Vadim G. Kessler

Bio: Vadim G. Kessler is an academic researcher from Swedish University of Agricultural Sciences. The author has contributed to research in topic(s): Alkoxide & Nanoparticle. The author has an hindex of 39, co-authored 284 publication(s) receiving 5262 citation(s). Previous affiliations of Vadim G. Kessler include Bar-Ilan University & Center for Advanced Materials.

New insight in the role of modifying ligands in the sol-gel processing of metal alkoxide precursors: A possibility to approach new classes of materials

Abstract: This paper summarizes recent literature data and presents new experimental data on the mechanisms of chemical modification, hydrolysis and polycondensation of the alkoxides and demonstrates possibilities to approach new classes of materials, exploiting these mechanisms. Low reactivity of silicon alkoxides is improved by either basic catalysis exploiting an SN2 mechanism or acidic catalysis facilitating a proton-assisted SN1 mechanism as well as by modification with chelating ligands. Metal alkoxides are much stronger Lewis bases compared to silicon alkoxides and the acidity of water is strong enough to achieve their rapid hydrolysis via proton-assisted SN1 pathway even in the absence of additional catalysts. Introduction of the modifying chelating ligands is leading generally to increased charge distribution in the precursor molecules. Modifying chelating ligands are also appreciably smaller than the alkoxide ligands they replace. The modification with chelating ligands is thus facilitating the kinetics of hydrolysis and polycondensation. The size and shape of the primary particles formed in sol-gel treatment of metal alkoxides are defined not by kinetic factors in their hydrolysis and polycondensation but by the interactions on the phase boundary, which is in its turn directed by the ligand properties. The products of the fast hydrolysis and condensation sequence consist of micelles templated by self-assembly of ligands (mainly oxo-species). This concept provides explanations for commonly observed material properties and allows for the development of new strategies for the preparation of materials. We discuss the formation of inverted micelles, obtained by the appropriate choice of solvents, which allows for the formation of hollow spheres. The modifying β-diketonate ligands act as the surfactant and form an interface between the hollow sphere and the solvent. Retention of ligands inside the gel particles is possible only if ligands possessing both chelating and bridging properties are applied. Application of such ligands, for example, diethanolamine, permits to prepare new transition metal oxide based microporous membranes.

Ordered Network of Interconnected SnO2 Nanoparticles for Excellent Lithium-Ion Storage

Abstract: An ordered network of interconnected tin oxide (SnO2) nanoparticles with a unique 3D architecture and an excellent lithium-ion (Li-ion) storage performance is derived for the first time through hydrolysis and thermal self-assembly of the solid alkoxide precursor. Mesoporous anodes composed of these ≈9 nm-sized SnO2 particles exhibit substantially higher specific capacities, rate performance, coulombic efficiency, and cycling stabilities compared with disordered nanoparticles and commercial SnO2. A discharge capacity of 778 mAh g–1, which is very close to the theoretical limit of 781 mAh g–1, is achieved at a current density of 0.1 C. Even at high rates of 2 C (1.5 A g–1) and 6 C (4.7 A g–1), these ordered SnO2 nanoparticles retain stable specific capacities of 430 and 300 mAh g–1, respectively, after 100 cycles. Interconnection between individual nanoparticles and structural integrity of the SnO2 electrodes are preserved through numerous charge–discharge process cycles. The significantly better electrochemical performance of ordered SnO2 nanoparticles with a tap density of 1.60 g cm–3 is attributed to the superior electrode/electrolyte contact, Li-ion diffusion, absence of particle agglomeration, and improved strain relaxation (due to tiny space available for the local expansion). This comprehensive study demonstrates the necessity of mesoporosity and interconnection between individual nanoparticles for improving the Li-ion storage electrochemical performance of SnO2 anodes.

Molecular structure design and synthetic approaches to the heterometallic alkoxide complexes (soft chemistry approach to inorganic materials by the eyes of a crystallographer).

Abstract: General principles of formation and stability of the heterometallic alkoxides existing due to Lewis Acid–Base interaction, isomorphous substitution and heterometallic metal–metal bonds are discussed. The molecular structure design approach based on the choice of a proper molecular structure type and completing it with the ligands, providing both the necessary number of donor atoms and the sterical protection of the metal–oxygen core, is presented. Its applications in prediction of the composition and structure of single source precursors of inorganic materials are demonstrated for such classes of compounds as oxoalkoxides, alkoxide β-diketonates, alkoxide carboxylates, derivatives of functional alcohols, metallatranes and metallasiloxanes.

Role of the Ancillary Ligand N,N-Dimethylaminoethanol in the Sensitization of EuIII and TbIII Luminescence in Dimeric β-Diketonates

