Kamil Sokołowski

Towards a New Family of Photoluminescent Organozinc 8- Hydroxyquinolinates with a High Propensity to Form Noncovalent Porous Materials

We report on investigations of reactions of tBu(2)Zn with 8-hydroxyquinoline (q-H) and the influence of water on the composition and structure of the final product. A new synthetic approach to photoluminescent zinc complexes with quinolinate ligands was developed that allowed the isolation of a series of structurally diverse and novel alkylzinc 8-hydroxyquinolate complexes: the trinuclear alkylzinc aggregate [tBuZn(q)](3) (1(3)), the pentanuclear oxo cluster [(tBu)(3)Zn(5)(μ(4) -O)(q)(5)] (2), and the tetranuclear hydroxo cluster [Zn(q)(2)](2)[tBuZn(OH)](2) (3). All compounds were characterized in solution by (1)H NMR, IR, UV/Vis, and photoluminescence (PL) spectroscopy, and in the solid state by X-ray diffraction, TGA, and PL studies. Density functional theory calculations were also carried out for these new Zn(II) complexes to rationalize their luminescence behavior. A detailed analysis of the supramolecular structures of 2 and 3 shows that the unique shape of the corresponding single molecules leads to the formation of extended 3D networks with 1D open channels. Varying the stoichiometry, shape, and supramolecular structure of the resulting complexes leads to changes in their spectroscopic properties. The close-packed crystal structure of 1(3) shows a redshifted emission maximum in comparison to the porous crystal structure of 2 and the THF-solvated structure of 3.

Permanent Porosity Derived From the Self-Assembly of Highly Luminescent Molecular Zinc Carbonate Nanoclusters†

Over the past two decades, crystalline microporous materials have attracted major interest, owing to their applications in gas sorption, separation, catalysis, and sensing. Microporous crystalline materials can be constructed from coordinatively or covalently linked building blocks where rigid or semi-rigid molecular scaffolds separate void spaces of different size and geometry. Prominent examples of porous materials showing polymeric structures include zeolites, hybrid metal–organic frameworks (MOFs) or porous coordination polymers (PCPs), covalent organic frameworks (COFs), and Hbonded supramolecular organic frameworks (SOFs). The formation of bonding interactions between building units is an important factor that defines and controls the stability and robustness of these porous polymeric materials. However, discrete molecules may also pack in the solid state to form 3D assemblies that exhibit high permanent porosity. The resulting noncovalent porous materials (NPMs) are distinct from the above polymeric systems, as they are held together by weak noncovalent crystal-packing forces. Modifications of structure by cocrystallization of different building blocks can tune the microcavities in the solid state, and the material can thus conform to the shape or functionality of guest molecules. Moreover, these materials can be highly solubile, an important advantage in their processing to form porous thin films. NPMs can exhibit extrinsic and/or intrinsic porosity. Intrinsic porosity is associated with the structure of the single-molecule-containing voids, clefts, or cavities, as has been demonstrated for calixarenes, cucurbiturils, cyclodextrins, organic cage compounds, or discrete small organic molecules. In contrast, materials with extrinsic porosity are those where individual molecules pack in the solid-state to form structures with empty spaces between the individual molecules. As discrete molecules tend to form close-packed solids with minimal void volume, extrinsic porosity in NPMs remains a rare phenomenon. The rational design and preparation of NPMs showing extrinsic porosity based on molecular metal complexes is highly challenging and few examples have been reported. We have demonstrated previously that alkylzinc hydroxides RZnOH can be efficiently transformed into multinuclear alkyzinc carbonate nanoclusters or nanomaterials, such as discrete nanoparticulate zinc carbonate aerogels and ZnO nanoparticles. As shown in Scheme 1a, the reactivity of the RZnOH species can be rationalized in terms of the presence of both a proton-reactive Zn C bond and CO2-reactive Zn OH groups. We argued that introduction of an additional auxiliary ligand L to the RZnOH system, followed by CO2 fixation, could lead to the formation of novel molecular building blocks for new extrinsic NPMs. Herein, we report such a strategy in which the construction of a nanosized cluster [Zn10(m6-CO3)4(L)12] (WUT-1; WUT=Warsaw University of Technology) is achieved by fixation of CO2 by the tetranuclear hydroxo precursor [Zn4(m3-OH)2(L)4(tBu)2] (1;

Hydrogen evolution with nanoengineered ZnO interfaces decorated using a beetroot extract and a hydrogenase mimic

Herein, we report a nano-hybrid photo-system based on abundant elements for H2 production with visible light. The photo-systems proficiency relates to the novel ZnO nanocrystals employed. The ZnO carboxylate oligoethylene glycol shell enhances charge separation and accumulates reactive electrons for the photocatalytic process.

