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Ag nanocubes (AgNCs) are predominantly synthesized by the polyol method, where the solvent (ethylene glycol) is considered the reducing agent and poly( N -vinylpyrrolidone) (PVP) the shape-directing agent. An experimental phase diagram for the formation of Ag nanocubes as a function of PVP monomer concentration ( C m ) and molecular weight ( M w ) demonstrated end groups of PVP impact the final Ag product. Measured rates of the initial Ag + reduction at different PVP C m and M w confirmed the reducing effect originates from end-groups. PVP with well-defined aldehyde and hydroxyl end groups lead to the formation of Ag nanocubes and nanowires respectively, indicating the faster reducing agent formed kinetically preferred nanowires. We demonstrate PVP end-groups induce initial reduction of Ag + to form seeds followed by autocatalytic reduction of Ag + by ethylene glycol (and not solvent oxidation products) to form Ag nanostructures. The current study enabled a quantitative description of the role of PVP in nanoparticle shape-control and demonstrates a unique opportunity to design nanostructures by combining nanoparticle synthesis with polymer design to introduce specific physicochemical properties.

Among the various reported post synthetic modifications of colloidal nanocrystals, cation exchange (CE) is one of the most promising and versatile approaches for the synthesis of nanostructures that cannot be directly synthesized from their constitutive precursors. Numerous studies have reported on the qualitative analysis of these reactions, but rigorous quantitative study of the thermodynamics of CE in colloidal nanoparticles is still lacking. We demonstrate using isothermal titration calorimetry (ITC), the thermodynamics of the CE between cadmium selenide (CdSe) nanocrystals and silver in solution can be quantified. We survey the influence of CdSe nanocrystal diameter, capping ligands and temperature on the thermodynamics of the exchange reaction. Results obtained from ITC provide a detailed description of overall thermodynamic parameters-equilibrium constant ( K eq ), enthalpy (Δ H), entropy (Δ S) and stoichiometry ( n)-of the exchange reaction. We compared the free energy change of reaction (Δ G) between CdSe and Ag + obtained directly from ITC for both CdSe bulk and nanoparticles with values calculated from previously reported methods. While the calculated value is closer to the experimentally obtained Δ G rxn for bulk particles, nanocrystals show an additional Gibbs free energy stabilization of ∼-14 kJ/mol Se. We discuss a thermochemical cycle elucidating the steps involved in the overall cation exchange process. This work demonstrates the application of ITC to probe the thermochemistry of nanoscale transformations under relevant solution conditions.

A discrete tetragonal tube-shaped complex (MT-1) has been synthesised by coordination-driven self-assembly of a carbazole-based tetraimidazole donor L and a Pd(II) 90° acceptor, that is, [cis-(dppf)Pd(OTf) 2 ] (dppf=diphenylphosphinoferrocene, OTf=CF 3 SO 3 - ). Complex MT-1 was characterised by multinuclear NMR, ESI-MS and single-crystal X-ray diffraction analysis (SCXRD), which showed its symmetrical tetrafacial tube-shaped architecture possessing a large cavity described by four aromatic walls. This coordination cage was successfully utilised as a molecular vessel to perform intramolecular cycloaddition reactions of O-allylated benzylidinebarbituric acid derivatives inside its confined nanospace. The presence of a catalytic amount of MT-1 promoted [4+2] cycloaddition reactions in a regio- and stereoselective manner, yielding the corresponding penta/tetracyclouracil derivatives in good yields under mild reaction conditions. This protocol is interesting compared with the literature reports for the synthesis of similar chromenopyran pyrimidinedione derivatives under high-temperature reflux conditions or solid-state melt reactions (SSMRs)., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)