Improvement of Solid Photoluminescence of Tridentate Schiff Base Pt(II) Foldamer by Hybridizing Poly (4‐Vinylpyridine)
Improvement of Solid Photoluminescence of Tridentate Schiff Base Pt(II) Foldamer by Hybridizing Poly (4‐Vinylpyridine)
复制标题
通过杂化聚（4-乙烯基吡啶）改进三齿希夫碱 Pt(II) 折叠体的固体光致发光
DOI：
10.1002/ejic.202200544
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发表时间：
2022
影响因子：
2.3
通讯作者：
Watase Seiji
中科院分区：
文献类型：
--
作者：
Achira Hiroto;Nakamura Masashi;Shidzuma Motohiro;Watase Seiji
合成了一系列与 2-亚甲基丙烷-1,3-二基连接的双（三齿席夫碱铂）络合物（Pt2L2），并检查了它们的光物理性质以分析不同的固态。 X射线晶体分析表明，以4-乙烯基吡啶（Pt2L24VP）为配体的Pt2L2具有螺旋折叠结构。与类似的单核配合物相比，它引起了高场化学位移和紫外-可见吸收光谱的红移。由于 DMSO 的空间排斥，含有二甲亚砜的 Pt2L2（Pt2L2DMSO）不具有这种螺旋折叠结构。由于晶体堆积，Pt2L24VP 没有表现出固体光致发光。聚（4-乙烯基吡啶）（P4VP）和Pt2L2DMSO（Pt2L2DMSO−P4VP）的混合物在紫外-可见吸收和激发光谱中表现出与Pt2L24VP相似的红移，这意味着Pt2L2具有P4VP配位的螺旋折叠结构。 Pt2L2DMSO−P4VP 表现出固体光致发光，其磷光寿命 (2.4 μs) 比 Pt2L24VP 晶体 (0.5 μs) 更长，表明 Pt2L2frames 在 P4VP 矩阵中的调节聚集。
A series of bis(tridentate Schiff base platinum) complex (Pt2L2) linked with 2‐methylenepropane‐1,3‐diyl were synthesized, and their photophysical properties were examined to analyze different solid states. X‐ray crystallographic analysis indicated that Pt2L2containing 4‐vinylpyridine (Pt2L24VP) as a ligand had a helically‐folded structure. It caused upfield chemical shifts and a redshift in UV‐Vis absorption spectra compared to the analogous mononuclear complex. Pt2L2containing dimethylsulfoxide (Pt2L2DMSO) had no such helically‐folded structure due to the steric repulsion of DMSO. Pt2L24VP did not exhibit solid photoluminescence owing to the crystal packing. The mixture of poly(4‐vinylpyridine) (P4VP) and Pt2L2DMSO (Pt2L2DMSO−P4VP) showed a similar redshift in UV‐Vis absorption and excitation spectra to Pt2L24VP, implying the helically‐folded structure of Pt2L2with P4VP coordination. The Pt2L2DMSO−P4VP exhibited solid photoluminescence with a longer phosphorescence lifetime (2.4 μs) than the Pt2L24VP crystals (0.5 μs), indicating regulated aggregation of the Pt2L2frames in the P4VP matrix.