| Dedicated |
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V | |
| In Praise of Synthesis |
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VII | |
| Preface |
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XIX | |
| List of Contributors |
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XXI | |
| Biographical Sketches |
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XXV | |
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1 Inter-electron Repulsion and Irregularities in the Chemistry of Transition Series |
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1 | (14) |
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1.1 Introduction: Irregularities in Lanthanide Chemistry |
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1 | (3) |
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1.2 A General Principle of Lanthanide Chemistry |
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4 | (2) |
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1.3 Extensions of the First Part of the Principle |
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6 | (2) |
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1.4 Extensions of the Second Part of the Principle |
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8 | (1) |
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9 | (2) |
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11 | (2) |
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13 | (2) |
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2 Stereochemical Activity of Lone Pairs in Heavier Main-group Element Compounds |
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15 | (14) |
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15 | (1) |
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2.2 When Does a Lone Pair of Electrons Become Stereochemically Active? — Observations |
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16 | (1) |
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17 | (8) |
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2.3.1 Molecular/Complex Compounds |
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18 | (2) |
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20 | (5) |
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25 | (1) |
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26 | (1) |
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26 | (3) |
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3 How Close to Close Packing? |
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29 | (16) |
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29 | (1) |
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3.2 Essential Features of Close Packing |
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30 | (1) |
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3.3 Parameter Definitions |
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30 | (3) |
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3.4 Correlation Between D and N |
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33 | (2) |
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3.5 Transformation of Close-packing Arrangements |
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35 | (3) |
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3.6 Close-packing of Cations or of Anions? |
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38 | (3) |
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3.7 What Determines the Structure? |
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41 | (1) |
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Appendix. ICSD Codes, D and N Parameters of the Structures Used |
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42 | (2) |
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44 | (1) |
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4 Forty-five Years of Praseodymium Di-iodide, PrI2 |
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45 | (16) |
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Gerd Meyer and Andriy Palasyuk |
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45 | (1) |
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46 | (1) |
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4.2 Phases and Structures in the System Praseodymium-Iodine |
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47 | (4) |
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4.2.1 Synthesis Generalities |
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47 | (1) |
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4.2.2 Structural Principles |
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48 | (3) |
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4.3 PrI2: Phases and Phase Analysis |
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51 | (7) |
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58 | (1) |
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59 | (1) |
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59 | (2) |
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5 Centered Zirconium Clusters: Mixed-halide Systems |
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61 | (18) |
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61 | (1) |
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5.1 The Basics of Zirconium Cluster Chemistry |
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61 | (1) |
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62 | (1) |
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5.3 Mixed-Chloride-Iodide Zirconium Cluster Phases with a 6:12 Metal: Halide Ratio |
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63 | (1) |
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5.4 Mixed Chloride–Iodide Zirconium Cluster Phases with a 6:13 Metal: Halide Ratio |
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64 | (3) |
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5.5 Mixed Chloride–Iodide Zirconium Cluster Phases with a 6:14 Metal: Halide Ratio |
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67 | (4) |
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5.6 Mixed Chloride–Iodide Zirconium Cluster Phases with a 6:15 Metal: Halide Ratio |
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71 | (5) |
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5.7 Mixed Chloride–Iodide Zirconium Cluster Phases with a 6:18 Metal: Halide Ratio Products from Solid-state Reactions |
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76 | (1) |
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77 | (1) |
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77 | (1) |
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77 | (2) |
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6 Titanium Niobium Oxychlorides: Ligand Combination Strategy for the Preparation of Low-dimensional Metal Cluster Materials |
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79 | (26) |
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Ekaterina V. Anokhina and Abdessadek Lachgar |
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79 | (1) |
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79 | (4) |
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6.1.1 Cluster Connectivity and Framework Dimension |
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81 | (1) |
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6.1.2 The Ligand Combination Approach to Creating Anisotropic Frameworks |
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82 | (1) |
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6.2 Overview of the Chemistry of Niobium Chloride and Niobium Oxide Cluster Compounds |
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83 | (2) |
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6.2.1 Synthesis and Chemical Properties |
