literature Review ........................................................................................................ 27 1.1 Introduction.......................................................................................................................27 1.2 Cluster chemistry nomenclature......................................................................................30 1.3 The structure of heterometallic cluster compounds.......................................................31 1.3.1 Triangular cluster complexes ............................................................................. 31 1.3.2 Tetrahedral cluster complexes ........................................................................... 33 1.3.3 Octahedral cluster complexes ............................................................................ 40 1.4 Preparation of heterometallic cluster compounds...........................................................47 1.4.1 High-temperature synthesis ................................................................................ 47 1.4.2 Preparation in solution ....................................................................................... 49 1.5 Reactivity of heterometallic clusters................................................................................52 1.5.1 Reactions with the modification of the metal core atoms .................................. 52 1.5.2 Ligand exchange reactions ................................................................................. 53 1.5.3 Reactions with metal cations with the formation of coordination polymers ..... 55 1.6 Electronic structure of heterometallic cluster complexes [M4-xM'xQ8Ln] and [M6-xM'xQ8L6]..........................................................................................................................57 1.6.1 Triangular clusters [M3Q4Ln] ............................................................................. 57 1.6.2 Tetrahedral cluster complexes [M4Q4Ln] ........................................................... 58 i a i a 1.6.3 Octahedral cluster complexes [M6L 8L 6] and [M6L 12L 6] .................................... 61 1.7 Redox properties of the heterometallic cluster complexes.............................................62 1.7.1 Triangular cluster complexes [M3Q4Ln] ............................................................ 62 1.7.2 Tetrahedral cluster complexes [M4Q4Ln] ........................................................... 63 1.7.3 Octahedral cluster complexes [M6Q8L6] ............................................................ 64 2. Experimental part ........................................................................................................ 66 2 2.1 Materials and methods......................................................................................................66 2.2 Preparation protocols........................................................................................................69 a- 2.2.1 The solution-melt preparation of polymeric phase K6[Re3Mo3Se8(CN) a a 2/2(CN) 4] and its depolymerization to the soluble salts: Catn[Re3Mo3Se8(CN)6], + Cat = K, Cs, Ph4P ....................................................................................................... 69 a-a a 2.2.2 The solution-melt preparation of K6[Re3.6Mo2.4Se8(CN) 2/2(CN) 4] and K5[Re5MoSe8(CN)6]∙11H2O ........................................................................................ 72 2.2.3 Methatesis reaction for preparation of (n-Bu4N)4[Re5MoSe8(CN)6] ................. 72 a-a a 2.2.4 Depolymerization of the polymer K6[Re3.6Mo2.4Se8(CN) 2/2(CN) 4] with the + formation of soluble salts Catn[Re3.6Mo2.4Se8(CN)6], Cat = K, Ph4P ........................ 73 n- n- 2.2.5 Separation of cluster anions [Re4Mo2Se8(CN)6] and [Re3Mo3Se8(CN)6] and + their isolation as salts Catn[Re6-xMoxSe8(CN)6], Cat = K, n-Bu4N ............................ 74 5- 2.2.6 Preparation of coordination polymers from [Re3Mo3Se8(CN)6] cyanocluster and transition metal ammine complexes ..................................................................... 76 5- 4- 2.2.7 The ligand exchange reactions of [Re3Mo3Se8(CN)6] and [Re4Mo2Se8(CN)6] : formation of [Re6-xMoxSe8L6], L = tbp, Ph3P ................................................................ 78 3. Results and Discussion ................................................................................................. 80 n- 3.1 Preparation of heterometallic cluster complexes [Re3Mo3Se8(CN)6] , n- n- [Re4Mo2Se8(CN)6] and [Re5MoSe8(CN)6] (n = 4, 5) as species with well-defined composition.............................................................................................................................80 a-a a 3.1.1 Synthetic route from solid state polymer K6[Re3Mo3Se8(CN) 2/2(CN) 4] to soluble species and their mass-spectrometry investigation ........................................ 80 n- n- 3.1.2 The separation of the cluster anions [Re4Mo2Se8(CN)6] and [Re3Mo3Se8(CN)6] + from the mixture and their isolation as salts Catn[Re6-xMoxSe8(CN)6], Cat = K, n-Bu4N ..................................................................................................................................... 86 3.2 Structural features and isomerism of the {Re6-xMox} (x = 1-3) metal cores in the solid state using SC XRD data........................................................................................................89 5- 3.3 Investigation of the isomeric composition of the clusters [Re3Mo3Se8(CN)6] and 4- [Re4Mo2Se8(CN)6] in solution.............................................................................................91 3.4 Quantum chemical calculations for heterometallic cluster anions n- [Re6xMoxSe8(CN)6] ..............................................................................................................92 3 3.5 X-ray absorption spectroscopy analysis of the local geometry of the metal core in 5- 4- [Re3Mo3Se8(CN)6] ∙and [Re4Mo2Se8(CN)6] clusters.........................................................97 4- 3.6 The electrochemical study of the cyanoclusters [Re6-xMoxSe8(CN)6] (x = 1, 2 and 3) in solution..............................................................................................................................100 n- 3.7 UV-Vis spectroscopic investigation of heterometallic anions [Re6-xMoxSe8(CN)6] (x = 1, 2, and 3) in solution...................................................................................................102 5- 3.8 The study of interaction of the heterometallic cyanocluster [Re3Mo3Se8(CN)6] with transition metals ammine complexes and the formation of coordination polymers..........105 5- 3.9 The apical ligand exchange reactions of the clusters [Re3Mo3Se8(CN)6] and 4- [Re4Mo2Se8(CN)6] : formation of the complexes [Re6-xMoxSe8L6] L = tbp, PPh3..........113 3.10 Principal outcome.........................................................................................................115 3.11 Conclusion....................................................................................................................116 4. Detailed description of the crystal structure of heterometallic Re/Mo cluster compounds ...................................................................................................................... 118 a-a a 4.1 Crystal structures of the polymeric phases: K6[Re3Mo3Se8(CN) 2/2(CN) 4] and a-a a K6[Re3.6Mo2.4Se8(CN) 2/2(CN) 4].......................................................................................118 4.2 Crystal structures of molecular complexes Cat5[Re3Mo3Se8(CN)6] (Cat = K, Cs) and (Ph4P)4[Re3Mo3Se8(CN)6]∙2CH3CN....................................................................................120 4.3 Crystal structures of tetrabutylammonium salts of