Rare earth benzotriazolates:: Coordination polymers incorporating decomposition products from ammonia to 1,2-diaminobenzene in 1∞[Ln(Btz)3(BtzH)] (Ln = Ce, Pr), 1∞[Ln(BtZ)3{Ph(NH2)2}] (Ln = Nd, Tb, Yb), and 1∞[Ho2(BtZ)6(BtzH)(NH3)]

The solvent-free melt reactions of benzotriazole (BtzH, C6H4N2NH) with rare earth metals result in three different types of benzotriazolate coordination polymers. Early 4f metals yield (1)(infinity)[Ln(Btz)(3)(BtzH)] [Ln = Ce (1), Pr (2)], from neodymium to ytterbium the type (1)(infinity)[Ln(Btz)(3){Ph(NH2)2}] is observed [Ln = Nd (3), Tb (4), Yb (5)], whereas the late 4f metal Ho gives (1)(infinity)[Ho-2(BtZ)(6)(BtzH)(NH3)] (6). Depending on the reaction conditions and the respective rare earth element, ligand fragments originating from decomposition products are incorporated in the coordination polymers. Compounds 1-3 and 6 were obtained as single crystals and their crystal structures determined by single-crystal X-ray analysis, whilst 4 and 5 were obtained as powders. X-ray powder diffraction shows the isotypic character of polymers 3, 4, and 5. The benzotriazolates contain trivalent lanthanide ions with complete nitrogen coordination. Decomposition of the ligand accompanies the formation of the coordination polymers. X-ray analysis was combined with thermal analysis and mass spectrometry to investigate the influence of reaction temperatures on ligand decomposition. Ln-benzotriazolates exhibit aspects of materials science such as luminescence {D-5(4) -> (7)Fj, J = 4-6 for (1)(infinity)[Tb(BtZ)(3){Ph(NH2)(2)}] (4)} without quenching by concentration. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006.