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83 | (1) |
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6.2.2 Electronic Structure, Redox and Magnetic Properties |
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84 | (1) |
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6.3 Niobium Oxychloride Cluster Compounds |
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85 | (8) |
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6.3.1 One-dimensional Cluster Frameworks |
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85 | (1) |
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6.3.1.1 Frameworks Built from Clusters with Five Oxygen Ligands |
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85 | (1) |
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6.3.1.2 Frameworks Built of Clusters with Six Oxygen Ligands |
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86 | (2) |
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6.3.2 Two-dimensional Cluster Frameworks |
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88 | (1) |
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6.3.2.1 2D Oxychloride Frameworks with a Honeycomb-like Structure |
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88 | (1) |
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6.3.2.2 Pillared 2D Oxychloride Frameworks |
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90 | (1) |
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6.3.2.3 2D Framework with Graphite-like Cluster Connectivity |
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90 | (3) |
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6.4 Summary of Crystallographic Data on Titanium Niobium Oxychlorides |
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93 | (6) |
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6.4.1 Effect of the Total Number of Ligands |
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93 | (2) |
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6.4.2 Cluster Configuration |
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95 | (1) |
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6.4.2.1 Relationships Between Ligand Arrangement and Direct Inter-cluster Linkages |
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95 | (1) |
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6.4.2.2 Relationships Between the Ligand Arrangement and Inter-cluster Linkages via Counter-ions |
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96 | (1) |
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97 | (1) |
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6.4.4 Structure-determining Factors in the Absence of "Hard" Cations |
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97 | (2) |
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6.5 Electronic Configuration of Niobium Oxychloride Clusters |
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99 | (1) |
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6.6 Conclusion and Outlook |
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100 | (1) |
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101 | (4) |
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7 Trinuclear Molybdenum and Tungsten Cluster Chalcogenides: From Solid State to Molecular Materials |
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105 | (16) |
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Rosa Llusar and Cristian Vicent |
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105 | (2) |
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7.2 Synthesis and Structure of Molecular M3Q4 and M3Q7 Cluster Complexes |
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107 | (8) |
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7.2.1 Solid-state Synthesis: Dimensional Reduction |
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108 | (1) |
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7.2.2 Solution Routes: Excision |
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109 | (3) |
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7.2.3 Ligand Exchange Reactions |
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112 | (1) |
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7.2.3.1 M3Q4 Cluster Complexes |
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112 | (1) |
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7.2.3.2 M3Q7 Cluster Complexes |
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113 | (2) |
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7.3 Trinuclear Clusters as Building Units |
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115 | (4) |
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7.3.1 Molecular Conductors Based on M3Q7 Cluster Complexes |
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115 | (2) |
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7.3.2 Formation of Supramolecular Adducts |
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117 | (2) |
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119 | (1) |
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119 | (2) |
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8 Current State on (B,C,N) Compounds of Calcium and Lanthanum |
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121 | (20) |
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121 | (1) |
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8.2 Problems and Pitfalls of some Calcium Compounds with (mixed) B,C,N Anions |
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121 | (8) |
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8.2.1 Borides of Calcium and Lanthanum |
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123 | (1) |
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8.2.2 The CaC2 Problem and Ca3C12C3 |
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124 | (2) |
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8.2.3 Calcium Nitride and Calcium Carbodiimides |
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126 | (1) |
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8.2.4 Calcium Nitridoborates |
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126 | (1) |
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8.2.5 A Comparison of Ca3(BN2)2 and Sr3(BN2)2 Structures |
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126 | (3) |
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129 | (2) |
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8.3.1 Electronic Considerations |
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129 | (2) |
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8.4 Lanthanum Nitridoborates |
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131 | (6) |
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Compounds in Ca-B-N and La-B-N systems |
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132 | (1) |
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133 | (1) |
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8.4.2 Structures of Lanthanum Nitridoborates |
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134 | (3) |
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137 | (1) |
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138 | (1) |
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138 | (3) |
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9 Compositional, Structural and Bonding Variations in Ternary Phases of Lithium with Main-group and Late-transition Elements |
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141 | (16) |
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Claude H. Belin, Monique Tillard |
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141 | (1) |
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9.2 Tuning Structures and Properties in Lithium Binary and Ternary Systems |
