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An anionic mechanism is used to create polymers and copolymers as confined to, or anchored to, high‐surface‐area porous nanoparticles. Linear polymers with soft and glassy chains, such as polyisoprene and polymethylmethacrylate, were produced by confined anionic polymerization in 3D networks of porous aromatic frameworks. Alternatively, multiple anions were generated on the designed frameworks which bear removal protons at selected positions, and initiate chain propagation, resulting in chains covalently connected to the 3D network. Such growth can continue outside the pores to produce polymer‐matrix nanoparticles coated with anchored chains. Sequential reactions were promoted by the living character of this anionic propagation, yielding nanoparticles that were covered by a second polymer anchored by anionic block copolymerization. The intimacy of the matrix and the grown‐in polymers was demonstrated by magnetization transfer across the interfaces in 2D 1H‐13C‐HETCOR NMR spectra. [ABSTRACT FROM AUTHOR]

The following AgI bis(pyrazolyl)methane complexes with BF4-/NO3- as counteranions were synthesized and characterized: [Ag(LpzH)]2(NO3)2 ( 1), [Ag(LpzMe)]2(NO3)2 ( 2), [Ag(LpzH)] n(BF4) n ( 3), and [Ag(LpzMe)] n(BF4) n ( 4) [LpzH = bis(pyrazolyl)methane; LpzMe = bis(3,5-dimethylpyrazolyl)methane]. These complexes were prepared to identify optimum precursors for the thermolytic deposition of metallic silver. The crystal structures of 1 and 2 show that the complexes are dinuclear and that the NO3- anions interact with the metals. In contrast, 3 is polymeric and the BF4- does not interact with the metal. When crystallizing 1- 4 in non-anhydrous solvents, the presence of adventitious water further reacts with 3 and 4 (but not with 1 and 2) to yield dinuclear complexes [Ag(LpzH)(H2O)2]2(BF4)2 ( 3a) and [Ag(LpzMe)(H2O)2]2(BF4)2 ( 4a). All of the dinuclear species 1, 2, 3a and 4a exhibit an argentophilic interaction with Ag ···Ag distances in the range 3.18-2.99 Å. Thermogravimetric analysis (TGA) shows that 1 and 2 have lower decomposition temperatures (231 and 255 °C, respectively) than 3 and 4 (298 and 331 °C, respectively). 2 was further investigated as a precursor for metallic silver deposition by spin-coating solutions (10-3 m, THF/DMSO, 4:1), followed by annealing at 310 °C on 52100 steel substrates. According to energy-dispersive X-ray spectroscopy (EDS) and scanning electron microscopy (SEM) the metal deposition proceeds primarily via an island growth (Volmer-Weber) mechanism. [ABSTRACT FROM AUTHOR]