Abstract: Two types of dimeric complexes [Ln2(hfa)6(i2-O(CH2)2NHMe2)2] and [Ln(thd)2(i2,e2-O(CH2)2NMe2)]2 (Ln ) YIII, EuIII, GdIII, TbIII, TmIII, LuIII; hfa- ) hexafluoroacetylacetonato, thd- ) dipivaloylmethanato) are obtained by reacting [Ln(hfa)3(H2O)2] and [Ln(thd)3], respectively, with N,N-dimethylaminoethanol in toluene and are fully characterized. X-ray single crystal analysis performed for the TbIII compounds confirms their dimeric structure. The coordination mode of N,N-dimethylaminoethanol depends on the nature of the â-diketonate. In [Tb2(hfa)6(i2-O(CH2)2NHMe2)2], eight-coordinate TbIII ions adopt distorted square antiprismatic coordination environments and are O-bridged by two zwitterionic N,N-dimethylaminoethanol ligands with a Tb1âââTb2 separation of 3.684(1) A. In [Tb(thd)2(i2,e2-O(CH2)2NMe2)]2, the N,N-dimethylaminoethanol acts as chelating-bridging O,N-donor anion and the TbIII ions are seven-coordinate; the Tb1âââTb1A separation amounts to 3.735(2) A within centrosymmetric dimers. The dimeric complexes are thermally stable up to 180 °C, as shown by thermogravimetric analysis, and their volatility is sufficient for quantitative sublimation under reduced pressure. The EuIII and TbIII dimers display metal-centered luminescence, particularly [Eu2(hfa)6(O(CH2)2NHMe2)2] (quantum yield QLn L ) 58%) and [Tb(thd)2(O(CH2)2NMe2)]2 (32%). Consideration of energy migration paths within the dimers, based on the study of both pure and EuIII- or TbIII-doped (0.01-0.1 mol %) LuIII analogues, leads to the conclusion that both the â-diketone and N,N-dimethylaminoethanol ligands contribute significantly to the sensitization process of the EuIII luminescence. The ancillary ligand increases considerably the luminescence of [Eu2(hfa)6(O(CH2)2NHMe2)2], compared to [Ln(hfa)3(H2O)2], through the formation of intra-ligand states while it is detrimental to TbIII luminescence in both â-diketonates. Thin films of the most luminescent compound [Eu2(hfa)6(O(CH2)2NHMe2)2] obtained by vacuum sublimation display photophysical properties analogous to those of the solid-state sample, thus opening perspectives for applications in electroluminescent devices.

The first depleted heterojunction TiO2-MOF-based solar cell.

Abstract: A single-step hydrothermal synthesis of a TiO2–Mil-125 composite was applied for the first time to produce a depleted perovskite/TiO2–MOF heterojunction solar cell with 6.4% power conversion efficiency (PCE), characterized by durable stability in air.

Controlled ring-opening polymerization of lactide and glycolide.

Abstract: 23 Stereocontrol of Lactide ROP 6164 231 Isotactic Polylactides 6164 232 Syndiotactic Polylactides 6166 233 Heterotactic Polylactides 6166 3 Anionic Polymerization 6166 4 Nucleophilic Polymerization 6168 41 Mechanistic Considerations 6168 42 Catalysts 6169 421 Enzymes 6169 422 Organocatalysts 6169 43 Stereocontrol of Lactide ROP 6170 44 Depolymerization 6170 5 Cationic Polymerization 6170 6 Conclusion and Perspectives 6171 7 Acknowledgments 6173 8 References and Notes 6173

Multiphoton Absorbing Materials : Molecular Designs, Characterizations, and Applications

Abstract: 4. Survey of Novel Multiphoton Active Materials 1257 4.1. Multiphoton Absorbing Systems 1257 4.2. Organic Molecules 1257 4.3. Organic Liquids and Liquid Crystals 1259 4.4. Conjugated Polymers 1259 4.4.1. Polydiacetylenes 1261 4.4.2. Polyphenylenevinylenes (PPVs) 1261 4.4.3. Polythiophenes 1263 4.4.4. Other Conjugated Polymers 1265 4.4.5. Dendrimers 1265 4.4.6. Hyperbranched Polymers 1267 4.5. Fullerenes 1267 4.6. Coordination and Organometallic Compounds 1271 4.6.1. Metal Dithiolenes 1271 4.6.2. Pyridine-Based Multidentate Ligands 1272 4.6.3. Other Transition-Metal Complexes 1273 4.6.4. Lanthanide Complexes 1275 4.6.5. Ferrocene Derivatives 1275 4.6.6. Alkynylruthenium Complexes 1279 4.6.7. Platinum Acetylides 1279 4.7. Porphyrins and Metallophophyrins 1279 4.8. Nanoparticles 1281 4.9. Biomolecules and Derivatives 1282 5. Nonlinear Optical Characterizations of Multiphoton Active Materials 1282

Atomically Precise Colloidal Metal Nanoclusters and Nanoparticles: Fundamentals and Opportunities

Abstract: Colloidal nanoparticles are being intensely pursued in current nanoscience research. Nanochemists are often frustrated by the well-known fact that no two nanoparticles are the same, which precludes the deep understanding of many fundamental properties of colloidal nanoparticles in which the total structures (core plus surface) must be known. Therefore, controlling nanoparticles with atomic precision and solving their total structures have long been major dreams for nanochemists. Recently, these goals are partially fulfilled in the case of gold nanoparticles, at least in the ultrasmall size regime (1–3 nm in diameter, often called nanoclusters). This review summarizes the major progress in the field, including the principles that permit atomically precise synthesis, new types of atomic structures, and unique physical and chemical properties of atomically precise nanoparticles, as well as exciting opportunities for nanochemists to understand very fundamental science of colloidal nanoparticles (such as the s...

Functionalizing nanoparticles with biological molecules: developing chemistries that facilitate nanotechnology.

Abstract: Chemistries that Facilitate Nanotechnology Kim E. Sapsford,† W. Russ Algar, Lorenzo Berti, Kelly Boeneman Gemmill,‡ Brendan J. Casey,† Eunkeu Oh, Michael H. Stewart, and Igor L. Medintz*,‡ †Division of Biology, Department of Chemistry and Materials Science, Office of Science and Engineering Laboratories, U.S. Food and Drug Administration, Silver Spring, Maryland 20993, United States ‡Center for Bio/Molecular Science and Engineering Code 6900 and Division of Optical Sciences Code 5611, U.S. Naval Research Laboratory, Washington, D.C. 20375, United States College of Science, George Mason University, 4400 University Drive, Fairfax, Virginia 22030, United States Department of Biochemistry and Molecular Medicine, University of California, Davis, School of Medicine, Sacramento, California 95817, United States Sotera Defense Solutions, Crofton, Maryland 21114, United States