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142 | (1) |
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9.3 Clustering in Condensed Lithium Ternary Phases: A Way Towards Quasicrystals |
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143 | (1) |
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9.4 Exploration of New Lithium Ternary Systems Containing Ag, Zn, Al, Si, Ge |
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144 | (5) |
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144 | (1) |
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9.4.2 The System Li-Al-Ag |
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145 | (1) |
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9.4.3 Compositional and Structural Variations in the System Li-Al-Si |
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146 | (2) |
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9.4.4 The Tetragonal Compound Li9AlSi3, a Good Anodic Material |
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148 | (1) |
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9.5 The Intermetallic Li-Zn-Ge System, from Electron-poor to Electron-rich Phases |
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149 | (5) |
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9.5.1 The Electron-poor Hexagonal Phase LiZnGe |
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149 | (1) |
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9.5.2 The True Cubic Configuration of the Compound Li2ZnGe |
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150 | (2) |
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9.5.3 The Li-rich Compound Li8Zn2Ge3 with an Open-layered Anionic Framework |
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152 | (2) |
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154 | (1) |
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154 | (3) |
| 10 Polar Intermetallics and Zintl Phases along the Zintl Border |
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157 | (16) |
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10.1 "First comes the synthesis..." |
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157 | (1) |
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10.2 What are Intermetallics? |
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157 | (3) |
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10.3 The Zintl-Klemm Concept |
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160 | (1) |
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10.4 "Electron-poor" Polar Intermetallics |
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161 | (1) |
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10.5 Intermetallic ft-Systems |
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162 | (6) |
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168 | (1) |
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169 | (4) |
| 11 Rare-earth Zintl Phases: Novel Magnetic and Electronic Properties |
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173 | (10) |
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Susan M. Kauzlarich and Jiong Jiang |
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173 | (1) |
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174 | (3) |
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177 | (1) |
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178 | (1) |
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179 | (1) |
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180 | (1) |
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181 | (1) |
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181 | (2) |
| 12 Understanding Structure-forming Factors and Theory-guided Exploration of Structure–Property Relationships in Intermetallics |
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183 | (12) |
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Dong-Kyun Seo, Li-Ming Wu and Sang-Hwan Kim |
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183 | (1) |
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12.2 Mn14Al56+xGe3-x (x=0.00, 0.32, 0.61) |
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184 | (4) |
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12.3 La5-xCaxGe4 (x=3.37, 3.66, 3.82) and Ce5-xCaxGe4 (x=3.00, 3.20, 3.26) |
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188 | (3) |
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191 | (1) |
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191 | (1) |
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192 | (3) |
| 13 Ternary and Quaternary Niobium Arsenide Zintl Phases |
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195 | (14) |
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Franck Gascoin and Slavi C. Sevov |
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195 | (2) |
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13.2 New Main-group Arsenides |
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197 | (2) |
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13.3 Compounds Based on Isolated [NbAs4] Tetrahedral Centers |
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199 | (5) |
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13.4 Compounds Based on Edge-sharing Dimers of [NbAs4] Tetrahedra |
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204 | (2) |
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206 | (3) |
| 14 The Building-block Approach to Understanding Main-group-metal Complex Structures – More than just "Attempting to Hew Blocks with a Razor" |
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209 | (16) |
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209 | (1) |
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14.2 The Building-block Approach |
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210 | (11) |
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14.2.1 Quaternary Rare-earth Metal Chalcophosphates |
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210 | (3) |
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14.2.2 Quaternary Rare-earth Metal Chalcoarsenites and Antimonites |
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213 | (2) |
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14.2.3 Quaternary Rare-earth Metal Chalcotrielates and Tetrelates |
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215 | (6) |
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221 | (1) |
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222 | (3) |
| 15 Cation-deficient Quaternary Thiospinels |
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225 | (14) |
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Ashok K. Ganguli, Shalabh Gupta and Gunjan Garg |
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225 | (2) |
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15.2 Cu5.5Si 1.5Fe4Sn12S32 |
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227 | (6) |
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15.3 Cu5.47Fe2.9Sni3.1532 |
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233 | (2) |
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15.4 Cu7.38Mn4Sn12S32 (1) and Cu7.07Ni4Sn12S32 (2) |
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235 | (1) |
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236 | (1) |
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236 | (3) |
| 16 A New Class of Hybrid Materials via Salt-inclusion Synthesis |
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239 | (12) |
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239 | (2) |
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16.2 General Approach to Salt-inclusion Synthesis |
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241 | (1) |
