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 2.1 μs), and EPR silence under standard conditions. The cytotoxicity of the resulting ZnO NCs toward normal (MRC-5) and cancer (A549) human lung cell lines was tested by MTT assay, which demonstrated that these brightly luminescent, quantum-sized ZnO NCs have a low negative impact on mammalian cell lines. These results substantiate that the self-supporting organometallic approach is a highly promising method to obtain high-quality, nontoxic, ligand-coated ZnO NCs with prospective biomedical applications.

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. For the OSSOM‐derived NCs, DPP moieties form stable and strongly‐anchored μ2‐ and μ3‐bridging‐ligand pairs that are resistant to competitive ligand exchange. The sol‐gel‐derived NCs contain a wide variety of coordination modes of DPP ligands and a ligand exchange process takes place between DPP and glycerol molecules. This highlights the power of DNP‐enhanced ssNMR for detailed NC surface analysis and of the OSSOM approach for the preparation of ZnO NCs.

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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.

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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., an X-type liquid-crystalline ligand) as a model LC system (termed ZnO-LC1 NCs). Langmuir and Langmuir-Blodgett films of the resulting hybrids are investigated. The observed behavior of the ZnO NCs at the air/water interface is rationalized by invoking a ZnO-interdigitation process mediated by the anchored liquid-crystalline shell. The ordered superstructures form according to mechanism based on a ZnO-interdigitation process mediated by liquid crystals (termed ZIP-LC). The external and directed force applied upon compression at the air/water interface and the packing of the ligands that stabilize the ZnO cores drives the formation of nanorods of ordered internal structure. To study the process in detail, we follow a nontraditional protocol of thin-film investigation. We collect the films from the air/water interface in powder form (ZnO-LC1 LB), resuspend the powder in organic solvents and utilize otherwise unavailable experimental techniques. The structural and physical properties of the resulting superlattices were studied by using electron microscopy, atomic force microscopy, X-ray studies, dynamic light scattering, thermogravimetric analysis, UV/Vis absorption, and photoluminescence spectroscopy.

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. The size and in consequence the emission color of the ZnO NCs could be simply adjusted by the characteristic of the aminoalcohol used.

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). The reactivities of alkylzinc phosphinate complexes toward H O and O have also been investigated, which resulted in the isolation of two oxo-zinc phosphinate clusters, that is, [Zn (μ -O)(dppha) ] and [Zn (μ -O)(dmppha) ], as well as the unique alkoxy(oxo)zinc cluster [Zn (μ -O)(μ -OtBu)(dppha) ]. Analysis of the crystal structures has revealed that organozinc complexes incorporating phosphinate ligands exhibit a unique capacity for shape-driven self-assembly to produce extended networks, including noncovalent quasi-porous materials. Finally, monodispersed and quantum-sized ZnO NCs coated with phosphinate ligands have been prepared using a non-external-surfactant-assisted wet-chemical organometallic approach based on well-defined [RZn(O PR' )]-type compounds. The resulting brightly luminescent ZnO NCs exhibit average core sizes and hydrodynamic diameters in the ranges 2-4.5 nm and 5-8 nm, respectively. The size of the inorganic core is slightly affected by the character of the incorporated phosphinate ligand, being smallest for ZnO NCs coated by asymmetrically substituted mppha ligands. Regardless of whether or not various phosphinate coating ligands could be controllably applied on the ZnO NC surface, no significant differences were found in the luminescence profiles of the analyzed nanosystems.