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N° d'ordre: THÈSE présentée à L'UNIVERSITÉ DE BORDEAUX 1 ÉCOLE DOCTORALE DES SC

N° d'ordre: THÈSE présentée à L'UNIVERSITÉ DE BORDEAUX 1 ÉCOLE DOCTORALE DES SCIENCES CHIMIQUES par JÜRGEN FEUERSENGER POUR OBTENIR LE GRADE DE DOCTEUR SPÉCIALITÉ : Physico-Chimie de la Matière Condensée SYNTHESIS AND CHARACTERISATION OF 3d-4f-COMPLEXES AND THEIR MAGNETIC PROPERTIES Soutenue le 20 décembre 2010 Après avis de : M. YVES JOURNAUX Directeur de Recherche au CNRS Rapporteur M. JEAN-PASCAL SUTTER Directeur de Recherche au CNRS Rapporteur Devant la commission d'examen formée de : Mme. CORINE MATHONIÈRE Professeur, Université Bordeaux 1 Présidente M. YVES JOURNAUX Directeur de Recherche au CNRS Rapporteurs M. JEAN-PASCAL SUTTER Directeur de Recherche au CNRS MME. ANNIE K. POWELL Professeur, Karlsruhe Institute of Technology (KIT) Examinateurs M. RODOLPHE CLÉRAC Chargé de Recherche au CNRS M. PHILIPPE RICHETTI Directeur de Recherche au CNRS Directeur de thèse : M. RODOLPHE CLÉRAC ET M. PHILIPPE RICHETTI tel-00755137, version 1 - 20 Nov 2012 tel-00755137, version 1 - 20 Nov 2012 Résumé: Ce travail de thèse décrit (i) la synthèse de complexes hétérométalliques d’ions 3d et 4f à partir de précuseurs de Mn, Fe et Co, de sels de lanthanides et de ligands organiques et (ii) l'étude de leurs structures et propriétés. 41 complexes polynucléaires ont été synthétisés dans le cadre de ce travail. Les structures moléculaires de tous les composés ont été déterminées par diffraction des rayons X. Les propriétés magnétiques de 22 complexes ont été étudiées, dont quatre montrent une relaxation lente de leur aimantation considérée comme la signature d’un comportement de molécule-aimant. L'activité catalytique du complexe {Mn4Dy6Li2} calciné a aussi été étudiée et s'est avérée efficace pour l'oxydation du monoxyde de carbone. L'étude systématique de complexes isostructuraux de lanthanides a montré que l'incorporation d’ions 4f peut introduire de l’anisotropie magnétique et que l’ion DyIII est généralement le meilleur candidat pour le ciblage de molécules-aimants hétérométalliques 3d- 4f. Mots clés : - Aimants moléculaires - Single-Molecule Magnet - Effet tunnel quantique - Relaxation lente de l’aimantation Abstract: This dissertation describes the syntheses of 3d-4f-metal complexes starting from preformed compounds of Mn, Fe and Co, lanthanide salts and organic ligands and also the investigation of their structures and properties. 41 new polynuclear heterometallic metal complexes were synthesised in the course of this work with different interesting properties. The structures of all obtained compounds have been confirmed using X-ray diffraction. The magnetic properties of 22 complexes were studied, of which four show frequency dependent out-of-phase signals as expected for SMMs. The catalytic activity of calcinated {Mn4Dy6Li2} was investigated and proved effective for the oxidation of CO. It was established, that the use of precursors leads to new families of compounds. Moreover the study of isostructural compounds across the lanthanide series showed 1) that the incorporation of 4f ions introduces magnetic anisotropy and 2) DyIII is usually the best candidate for targeting 3d-4f- SMMs. Keywords: - Single-Molecule Magnet - Quantum tunnelling of magnetisation (QTM) - 3d-4f complexes - Slow relaxation of magnetisation tel-00755137, version 1 - 20 Nov 2012 tel-00755137, version 1 - 20 Nov 2012 TABLE OF CONTENTS Table of contents 1 Introduction ______________________________________________________________ 1 1.1 General introduction _____________________________________________________ 1 1.2 Magnetic susceptibility __________________________________________________ 2 1.3 Basic principles of magnetism___________________________________________ 2 1.3.1 Diamagnetism ___________________________________________________________________ 3 1.3.2 Paramagnetism __________________________________________________________________ 3 1.3.3 Curie paramagnetism ___________________________________________________________ 4 1.3.4 Curie-Weiss paramagnetism ____________________________________________________ 6 1.3.5 Ferromagnetism _________________________________________________________________ 8 1.3.6 Antiferromagnetism _____________________________________________________________ 9 1.3.7 9 1.3.8 Ferrimagnetism _________________________________________________________________ 10 1.3.9 Interaction types________________________________________________________________ 10 1.3.9.1 Direct interaction exchange ______________________________________________ 11 1.3.9.2 Superexchange ____________________________________________________________ 12 1.3.9.3 RKKY-exchange ___________________________________________________________ 12 1.3.9.4 Double-exchange _________________________________________________________ 13 1.4 Single molecule magnets (SMMs) _____________________________________ 14 1.4.1 The role of the spin ground state for SMM’s _________________________________ 19 1.4.2 Synthetic approaches for isolating polynuclear complexes___________________ 20 1.5 Introduction to manganese chemistry _________________________________ 22 1.6 Introduction to iron chemistry __________________________________________ 23 1.7 Introduction to cobalt chemistry _______________________________________ 23 1.8 Introduction to rare-earth metal chemistry ____________________________ 24 1.9 Introduction to 3d-4f complexes _______________________________________ 25 1.10 Ligand selection _________________________________________________________ 27 1.11 Co-ligand selection ______________________________________________________ 29 1.12 Precursors as starting materials ________________________________________ 30 1.12.1 [MnII 4MnIII 2O2(O2CCMe3)10(py)2.5]·(HO2CCMe3)1.5] (1) __________________________ 30 1.12.2 [MnIII 8MnIV 4O12(CH3COO)12(CHCl2COO)4]·4H2O (3) _____________________________ 31 1.12.3 [CoII 2(µ-OH2)(O2CCMe3)4(HO2CCMe3)4] (4) _____________________________________ 33 1.12.4 [CoIII 3(µ3-O)(O2CCMe3)6(py)3]∙O2CCMe3∙H2O∙3.5HO2CCMe3 (5) ________________ 33 1.12.5 [FeIII 3O(O2CCMe3)6(H2O)3]·O2CCMe3·2HO2CCMe3 (6) __________________________ 34 1.12.6 [(FeIII 3O)2(O)2(O2CCMe3)12(HO2CCMe3)2] (7) ____________________________________ 35 1.12.7 [Dy2(O2CCMe3)6(HO2CCMe3)6]·HO2CCMe3 (8) _________________________________ 35 1.13 Crystallisation methods _________________________________________________ 36 1.13.1 Evaporation _____________________________________________________________________ 