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16.3 Examples and Discussion |
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242 | (6) |
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16.3.1 Zeolite-like Transition Metal Containing Porous Compounds |
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242 | (2) |
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16.3.2 Non-centrosymmetric Solids (NCSs) |
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244 | (3) |
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16.3.3 Solids Containing Periodic Arrays of Transition-metal Nanostructures |
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247 | (1) |
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248 | (1) |
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249 | (1) |
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249 | (2) |
| 17 Layered Perrhenate and Vanadate Hybrid Solids: On the Utility of Structural Relationships |
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251 | (16) |
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Paul A. Maggard and Bangbo Yan |
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251 | (1) |
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17.2 Heterometallic Perrhenates |
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252 | (7) |
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17.2.1 Background: Molecular and Condensed Metal-perrhenates |
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252 | (1) |
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17.2.2 Copper- and Silver-perrhenate Hybrids |
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253 | (3) |
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17.2.3 Metal-coordinated Pillars in Perrhenate Hybrids |
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256 | (3) |
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17.3 Heterometallic Vanadates |
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259 | (6) |
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17.3.1 Background: Layered Vanadate Species |
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259 | (2) |
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17.3.2 Layered Heterometallic Vanadates: Charge Density Matching |
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261 | (1) |
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17.3.3 Heterometallic Reduced Layered Vanadates |
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262 | (3) |
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17.4 Conclusions 265 Acknowledgments |
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265 | (1) |
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265 | (2) |
| 18 Hydrogen Bonding in Metal Halides: Lattice Effects and Electronic Distortions |
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267 | (12) |
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267 | (1) |
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18.2 A Hierarchy of Structure-directing Forces |
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268 | (1) |
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18.3 Hydrogen Bond Influence on Melts and Crystallization |
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269 | (3) |
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18.4 Electronic Implications of Hydrogen Bonding |
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272 | (3) |
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275 | (1) |
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276 | (1) |
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276 | (3) |
| 19 Syntheses and Catalytic Properties of Titanium Nitride Nanoparticles |
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279 | (16) |
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279 | (1) |
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19.2 Synthesis of TiN Nanoparticles |
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280 | (5) |
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19.3 Titanium Nitride Nanoparticles in Hydrogen Storage Applications |
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285 | (3) |
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19.4 Catalytic Properties of TiN Nanoparticles in Solution |
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288 | (1) |
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19.5 Catalytic Properties |
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289 | (3) |
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292 | (3) |
| 20 Solventless Thermolysis: A Possible Bridge Between Crystal Structure and Nanosynthesis? |
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295 | (10) |
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295 | (1) |
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295 | (1) |
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20.3 Solventless Thermolysis and Some Examples |
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296 | (3) |
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297 | (1) |
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20.3.2 NiS Nanorods and Nanotrigonal Prisms |
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297 | (1) |
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20.3.3 Bi2S3 Nanowires, Rods and Fabric |
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298 | (1) |
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20.3.4 Pb3O2Cl2 Nanobelts |
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298 | (1) |
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20.4 Control of the Nanoproduct Morphology Through the State of the Precursor |
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299 | (1) |
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20.5 Crystal Structure of the Precursor versus the Morphology and Distribution of the As-synthesized Nanoproduct: A Possible Bridge Between these Two? |
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300 | (2) |
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20.6 Conclusion and Prospects |
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302 | (1) |
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302 | (1) |
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303 | (2) |
| 21 New Potential Scintillation Materials in Borophosphate Systems |
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305 | (20) |
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Jing-Tai Zhao and Cheng-Jun Duan |
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305 | (1) |
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21.2 Recent Studies on the Scintillation Luminescence Properties of Borophosphates |
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306 | (16) |
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21.2.1 The Crystal Structures of Ba3BP3O12, BaBPO5 and Ba3BPO7 |
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306 | (2) |
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21.2.2 The Preparation and X-ray-excited Intrinsic Scintillation Luminescence Properties of Ba3BP3O12, BaBPO5 and Ba3BPO7 |
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308 | (8) |
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21.2.3 The X-ray-excited Luminescence Properties of Ce3+ -activated Ba3BP3O12, BaBPO5 and Ba3BPO7 |
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316 | (2) |
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21.2.4 Potential Scintillation Material of Ba3BP3O12: Eu²+ |
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318 | (4) |
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322 | (1) |
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323 | (2) |
| Subject Index |
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325 | |