Activation of CO2 by tBuZnOH species: efficient routes to novel nanomaterials based on zinc carbonates

We report on the activation of CO2 by the well-defined alkylzinc hydroxide (tBuZnOH)6 in the absence and presence of tBu2Zn as an external proton acceptor. The slight modifications in reaction systems involving organozinc precursors enable control of the reaction products with high selectivity leading to the isolation of the mesoporous solid based on ZnCO3 nanoparticles or an unprecedented discrete alkylzinc carbonate [(tBuZn)2(μ5-CO3)]6 cluster with the Zn-C bond intact, respectively.

Applying Mechanochemistry for Bottom-Up Synthesis and Host-Guest Surface Modification of Semiconducting Nanocrystals: A Case of Water-Soluble β-Cyclodextrin-Coated Zinc Oxide.

Mechanochemistry has recently emerged as an environmentally friendly solventless synthesis method enabling a variety of transformations including those impracticable in solution. However, its application in the synthesis of well-defined nanomaterials remains very limited. Here, we report a new bottom-up mechanochemical strategy to rapid mild-conditions synthesis of organic ligand-coated ZnO nanocrystals (NCs) and their further host-guest modification with β-cyclodextrin (β-CD) leading to water-soluble amide-β-CD-coated ZnO NCs. The transformations can be achieved by either one-pot sequential or one-step three-component process. The developed bottom-up methodology is based on employing oxo-zinc benzamidate, [Zn4 (μ4 -O)(NHOCPh)6 ], as a predesigned molecular precursor undergoing mild solid-state transformation to ZnO NCs in the presence of water in a rapid, clean and sustainable process.

Experimental and Computational Insights into Carbon Dioxide Fixation by RZnOH Species

Organozinc hydroxides, RZnOH, possessing the proton-reactive alkylzinc group and the CO2 -reactive Zn-OH group, represent an intriguing group of organometallic precursors for the synthesis of novel zinc carbonates. Comprehensive experimental and computational investigations on 1) solution and solid-state behavior of tBuZnOH (1) species in the presence of Lewis bases, namely, THF and 4-methylpyridine; 2) step-by-step sequence of the reaction between 1 and CO2; and 3) the effect of a donor ligand and/or an excess of tBu2Zn as an external proton acceptor on the reaction course are reported. DFT calculations for the insertion of carbon dioxide into the dinuclear alkylzinc hydroxide 12 are fully consistent with (1)H NMR spectroscopy studies and indicate that this process is a multistep reaction, in which the insertion of CO2 seems to be the rate-determining step. Moreover, DFT studies show that the mechanism of the rearrangement between key intermediates, that is, the primary alkylzinc bicarbonate with a proximal position of hydrogen and the secondary alkylzinc bicarbonate with a distal position of hydrogen, most likely proceeds through internal rotation of the dinuclear bicarbonate.

Hidden gapless states during thermal transformations of preorganized zinc alkoxides to zinc oxide nanocrystals

Zinc oxide (ZnO) is one of the most versatile semiconductor materials with multifarious potential applications. Easily accessible alkylzinc alkoxides have been widely exploited as single-source precursors of ZnO-based nanomaterials but their multi-step decomposition pathways have not been understood in detail. Herein, the formation mechanism of ZnO nanocrystals via solid-state thermal decomposition of a model pre-organised alkylzinc alkoxide precursor, i.e. [tBuZn(μ3-OtBu)]4, is elucidated using in situ valence-to-core X-ray emission (v2c-XES) and high energy resolution off-resonant spectroscopy (HEROS) in conjunction with theoretical calculations. Combination of in situ spectroscopic measurements and theoretical simulations indicates that the precursor structural evolution is initiated by the homolytic cleavage of the R–Zn bond, which leads to the formation of a transient radical ([˙Zn(μ3-OR)][RZn(μ3-OR)]3) species, which is responsible for the initial decomposition process. The ensuing multistep transformations involve the formation of intermediate radical zinc oxo-alkoxide clusters with gapless electronic states. Hitherto, the formation of clusters of this type has not been considered either as intermediate structures en route to a semiconductor ZnO phase or as potential species accounting for various defect states of ZnO NCs, particularly the singly charged oxygen vacancy, Vo+.