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A novel bis(diphenylphosphino)methane (DPPM) functionalized amidine ligand (DPPM-C(N-Dipp) 2 H) (Dipp=2,6-diisopropylphenyl) was synthesized. Subsequent deprotonation with suitable alkali metal bases resulted in the corresponding complexes [M{DPPM-C(N-Dipp) 2 }(L n )] (M=Li, Na, K, Rb, Cs; L=thf, Et 2 O). The alkali metal complexes form monomeric species in the solid state, exhibiting intramolecular metal-π-interactions. In addition, a caesium derivative [Cs{PPh 2 CH 2 -C(N-Dipp) 2 }] 6 was obtained by cleavage of a diphenylphosphino moiety, forming an unusual six-membered ring structure in the solid state. All complexes were fully characterized by single crystal X-ray diffraction, NMR spectroscopy, IR spectroscopy as well as elemental analysis. Furthermore, the photoluminescent properties of the complexes were thoroughly investigated, revealing differences in emission with regards to the respective alkali metal. Interestingly, the hexanuclear [Cs{PPh 2 CH 2 -C(N-Dipp) 2 }] 6 metallocycle exhibits a blue emission in the solid state, which is significantly red-shifted at low temperatures. The bifunctional design of the ligand, featuring orthogonal donor atoms (N vs. P) and a high steric demand, is highly promising for the construction of advanced metal and main group complexes., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The controlled incorporation of phenanthroline moieties into polymers is introduced, demonstrating their application as metal-ion complexing ligands for the construction of advanced macromolecular structures. Specifically, two phenanthroline-containing monomers based on acrylate and styrene functionalities, were synthesized. Each monomer was readily copolymerized with either N,N-dimethylacrylamide or styrene via nitroxide-mediated polymerization, resulting in narrowly distributed polar or non-polar copolymers. To demonstrate the versatility of the established polymer systems, the polar polymer was employed for transition metal induced single-chain nanoparticle formation, verified by diffusion-ordered NMR and UV/Vis spectroscopy. Furthermore, the non-polar polymer allows facile incorporation of lanthanide ions, creating luminescent metallo-polymers, in-depth characterized by advanced photophysical experiments and 2D NMR measurements., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)