RESUMO
Defined arrays of transition metal ions embedded in tailored polydentate ligand scaffolds allow for a systematic design of their physical properties. Such molecular strings of closed-shell transition metal centers are particularly interesting for Group 11 metal ions in the oxidation state +1 if they undergo metallophilic d10···d10 contact interactions since these clusters are oftentimes efficient photoluminescence (PL) emitters. Copper is particularly attractive as a sustainable earth-abundant coinage metal source and because of the ability of several CuI complexes to serve as powerful thermally activated delayed fluorescence (TADF) emitters in molecular/organic light-emitting devices (OLEDs). Our combined synthetic, crystallographic, photophysical, and computational study describes a straight tetracuprous array possessing a centrally disconnected CuI2···CuI2 chain and a continuous helically bent CuI4 complex. This molecular helix undergoes a facile rearrangement in diethyl ether solution, yielding an unprecedented nanosized CuI10 cluster (2.9 × 2.0 nm) upon crystallization. All three clusters show either bright blue phosphorescence, TADF, or green/yellow multiband phosphorescence with quantum yields between 6.5 and 67%, which is persistent under hydrostatic pressure up to 30 kbar. Temperature-dependent PL investigations in combination with time-dependent density-functional theory (TD-DFT) calculations and void space analyses of the crystal packings complement a comprehensive correlation between the molecular structures and photoluminescence properties.
RESUMO
Synthesis and characterization of Lewis base free coordination polymers of selected lanthanides are presented. For this purpose, the substituted CotTIPS ligand (CotTIPS = 1,4-bis-triisopropylsilyl-cyclo-octatetraendiide) was used to synthesize homoleptic, anionic multidecker compounds of the type [K{LnIII(ɳ8-CotTIPS)2}]n. Depending on the solvent used for crystallization and the ionic radii of the lanthanide cations, three different categories of one-dimensional heterobimetallic coordination polymers were obtained in the solid state. For the early lanthanides La and Ce a unique helical conformation was obtained by crystallization from toluene, while the ionic radius of Pr seems to be a turning point towards the crystallization of zigzag polymers. For Er a third structural motif, a trapezoidal wave polymer was observed. Additionally, the zigzag polymer for all compounds could be obtained by changing the solvent from toluene to Et2O, reavealing a correlation between solid-state structure and ionic radii as well as solvent. While photoluminescence (PL) properties of Cot-lanthanide compounds are scarce, the La complexes show ligand centered green luminescence, whereas the Ce complexes reveal deep red emission origin from d-f transitions. The Er-compounds are single-molecule magnets, in which the magnetic relaxation of each Er ion occurs isolated from its neighbors at temperatures above 10 K, while below 9 K a strong antiferromagnetic coupling between the Er ions was seen.