Atomic-Level Structure of the Organic-Inorganic Interface of Colloidal ZnO Nanoplatelets from Dynamic Nuclear Polarization-Enhanced NMR.

Colloidal semiconductor nanoplatelets (NPLs) have emerged as a new class of nanomaterials that can exhibit substantially distinct optical properties compared to those of isotropic quantum dots, which makes them prime candidates for new-generation optoelectronic devices. Insights into the structure and anisotropic growth of NPLs can offer a blueprint for their controlled fabrication. Here, we present an atomic-level investigation of the organic-inorganic interface structure in ultrathin and stable benzamidine ()-supported ZnO NPLs prepared by the modified ne-pot elf-upporting rganoetallic approach.

On the Fate of Lithium Ions in Sol-Gel Derived Zinc Oxide Nanocrystals.

Among diverse chemical synthetic approaches to zinc oxide nanocrystals (ZnO NCs), ubiquitous inorganic sol-gel methodology proved crucial for advancements in ZnO-based nanoscience. Strikingly, unlike the exquisite level of control over morphology and size dispersity achieved in ZnO NC syntheses, the purity of the crystalline phase, as well as the understanding of the surface structure and the character of the inorganic-organic interface, have been limited to vague descriptors until very recently. Herein, ZnO NCs applying the standard sol-gel synthetic protocol are synthesized with zinc acetate and lithium hydroxide and tracked the integration of lithium (Li) cations into the interior and exterior of nanoparticles by combining various techniques, including advanced solid-state NMR methods.

AsymPol-TEKs as efficient polarizing agents for MAS-DNP in glass matrices of non-aqueous solvents.

Two polarizing agents from the AsymPol family, AsymPol-TEK and cAsymPol-TEK (methyl-free version) are introduced for MAS-DNP applications in non-aqueous solvents. The performance of these new biradicals is rationalized in detail using a combination of electron paramagnetic resonance spectroscopy, density functional theory, molecular dynamics and quantitative MAS-DNP spin dynamics simulations. By slightly modifying the experimental protocol to keep the sample temperature low at insertion, we are able to obtain reproducable DNP-NMR data with 1,1,2,2-tetrachloroethane (TCE) at 100 K, which facilitates optimization and comparison of different polarizing agents.

Exploring the reactivity of homoleptic organozincs towards SO: synthesis and structure of a homologous series of organozinc sulfinates.

Studies on the reactivity of zinc alkyl compounds towards SO are relatively less explored than either oxygenation or hydrolysis reactions. We report on the environmentally friendly and efficient syntheses of a homologous series of [(RSO)ZnR] complexes from reactions involving homoleptic RZn (R = Me, Bu, Ph) compounds and SO. Diffusion ordered spectroscopy experiments indicate that the resulting compounds predominately occur as solvated dimers, [(RSO)ZnR(THF)], in THF solution irrespective of the character of the group bonded to the zinc centres.

Langmuir and Langmuir Blodgett films of zinc oxide (ZnO) nanocrystals coated with polyhedral oligomeric silsesquioxanes (POSS).

Hypothesis: The type and properties of ligands capping nanoparticles affect the characteristics of corresponding Langmuir and Langmuir-Blodgett films. When ligands are firmly anchored to the surface, as in zinc oxide nanocrystallites (ZnO NCs), compression at the air/water interface might cause ligands interdigitation and then the formation of supra-structures. Here, we evaluate how the introduction of bulky ligands, namely polyhedral oligomeric silsesquioxanes (POSSs), influences the self-assembly of POSS@ZnO NCs and the properties of corresponding thin films.

ZnO nanocrystals derived from organometallic approach: Delineating the role of organic ligand shell on physicochemical properties and nano-specific toxicity.

The surface organic ligands have profound effect on modulation of different physicochemical parameters as well as toxicological profile of semiconductor nanocrystals (NCs). Zinc oxide (ZnO) is one of the most versatile semiconductor material with multifarious potential applications and systematic approach to in-depth understand the interplay between ZnO NCs surface chemistry along with physicochemical properties and their nano-specific toxicity is indispensable for development of ZnO NCs-based devices and biomedical applications. To this end, we have used recently developed the one-pot self-supporting organometallic (OSSOM) approach as a model platform to synthesize a series of ZnO NCs coated with three different alkoxyacetate ligands with varying the ether tail length which simultaneously act as miniPEG prototypes.

Disclosing Interfaces of ZnO Nanocrystals Using Dynamic Nuclear Polarization: Sol-Gel versus Organometallic Approach.

The unambiguous characterization of the coordination chemistry of nanocrystal surfaces produced by wet-chemical synthesis presently remains highly challenging. Here, zinc oxide nanocrystals (ZnO NCs) coated by monoanionic diphenyl phosphate (DPP) ligands were derived by a sol-gel process and a one-pot self-supporting organometallic (OSSOM) procedure. Atomic-scale characterization through dynamic nuclear polarization (DNP-)enhanced solid-state NMR (ssNMR) spectroscopy has notably enabled resolving their vastly different surface-ligand interfaces.

