Effect of phosphine ligand on the optical absorption/emission properties of platinum-containing conjugated polymers
Effect of phosphine ligand on the optical absorption/emission properties of platinum-containing conjugated polymers
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DOI：
10.1039/c7py01886j
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发表时间：
2018-04
影响因子：
4.6
通讯作者：
Yuko Miyagi;Taichi Sotani;T. Yajima;N. Sano;F. Sanda
中科院分区：
文献类型：
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作者：
Yuko Miyagi;Taichi Sotani;T. Yajima;N. Sano;F. Sanda
D-羟基苯基甘氨酸衍生的二碘亚芳基单体和具有各种取代基的含铂二乙炔基亚苯基单体的Sonogashira-Hagihara偶联聚合，HCC-C6 H 4-CC-Pt（PR 3）2-CC-C6 H 4-CCH，1：R = C4 H 9，2：R = C8 H 17，3：R =环己基，4：R =苯基，和5：R = 4-甲氧基苯基，得到相应的聚合物1′ ~ 5 ′，数均分子量为4600 ~ 22000。聚合物可溶于CHCl_3、CH_2Cl_2、THF和DMF。CD/UV-vis光谱分析和动态光散射研究表明，1′-5′在THF/甲苯混合溶剂中形成手性调控的单分子结构，而在THF/MeOH混合溶剂中形成手性聚集体.聚合物主链的共轭与芳基基团键合到P的单体相比，与烷基基团键合到P的单体。HOMO-LUMO间隙和膦配体之间的关系合理地解释了DFT计算。聚合物表现出光致发光，量子产率范围从0.003%到0.9%。光致发光强度通过改变膦取代基来控制。随着膦配体烷基链长的增加，聚合物的热稳定性增加，折射率降低。
The Sonogashira–Hagihara coupling polymerization of a D-hydroxyphenylglycine-derived diiodoarylene monomer and platinum-containing diethynylphenylene monomers with various substituents, HCC–C6H4–CC–Pt(PR3)2–CC–C6H4–CCH, 1: R = C4H9, 2: R = C8H17, 3: R = cyclohexyl, 4: R = phenyl, and 5: R = 4-methoxyphenyl, gave the corresponding polymers 1′–5′ with number-average molecular weights of 4600–22 000. The polymers were soluble in CHCl3, CH2Cl2, THF and DMF. CD/UV–vis spectroscopic analysis and dynamic light scattering measurements revealed that 1′–5′ formed chirally regulated unimolecular structures in THF/toluene mixtures, while formed chiral aggregates in THF/MeOH mixtures. The conjugation of the polymer main chain was longer for monomers with aryl groups bonded to P compared to monomers with alkyl groups bonded to P. The relationship between the HOMO–LUMO gaps and phosphine ligands was reasonably explained by DFT calculations. The polymers exhibited photoluminescence with quantum yields ranging from 0.003% to 0.9%. The photoluminescence intensity was controlled by changing the phosphine substituents. The thermal stability of the polymers increased and the refractive index decreased as the alkyl chain length of the phosphine ligand was increased.