Youssef Heba, Sedykh Alexander E, Becker Jonathan, Schäfer Thomas, Taydakov Ilya V, Li Huanrong R, Müller-Buschbaum Klaus
Institute of Inorganic and Analytical Chemistry, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, 35392, Giessen, Germany.
Department of Chemistry, Faculty of Science, Mansoura University, El Gomhouria, Mansoura Qism 2, Dakahlia Governorate, 11432, Mansoura, Egypt.
Chemistry. 2021 Dec 1;27(67):16634-16641. doi: 10.1002/chem.202103068. Epub 2021 Nov 5.
Homoleptic, 3D coordination polymers of the formula [Ln(3-PyPz) ] and [Ln(4-PyPz) ], (3-PyPz) =3-(3-pyridyl)pyrazolate anion, (4-PyPz) =3-(4-pyridyl)pyrazolate anion, both C H N , Ln=Sm, Eu, Gd, Tb, Dy, were obtained as highly luminescent frameworks by reaction of the lanthanide metals (Ln) with the aromatic heterocyclic amine ligands 3-PyPzH and 4-PyPzH. The compounds form two isotypic series of 3D coordination polymers and exhibit fair thermal stability up to 360 °C. The luminescence properties of all ten compounds were determined in the solid state, with an antenna effect through ligand-metal energy transfer leading to high efficiency of the luminescence displayed by good quantum yields of up to 74 %. The emission is mainly based on ion-specific lanthanide-dependent intra 4 f-4 f transitions for Tb : green, Dy : yellow, Sm : orange-red, Eu : red. For the Gd -containing compounds, the yellow emission of ligand triplet-based phosphorescence is observed at room temperature and 77 K. Co doping of the Gd-containing frameworks with Eu and Tb allow further shifting of the chromaticity towards white light emission.
通式为[Ln(3-PyPz)₃]和[Ln(4-PyPz)₃]的均配型三维配位聚合物（其中(3-PyPz)=3-(3-吡啶基)吡唑酸根阴离子，(4-PyPz)=3-(4-吡啶基)吡唑酸根阴离子，二者均为C₉H₇N₂，Ln=Sm、Eu、Gd、Tb、Dy）是通过镧系金属（Ln）与芳香杂环胺配体3-PyPzH和4-PyPzH反应得到的高发光框架材料。这些化合物形成了两个同型系列的三维配位聚合物，在高达360 °C的温度下表现出良好的热稳定性。所有十种化合物的发光性质均在固态下测定，通过配体-金属能量转移产生的天线效应导致发光效率高，量子产率高达74 %。发射主要基于特定离子的镧系元素依赖性4f-4f内跃迁：Tb为绿色，Dy为黄色，Sm为橙红色，Eu为红色。对于含Gd的化合物，在室温及77 K下观察到基于配体三线态磷光的黄色发射。用Eu和Tb对含Gd的框架进行共掺杂可使色度进一步向白光发射偏移。
