CONTENTS 1. Introduction and Scope of Review 4124 2. Synthesis of LDH Nanosheets 4125 2.1. Delamination or Top Down Methods 4125 2.1.1. Delamination in Butanol 4125 2.1.2. Delamination in Acrylates 4126 2.1.3. Delamination in CCl 4 and Toluene 4126 2.1.4. Delamination in Formamide 4127 2.1.5. Delamination in N,N-Dimethylformamide−Ethanol Mixture 4130 2.1.6. Delamination in Water 4130 2.1.7. Partial Delamination in Dimethyl Sulfoxide and N-Methylpyrrolidone 4131 2.2. Controlled Nucleation or "Bottom Up" Methods 4132 3. Practical Applications of Delaminated LDHs 4132 3.1. Synthesis of Polymer/LDH Nanocomposites 4133 3.1.1. Intercalation of the Monomers and in Situ Polymerization 4133 3.1.2. Direct Intercalation of Extended Polymer Chains 4136 3.1.3. Pre-exfoliation Followed by Mixing with Polymer 4137 3.2. Synthesis of Core/Shell Multifunctional Materials 4140 3.3. Synthesis of Thin Films 4140 3.4. Synthesis of Catalysts 4145 3.5. Synthesis of Electrode Materials 4146 3.5.1. Application in Supercapacitors 4147 3.5.2. Application in Lithium Ion Batteries 4147 3.5.3.Application in Dye-Sensitized Solar Cells 4148 3.6. Synthesis of Hybrid Magnets 4148 3.7. Synthesis of Bioinorganic Hybrid Materials 4150 4. Conclusions 4151 Author Information 4152 Corresponding Author 4152 Notes 4152 Biographies 4152 Acknowledgments 4152 References 4152

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Faceted NiO nanoparticles preferentially exposing high surface energy planes demand attention due to their excellent electrocatalytic properties. However, the activity of faceted NiO nanoparticles generally remains suboptimal due to their large lateral size and thickness, which severely limits the availability of coordinatively unsaturated active reactive edge and corner sites. Here, ultrafine NiO nanosheets with a platelet size of ∼4.0 nm and thickness (∼1.1 nm) stabilized by TiO2 were successfully prepared by calcination of a monolayer layered double hydroxide precursor. The ultrafine NiO nanosheets displayed outstanding performance in electrochemical water oxidation due to a high proportion of reactive NiO {110} facets, intrinsic Ni(3+) and Ti(3+) sites, and abundant interfaces, which act synergistically to promote H2O adsorption and facilitate charge-transfer.

Contents 1. Introduction and Scope of Review 4839 2. Theoretical Aspects 4840 2.1. Mixed-Valence Systems 4840 2.2. Electron-Transfer Theory 4840 2.3. Electrochemistry 4842 2.4. EPR and 57 Fe-Mo ¨ssbauer Spectroscopy 4843 2.5. NMR Spectroscopy and X-ray Crystallography 4843 2.6. Theoretical Calculations 4844 2.7. IR Spectroscopy 4844 2.8. Classification and General Properties 4844 3. Systems with Unsaturated Carbon Chain Bridges 4844 3.1. All-Carbon sp-Bridged Systems 4845 3.2. Carbon-Based sp 2 -Bridged Systems 4848 3.3. Carbon-Based sp/sp 2 -Bridged Systems 4851 4. Systems with Aromatic Rings as Bridges 4856 4.1. Fulvalene and Fulvalene-like Bridged Systems 4856 4.

A new family of electron-deficient tris(aryl)boranes, B(C(6)F(5))(3-n)(C(6)Cl(5))(n) (n = 1-3), has been synthesized, permitting an investigation into the steric and electronic effects resulting from the gradual replacement of C(6)F(5) with C(6)Cl(5) ligands. B(C(6)F(5))(2)(C(6)Cl(5)) (3) is accessed via C(6)Cl(5)BBr(2), itself prepared from donor-free Zn(C(6)Cl(5))(2) and BBr(3). Reaction of C(6)Cl(5)Li with BCl(3) in a Et(2)O/hexane slurry selectively produced B(C(6)Cl(5))(2)Cl, which undergoes B-Cl exchange with CuC(6)F(5) to afford B(C(6)F(5))(C(6)Cl(5))(2) (5). While 3 forms a complex with H(2)O, which can be rapidly removed under vacuum or in the presence of molecular sieves, B(C(6)Cl(5))(3) (6) is completely stable to refluxing toluene/H(2)O for several days. Compounds 3, 5, and 6 have been structurally characterized using single crystal X-ray diffraction and represent the first structure determinations for compounds featuring B-C(6)Cl(5) bonds; each exhibits a trigonal planar geometry about B, despite having different ligand sets. The spectroscopic characterization using (11)B, (19)F, and (13)C NMR indicates that the boron center becomes more electron-deficient as n increases. Optimized structures of B(C(6)F(5))(3-n)(C(6)Cl(5))(n) (n = 0-3) using density functional theory (B3LYP/TZVP) are all fully consistent with the experimental structural data. Computed (11)B shielding constants also replicate the experimental trend almost quantitatively, and the computed natural charges on the boron center increase in the order n = 0 (0.81) < n = 1 (0.89) < n = 2 (1.02) < n = 3 (1.16), supporting the hypothesis that electrophilicity increases concomitantly with substitution of C(6)F(5) for C(6)Cl(5). The direct solution cyclic voltammetry of B(C(6)F(5))(3) has been obtained for the first time and electrochemical measurements upon the entire series B(C(6)F(5))(3-n)(C(6)Cl(5))(n) (n = 0-3) corroborate the spectroscopic data, revealing C(6)Cl(5) to be a more electron-withdrawing group than C(6)F(5), with a ca. +200 mV shift observed in the reduction potential per C(6)F(5) group replaced. Conversely, use of the Guttmann-Beckett and Childs' methods to determine Lewis acidity on B(C(6)F(5))(3), 3, and 5 showed this property to diminish with increasing C(6)Cl(5) content, which is attributed to the steric effects of the bulky C(6)Cl(5) substituents. This conflict is ascribed to the minimal structural reorganization in the radical anions upon reduction during cyclic voltammetric experiments. Reduction of 6 using Na((s)) in THF results in a vivid blue paramagnetic solution of Na(+) [6](•-); the EPR signal of Na(+)[6](•-) is centered at g = 2.002 with a((11)B) 10G. Measurements of the exponential decay of the EPR signal (298 K) reveal [6](•-) to be considerably more stable than its perfluoro analogue.

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Water-soluble, high-molecular-weight polycobaltocenium polyelectrolytes have been prepared by ring-opening polymerization (ROP) techniques. Anionic polymerization of a strained 19-electron dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium chloride resulted in the formation of oligomers with up to nine repeat units. Thermal ROP of dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium nitrate resulted in the formation of high-molecular-weight polycobaltocenium nitrate, a redox-active cobalt-containing polyelectrolyte.

A series of pharmaceutically active compounds including diclofenac, gemfibrozil, ibuprofen, naproxen, 2-propylpentanoic acid, 4-biphenylacetic acid and tolfenamic acid can be reversibly intercalated into a layered double hydroxide, initial studies suggest that these materials may have application as the basis of a novel tuneable drug delivery system.