Photoluminescent One‐Dimensional Coordination Polymers from Suitable Pyridine Antenna and LnCl3 for Visible and Near‐IR Emission
Photoluminescent One‐Dimensional Coordination Polymers from Suitable Pyridine Antenna and LnCl3 for Visible and Near‐IR Emission
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DOI：
10.1002/ejic.201402973
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发表时间：
2015-02
影响因子：
2.3
通讯作者：
P. Matthes;J. Eyley;J. H. Klein;A. Kuzmanoski;C. Lambert;C. Feldmann;K. Müller‐Buschbaum
中科院分区：
文献类型：
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作者：
P. Matthes;J. Eyley;J. H. Klein;A. Kuzmanoski;C. Lambert;C. Feldmann;K. Müller‐Buschbaum
通过无水LnCl 3与bipy和py反应，合成了一维配位聚合物∞1[LnCl 3（bipy）（py）2]·py [bipy = 4，4 ′-bipyridine，py = pyridine; Ln = Gd，Tb，Dy，Ho，Er，Yb]和∞1[Lu 2Cl 5（bipy）2（py）4]∞1[LuCl 4（bipy）].观察到延伸的锯齿形链和盐状带结构与阳离子和阴离子链的形成。吡啶和4，4 ′-联吡啶配体通过配体的有效敏化，然后通过Ln 3+（Tb 3+，Dy 3+，Er 3+，Yb 3+）离子的发射性4f内跃迁发射，作为镧系元素在可见光和近红外范围内的发光的合适天线。对于∞1[GdCl 3（bipy）（py）2]·py，配位的4，4 ′-联吡啶配体的磷光具有激发态依赖性，导致可见光范围内的配体发射。对于游离配体，这些过程不能观察到。配位聚合物还扩展了相关配合物和金属有机框架（MOFs）的光致发光性质的范围，并显示出高效率，对于Tb 3+化合物的量子产率为86%。
The series of one-dimensional coordination polymers ∞1[LnCl3(bipy)(py)2]·py [bipy = 4,4′-bipyridine, py = pyridine; Ln = Gd, Tb, Dy, Ho, Er, Yb] as well as ∞1[Lu2Cl5(bipy)2(py)4]∞1[LuCl4(bipy)] were synthesized by the reactions of anhydrous LnCl3 with bipy and py. The formation of extended zigzag chains and saltlike band structures with cationic and anionic strands is observed. Pyridine and 4,4′-bipyridine ligands serve as suitable antennas for lanthanide-based luminescence in the visible and near-infrared range through effective sensitization by the ligands followed by emission through the emissive intra-4f transitions of the Ln3+ (Tb3+, Dy3+, Er3+, Yb3+) ions. For ∞1[GdCl3(bipy)(py)2]·py, phosphorescence of the coordinated 4,4′-bipyridine ligand with excitation-dependent chromaticity leads to ligand-based emission in the visible range. These processes cannot be observed for the free ligand. The coordination polymers also extend the range of photoluminescence properties of related complexes and metal–organic frameworks (MOFs) and show high efficiency with a quantum yield of 86 % for the Tb3+ compound.