Towards Extended Zinc Ethylsulfinate Networks by Stepwise Insertion of Sulfur Dioxide into Zn-C Bonds.

The ability to utilize polluting gases in efficient metal-mediated transformations is one of the most pressing challenges of modern chemistry. Despite numerous studies on the insertion of SO into M-C bonds, the chemical reaction of SO with organozinc compounds remains little explored. To fill this gap, we report here the systematic study of the reaction of Et Zn towards SO as well as the influence of Lewis bases on the reaction course.

Safe-by-Design Ligand-Coated ZnO Nanocrystals Engineered by an Organometallic Approach: Unique Physicochemical Properties and Low Toxicity toward Lung Cells.

The unique physicochemical properties and biocompatibility of zinc oxide nanocrystals (ZnO NCs) are strongly dependent on the nanocrystal/ligand interface, which is largely determined by synthetic procedures. Stable ZnO NCs coated with a densely packed shell of 2-(2-methoxyethoxy)acetate ligands, which act as miniPEG prototypes, with average core size and hydrodynamic diameter of 4-5 and about 12 nm, respectively, were prepared by an organometallic self-supporting approach, fully characterized, and used as a model system for biological studies. The ZnO NCs from the one-pot, self-supporting organometallic procedure exhibit unique physicochemical properties such as relatively high quantum yield (up to 28 %), ultralong photoluminescence decay (up to 2.

An organometallic route to chiroptically active ZnO nanocrystals.

The unique optical properties of zinc oxide nanocrystals (ZnO NCs) are strongly dependent on both the properties and the composition of the inorganic core-organic ligand interface. Developing a novel organometallic self-supporting approach, we report on the synthesis and characterization of ZnO nanocrystals coated by chiral monoanionic aminoalcoholate ligands. The resulting ZnO NCs are both chiroptically active and possess size dependent optical properties.

From Well-Defined Alkylzinc Phosphinates to Quantum-Sized ZnO Nanocrystals.

Despite various applications of alkylzinc carboxylates in chemistry and materials science, the corresponding organozinc derivatives of organophosphorus compounds still represent an insufficiently explored area. To fill this gap, we report on the synthesis of alkylzinc phosphinates and their use as efficient precursors of phosphinate-coated ZnO nanocrystals in the quantum size regime. Examples of a series of alkylzinc phosphinates with the general formula [RZn(O PR' )] (R=tBu or Et) have been prepared through equimolar reactions between ZnR and a selected phosphinic acid, namely dimethylphosphinic acid (dmpha-H), methylphenylphosphinic acid (mppha-H), diphenylphosphinic acid (dppha-H), or bis(4-methoxyphenyl)phosphinic acid (dmppha-H).

Alkylzinc diorganophosphates: synthesis, structural diversity and unique ability to incorporate zincoxane units.

Equimolar reactions between ZntBu and diphenyl phosphate (dpphe-H) or dimethyl phosphate (dmphe-H) result in the formation of [tBuZn(OP(OR'))]-type compounds which crystallize as tetranuclear aggregates, [tBuZn(dpphe)] (14) or [tBuZn(dmphe)] (24), with the phosphate ligands spanning 4-coordinate Zn centers. The utility of ZnMe instead of ZntBu dramatically changes the reaction outcome and leads to [MeZn(OP(OR'))]-type moieties incorporating zincoxane units, i.e.

Photoactive Langmuir-Blodgett, Freely Suspended and Free Standing Films of Carboxylate Ligand-Coated ZnO Nanocrystals.

A new possibility for the formation of macroscopic and photoactive structures from zinc oxide nanocrystals is described. Photoactive freely suspended and free-standing films of macroscopic area (up to few square millimeters) and submicrometer thickness (up to several hundreds of nanometers) composed of carboxylate ligand-coated zinc oxide nanocrystallites (RCO2-ZnO NCs) of diameter less than 5 nm are prepared according to a modified Langmuir-Schaefer method. First, the suspension of RCO2-ZnO NCs is applied onto the air/water interface.

'Clickable' ZnO nanocrystals: the superiority of a novel organometallic approach over the inorganic sol-gel procedure.

We demonstrate for the first time a highly efficient Cu(i)-catalyzed alkyne-azide cycloaddition reaction on the surface of ZnO nanocrystals with retention of their photoluminescence properties. Our comparative studies highlight the superiority of a novel self-supporting organometallic method for the preparation of brightly luminescent and well-passivated ZnO nanocrystals over the traditional sol-gel procedure.

Towards Organized Hybrid Nanomaterials at the Air/Water Interface Based on Liquid-Crystal/ZnO Nanocrystals.

The ability to self-assemble nanosized ligand-stabilized metal oxide or semiconductor materials offers an intriguing route to engineer nanomaterials with new tailored properties from the disparate components. We describe a novel one-pot two-step organometallic approach to prepare ZnO nanocrystals (NCs) coated with deprotonated 4-(dodecyloxy)benzoic acid (i.e.