39 1.13.2 Vapour and Liquid Diffusion ___________________________________________________ 39 tel-00755137, version 1 - 20 Nov 2012 TABLE OF CONTENTS 1.13.3 Thermal Gradient _______________________________________________________________ 40 2 Structure and magnetic properties of manganese-lanthanide aggregates ______________________________________________________________ 41 2.1 Structure of tetranuclear complexes ___________________________________ 41 2.1.1 Structure of [MnIII 2LaIII 2(hmp)6(piv)2(NO3)4] (9) _________________________________ 41 2.2 Structure and magnetic properties of hexanuclear complexes _______ 43 2.2.1 Structure of MnIII 4LaIII 2(µ4-O)(µ3-O)(hmp)7(O2CMe)(O2CCHCl2)(NO3)5(OH2)0.5] ·3acetone (10) __________________________________________________________________ 43 2.2.2 Magnetic properties of [MnIII 4LaIII 2(µ4-O)(µ3-O)(hmp)7(OAc)2 (NO3)5]___________ 47 2.2.3 Structure of [MnIII 2DyIII 4(µ4-O)2(hmp)4(pic)2(piv)6(µ-N3)2]·4CH3CN (14) _________ 51 2.2.4 Magnetic properties of [MnIII 2LnIII 4(µ4-O)2(hmp)4(pic)2(piv)6(µ-N3)2]·4CH3CN __ 56 2.3 Structure and magnetic properties of heptanuclear complexes ______ 60 2.3.1 Structure of [MnIIMnIII 2MnIVHoIII 3(µ4-O)(µ3-OH)2(n-bdea)3 (piv)9(N3)(NO3)]·MeCN (19) ______________________________________________________________________________ 60 2.3.2 Magnetic properties of [MnIIMnIII 2MnIVLnIII 3(µ4-O)(µ3-OH)2(n-bdea)3(piv)9(N3) (NO3)]·MeCN ____________________________________________________________________ 65 2.4 Structure and magnetic properties of dodecanuclear complexes _____ 68 2.4.1 Structure of [Mn3.5 4GdIII 6Li2(µ3-O)2(µ5-CO3)2(n-bdea)6(piv)12 (NO3)2]∙3CH3CN (25) __________________________________________________________________________________ 68 2.4.2 Magnetic properties of [Mn3.5 4LnIII 6Li2(µ3-O)2(µ5-CO3)2(n-bdea)6(piv)12(NO3)2] ∙3CH3CN ________________________________________________________________________ 77 2.4.3 Catalytic Oxidation properties of calcinated [MnIV 2MnIII 2DyIII 6Li2(µ3-O)2(µ5- CO3)2(n-bdea)6(piv)12(NO3)2] ∙3CH3CN __________________________________________ 84 3 Structure and magnetic properties of iron-lanthanide aggregates ___ 86 3.1 Structure and magnetic properties of hexanuclear complexes _______ 86 3.1.1 Structure of [FeIII 4PrIII 2(µ4-O)2(n-bdea)4(piv)4(NO3)2(H2O)2]·MeCN (30) _________ 86 3.1.2 Magnetic properties of [FeIII 4LnIII 2(µ4-O)2(n-bdea)4(piv)4(NO3)2 (H2O)2] _________ 93 3.1.3 Mößbauer measurement on [FeIII 4PrIII 2(µ4-O)2(n-bdea)4(piv)4(NO3)2(H2O)2] ____ 97 3.2 Structure and magnetic properties of hexanuclear Fe(III) complexes_ 98 3.2.1 Structure of [FeIII 6(µ3-O)2(hmp)6(piv)6]2+[Gd(NO3)5]2- (37) ______________________ 98 3.2.2 Magnetic properties of [FeIII 6(µ3-O)2(hmp)6(piv)6]2+[Ln(NO3)5]2- ______________ 101 4 Structure and magnetic properties of cobalt-lanthanide aggregates 105 4.1 Structure and magnetic properties of hexanuclear complexes ______ 105 4.1.1 Structure of [CoIII 2DyIII 4(µ3-OH)2(hmp)4(piv)8(N3)2(NO3)2]·2CH3CN (46) ______ 105 4.1.2 Magnetic properties of [CoIII 2LnIII 4(µ3-OH)2(hmp)4(piv)8 (N3)2(NO3)2]·2CH3CN 113 5 Summary _______________________________________________________________ 121 6 Conclusion______________________________________________________________ 123 7 Experimental section ___________________________________________________ 124 7.1 Elemental analysis _____________________________________________________ 124 tel-00755137, version 1 - 20 Nov 2012 TABLE OF CONTENTS 7.2 Fourier-Transform-Infrared-Spectroscopy (FT-IR) ____________________ 124 7.3 X-ray diffraction on single crystals ____________________________________ 124 7.4 X-ray Powder diffraction _______________________________________________ 126 7.5 Magnetic measurements ______________________________________________ 126 7.6 Mößbauer spectroscopy _______________________________________________ 127 7.7 Some magnetic parameters for lanthanides ions _____________________ 127 7.8 Synthetic approach ____________________________________________________ 128 7.9 Synthesis of precursor compounds ___________________________________ 128 7.9.1 Manganese Precursor Compounds __________________________________________ 128 7.9.1.1 [MnIII 2MnII 4O2(O2CCMe3)10(py)2.5]·(HO2CCMe3)1.5 (1) ___________________ 128 7.9.1.2 MnII(CHCl2COO)3·4H2O (2) ______________________________________________ 129 7.9.1.3 [MnIII 8MnIV 4O12(CH3COO)12(CHCl2COO)4]·4H2O (3) _____________________ 129 7.9.2 Cobalt Precursor Compounds ________________________________________________ 129 7.9.2.1 [CoII 2(µ-OH2)(O2CCMe3)4(HO2CCMe3)4] (4) ______________________________ 129 7.9.2.2 [CoIII 3(µ3-O)(O2CCMe3)6(py)3]∙O2CCMe3∙H2O∙3.5HO2CCMe3 (5) ________ 130 7.9.3 Iron Precursor Compounds __________________________________________________ 130 7.9.3.1 [FeIII 3O(O2CCMe3)6(H2O)3]+[O2CCMe3]·2HO2CCMe3 (6) _________________ 130 7.9.3.2 [Fe6(O2)(O2)(O2CCMe3)12(HO2CCMe3)2] (7) ______________________________ 130 7.9.4 Lanthanide Precursor Compounds __________________________________________ 131 7.9.4.1 [Dy2(O2CCMe3)6(HO2CCMe3)6]·HO2CCMe3 (8) __________________________ 131 7.10 Synthetic procedure for the described compounds __________________ 131 7.10.1 [MnII 2LaIII 2(hmp)6(piv)2(NO3)4]·2acetone (9) __________________________________ 131 7.10.2 MnIII 4LaIII 2(µ4-O)(µ3-O)(hmp)7(OAc)(DCAc)(NO3)5(OH2)0.5] ·3acetone (10) ____ 132 7.10.3 [MnIII 2EuIII 4(µ4-O)2(hmp)4(pic)2(piv)6(µ-N3)2]·2CH3CN (11)_____________________ 132 7.10.4 [MnIII 2GdIII 4(µ4-O)2(hmp)4(pic)2(piv)6(µ-N3)2]·2CH3CN (12) ____________________ 133 7.10.5 [MnIII 2TbIII 4(µ4-O)2(hmp)4(pic)2(piv)6(µ-N3)2]·4CH3CN (13) ____________________ 133 7.10.6 [MnIII 2DyIII 4(µ4-O)2(hmp)4(pic)2(piv)6(µ-N3)2]·4CH3CN (14) ____________________ 134 7.10.7 [MnIII 2HoIII 4(µ4-O)2(hmp)4(pic)2(piv)6(µ-N3)2]·4CH3CN (15) ____________________ 135 7.10.8 [MnIII 2ErIII 4(µ4-O)2(hmp)4(pic)2(piv)6(µ-N3)2]·4CH3CN (16) _____________________ 135 7.10.9 [MnIIMnIII 2MnIVGdIII 3(µ4-O)(µ3-OH)2(n-bdea)3(piv)9(N3)(NO3)] ·MeCN (17) ____ 136 7.10.10 [MnIIMnIII 2MnIVDyIII 3(µ4-O)(µ3-OH)2(n-bdea)3(piv)9(N3)(NO3)] ·MeCN (18) ____ 136 7.10.11 [MnIIMnIII 2MnIVHoIII 3(µ4-O)(µ3-OH)2(n-bdea)3(piv)9(N3)(NO3)] ·MeCN (19) ____ 137 7.10.12 MnIIMnIII 2MnIVErIII 3(µ4-O)(µ3-OH)2(n-bdea)3(piv)9(N3)(NO3)]·MeCN (20) ______ 137 7.10.13 [Mn3.5 4PrIII 6Li2(µ3-O)2(µ5-CO3)2(n-bdea)6(piv)12(NO3)2]∙4CH3CN (21) __________ 137 7.10.14 [Mn3.5 4NdIII 6Li2(µ3-O)2(µ5-CO3)2(n-bdea)6(piv)12(NO3)2]∙3CH3CN (22) _________ 138 7.10.15 Mn3.5 4SmIII 6Li2(µ3-O)2(µ5-CO3)2(n-bdea)6(piv)12(NO3)2]∙3CH3CN (23)__________ 138 