3–(2–Pyridyl)pyrazole Based Luminescent 1D-Coordination Polymers and Polymorphic Complexes of Various Lanthanide Chlorides Including Orange-Emitting Cerium(III)

Abstract

A series of 18 lanthanide-containing 1D-coordination polymers 1∞[Ln2(2–PyPzH)4Cl6], Ln = La, Nd, Sm, dinuclear polymorphic complexes α–, β–[Ln2(2–PyPzH)4Cl6], Ln = Sm, Eu, Gd, α–[Tb2(2–PyPzH)4Cl6], and [Gd2(2–PyPzH)3(2–PyPz)Cl5], mononuclear complexes [Ce(2–PyPzH)3Cl3], [Ln(2–PyPzH)2Cl3], Ln = Tb, Dy, Ho, and Er, and salt-like complexes [Gd3(2–PyPzH)8Cl8]Cl and [PyH][Tb(2–PyPzH)2Cl4] were obtained from the reaction of the respective lanthanide chloride with the 3–(2–pyridyl)pyrazole (2–PyPzH) ligand at different temperatures. An antenna effect through ligand-to-metal energy transfer was observed for several products, leading to the highest luminescence efficiency displayed by a quantum yield of 92% in [Tb(2–PyPzH)2Cl3]. The Ce3+ ion in the complex [Ce(2–PyPzH)3Cl3] exhibits a bright and orange 5d-based broadband emission with a maximum at around 600 nm, marking an example of a strong reduction of the 5d-excited states of Ce(III). The absorption spectroscopy shows ion-specific 4f–4f transitions, which can be assigned to Nd3+, Sm3+, Eu3+, Dy3+, Ho3+, and Er3+ in a wide spectral range from UV–VIS to the NIR region.