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Four new coordination polymers (CPs) were obtained under hydrothermal reaction conditions using 2,4,6-pyridinetricarboxylic acid (H 3 PTC) and Bi(NO 3 ) 3 ·5H 2 O. The systematic high-throughput investigation of the system Bi 3+ /H 3 PTC/NaOH/(3) and -[Bi(PTC)] (4), which were structurally characterised by single-crystal Xray diffraction. Compounds 1 and 2 crystallise in 2D layered structures, whereas 3 and 4 form 3D coordination networks. Employing the nomenclature proposed by Cheetham et al. 1 and 2 are classified as I 1 O 1 (mixed inorganic-organic layers), 3 as I 0 O 3 (3D coordination polymers) and 4 as I 1 O 2 (mixed inorganic-organic 3D framework). In all cases the nitrogen atom of [a]

Abstract. Reaction of Cd(NCS) 2 or Zn(NCS) 2 with 3-aminomethylpyridine (3-AMPy) leads to the formation of five compounds with the com-and [Zn(NCS) 2 (3-AMPy)] 2 (3-Zn). In 1-Cd the Cd cations are linked by the 3-AMPy ligands into layers that consist of rings, built up of four Cd cations and four 3-AMPy ligands. These layers are stacked to form channels, in which the 3-AMPy solvate molecules are located. In the isotypic compounds 2-Cd and 2-Zn the metal cations are also linked into layers by the 3-AMPy ligands with an identical layer topology as that in 1-Cd,

Abstract. The reaction of Cd(NCS) 2 with 3-hydroxymethylpyridine (3-HMPy) leads to the formation of compounds with the composition Cd(NCS) 2 (3-HMPy) 4 (1-Cd),Cd(NCS) 2 (3-HMPy) 2 (2-Cd)(Cd(NCS) 2 ) 2 -(3-HMPy) 3 (3-Cd), and (Cd(NCS) 2 ) 3 (3-HMPy) 4 (4-Cd). Compound 1-Cd consists of discrete complexes and in 2-Cd the Cd cations are linked into chains by the anionic and the organic co-ligands. In 3-Cd as well as 4-Cd the Cd cations are connected into chains by the thiocyanate anions, which are further linked into layers by the 3-HMPy coligands. In contrast, with Zn only one compound with the composition Zn(NCS) 2 (3-HMPy) 2 ·H 2 O (1-Zn-H 2 O) was characterized by single-

Despite the strong technological importance of lanthanide complexes, their formation processes are rarely investigated. This work is dedicated to determining the influence of synthesis parameters on the formation of [Ce(bipy)2(NO3)3] as well as Ce3+‐ and Tb3+‐substituted [La(bipy)2(NO3)3] (bipy = 2,2′‐bipyridine) complexes. To this end, we performed in situ luminescence measurements, synchrotron‐based X‐ray diffraction (XRD) analysis, infrared spectroscopy (IR), and measured pH value and/or ion conductivity during their synthesis process under real reaction conditions. For the [Ce(bipy)2(NO3)3] complex, the in situ luminescence measurements initially presented a broad emission band at 490 nm, assigned to the 5d→4f Ce3+ ions within the ethanolic solvation shell. Upon the addition of bipy, a red shift to 700 nm was observed. This shift was attributed to the changes in the environment of the Ce3+ ions, indicating their desolvation and incorporation into the [Ce(bipy)2(NO3)3] complex. The induction time was reduced from 8 to 3.5 min, by increasing the reactant concentration by threefold. In contrast, [La(bipy)2(NO3)3] crystallized within days instead of minutes, unless influenced by high Ce3+ and Tb3+ concentrations. Monitoring and controlling the influence of the reaction parameters on the structure of emissive complexes is important for the development of rational synthesis approaches and optimization of their structure‐related properties like luminescence.

Reaction of Cd(NCS)2 and Zn(NCS)2 with 3-ethylpyridine leads to the formation of compounds of compositions M(NCS)2(3-ethylpyridine)4 (M=Cd, 1-Cd; Zn, 1-Zn) and M(NCS)2(3-ethylpyridine)2 (M=Cd, 2-Cd; Zn, 2-Zn). 1-Cd and 1-Zn are isotypic and form discrete complexes in which the metal cations are octahedrally coordinated by two trans-coordinating N-bonded thiocyanate anions and four 3-ethylpyridine co-ligands. In 2-Cd the cations are also octahedrally coordinated but linked into chains by pairs of μ-1,3-bridging anionic ligands. 2-Zn is built up of discrete complexes, in which the Zn cation is tetrahedrally coordinated by two N-bonded thiocyanate anions and two 3-ethylpyridine co-ligands. Compounds 1-Cd, 2-Cd and 2-Zn can be prepared in a pure state, whereas 1-Zn is unstable and transforms on storage into 2-Zn. If 1-Cd and 1-Zn are heated, a transformation into 2-Cd, respectively 2-Zn is observed. Luminescence measurements reveal that 1-Cd, 2-Cd and 2-Zn emit light in the blue spectral range with maxima at, respectively, 21724, 21654 and 22055 cm−1, assigned to ligand-based luminescence.

Nanostructured Er3+‐ and Er3+/Yb3+‐activated hafnium oxide films and nanoparticles were prepared from a stable colloidal suspension and investigated by several techniques such as transmission electron microscopy, X‐ray diffraction, dynamic light scattering, atomic force microscopy, Fourier‐transform infrared spectroscopy, and photoluminescence. Low roughness and crack‐free films were deposited by dip‐coating and spin‐coating techniques on vitreous SiO2 and Si substrates. Nanostructured particles were also synthesized. Remarkable structural and spectroscopic differences were observed for hafnium oxide‐based materials as a function of the Er3+ and Er3+/Yb3+ concentration. The 4I13/2 → 4I15/2 emission bandwidth and the lifetime of the 4I13/2 metastable state of Er3+ was tailored through the rare‐earth concentration. The Er3+ emission in HfO2 can be explored for photonic applications.