7.10.16 [Mn3.5 4EuIII 6Li2(µ3-O)2(µ5-CO3)2(n-bdea)6(piv)12(NO3)2]∙3CH3CN (24) __________ 139 7.10.17 [Mn3.5 4GdIII 6Li2(µ3-O)2(µ5-CO3)2(n-bdea)6(piv)12(NO3)2]∙3CH3CN (25) _________ 139 7.10.18 [Mn3.5 4TbIII 6Li2(µ3-O)2(µ5-CO3)2(n-bdea)6(piv)12(NO3)2]∙3CH3CN (26) __________ 140 7.10.19 [Mn3.5 4DyIII 6Li2(µ3-O)2(µ5-CO3)2(n-bdea)6(piv)12(NO3)2]∙3CH3CN (27) _________ 140 tel-00755137, version 1 - 20 Nov 2012 TABLE OF CONTENTS 7.10.20 [Mn3.5 4HoIII 6Li2(µ3-O)2(µ5-CO3)2(n-bdea)6(piv)12(NO3)2]∙8CH3CN (28) _________ 140 7.10.21 [Mn3.5 4YIII 6Li2(µ3-O)2(µ5-CO3)2(n-bdea)6(piv)12(NO3)2]∙8CH3CN (29) ___________ 141 7.10.22 [FeIII 4PrIII 2(µ4-O)2(n-bdea)4(piv)4(NO3)2(H2O)2]·MeCN (30) _____________________ 141 7.10.23 [FeIII 4NdIII 2(µ4-O)2(n-bdea)4(piv)4(NO3)2(H2O)2]·acetone (31) __________________ 142 7.10.24 [FeIII 4SmIII 2(µ4-O)2(n-bdea)4(piv)4(NO3)2(H2O)2]·acetone (32)__________________ 142 7.10.25 [FeIII 4EuIII 2(µ4-O)2(n-bdea)4(piv)4(NO3)2(H2O)2]· acetone (33) __________________ 143 7.10.26 [FeIII 4GdIII 2(µ4-O)2(n-bdea)4(piv)4(NO3)2(H2O)2]· acetone (34) _________________ 143 7.10.27 [FeIII 4YIII 2(µ4-O)2(n-bdea)4(piv)4(NO3)2(H2O)2]· acetone (35) ___________________ 144 7.10.28 [FeIII 6(µ3-O)2(hmp)6(piv)6]2+[EuIII(NO3)5 2-]·2acetone (36)_______________________ 144 7.10.29 [FeIII 6(µ3-O)2(hmp)6(piv)6]2+[GdIII(NO3)5 2-]·2acetone (37) ______________________ 144 7.10.30 [FeIII 6(µ3-O)2(hmp)6(piv)6]2+[DyIII(NO3)5 2-]·2acetone (38) ______________________ 145 7.10.31 [FeIII 6(µ3-O)2(hmp)6(piv)6]2+[HoIII(NO3)5]2-·2acetone (39) ______________________ 145 7.10.32 [FeIII 6(µ3-O)2(hmp)6(piv)6]2+[ErIII(NO3)5 2-]·2acetone (40) _______________________ 146 7.10.33 [CoIII 2PrIII 4(µ3-OH)2(hmp)4(piv)8(µ-N3)2(NO3)2]∙2CH3CN (41) ___________________ 146 7.10.34 [CoIII 2SmIII 4(µ3-OH)2(hmp)4(piv)8(µ-N3)2(NO3)2]∙2CH3CN (42)__________________ 147 7.10.35 [CoIII 2EuIII 4(µ3-OH)2(hmp)4(piv)8(µ-N3)2(NO3)2]∙2CH3CN (43) __________________ 147 7.10.36 [CoIII 2GdIII 4(µ3-OH)2(hmp)4(piv)8(µ-N3)2(NO3)2]∙2CH3CN (44) __________________ 147 7.10.37 [CoIII 2TbIII 4(µ3-OH)2(hmp)4(piv)8(µ-N3)2(NO3)2]∙2CH3CN (45) __________________ 148 7.10.38 [CoIII 2DyIII 4(µ3-OH)2(hmp)4(piv)8(µ-N3)2(NO3)2]∙2CH3CN (46) __________________ 148 7.10.39 [CoIII 2HoIII 4(µ3-OH)2(hmp)4(piv)8(µ-N3)2(NO3)2]∙2CH3CN (47) __________________ 149 7.10.40 [CoIII 2ErIII 4(µ3-OH)2(hmp)4(piv)8(µ-N3)2(NO3)2]∙2CH3CN (48) ___________________ 149 8 Crystal structure data __________________________________________________ 151 9 Bibliography ____________________________________________________________ 167 10 Affix _____________________________________________________________________ 182 10.1 List of Abbreviations ___________________________________________________ 182 10.2 List of figures ___________________________________________________________ 183 10.3 List of tables ____________________________________________________________ 187 11 Acknowledgments _____________________________________________________ 189 12 Conference contributions ______________________________________________ 191 tel-00755137, version 1 - 20 Nov 2012 1 INTRODUCTION 1 1 Introduction 1.1 General introduction Historically, magnetism is an effect recognised for thousands of years. uploads/Litterature/ feuersenger-juergen-2010 1 .pdf