A highly efficient photomediated atom transfer radical polymerization protocol is reported for semi-fluorinated acrylates and methacrylates. Use of the commercially available solvent, 2-trifluoromethyl-2-propanol, optimally balances monomer, polymer, and catalyst solubility while eliminating transesterification as a detrimental side reaction. In the presence of UV irradiation and ppm concentrations of copper(II) bromide and Me-TREN (TREN = tris(2-aminoethyl amine)), semi-fluorinated monomers with side chains containing between three and 21 fluorine atoms readily polymerize under controlled conditions. The resulting polymers exhibit narrow molar mass distributions (Đ ≈ 1.1) and high end group fidelity, even at conversions greater than 95%. This level of control permits the in situ generation of chain-end functional homopolymers and diblock copolymers, providing facile access to semi-fluorinated macromolecules using a single methodology with unprecedented monomer scope. The results disclosed herein should create opportunities across a variety of fields that exploit fluorine-containing polymers for tailored bulk, interfacial, and solution properties.

Metal-organic networks (MONs) were created by a stepwise solution deposition approach from vinylpyridine-based building blocks and PdCl(2). The combined experimental and computational study demonstrates the formation of saturated, structurally organized systems on solid supports. The rigid nature and geometry of the components are well-suited to form honeycomb and parallelogram structures, as predicted by a computational study. Detailed structural information of the new MONs was obtained by optical (UV/vis) spectroscopy, ellipsometry, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and synchrotron X-ray reflectivity (XRR). Notably, the XPS elemental composition indicates the formation of a palladium coordination-based network.

Here we present the critical role of the molecular structure and reaction parameters on the nature of thin-film growth, using a versatile two-step assembly method with organic and metal-organic chromophores cross-linked with palladium. It was found that the polypyridyl complexes exhibit exponential growth, whereas, under identical conditions, the organic systems exhibit linear behavior. The internal film morphology plays a pivotal role in the storage and usage of the palladium, where a more porous structure results in exponential growth. Interestingly, through proper tuning of the reaction conditions, the growth of the molecular assemblies can be controlled, resulting in a changeover from exponential to linear growth. These findings unequivocally demonstrate the importance of both the internal film structure and deposition conditions on the assembly of molecular-based films.

Geometrische Vorgaben: Die Form einer Reihe von molekularen Vernetzern, die eine bis vier Pyridyleinheiten tragen, bestimmt die optischen Eigenschaften von Aggregaten aus Goldnanopartikeln (AuNPs; siehe Bild). Wie eine TEM‐Analyse belegt, übertragen sich die unterschiedlichen Molekülstrukturen bei der Aggregation der AuNPs auf die Submikrometerebene.