取代基对咪唑[4,5-f]-1,10-邻菲罗啉Ru(Ⅱ)配合物的温敏性能影响

The Effect of Substituent on the Temperature Sensitive Properties of Imidazo[4,5-f]-1,10-phenanthroline Ruthenium(Ⅱ)Complex

合成了3种具有不同取代基的咪唑[4，5-f]-1，10-邻菲罗啉配体L1～L3及其Ru（Ⅱ）配合物[Ru（L1）3]、[-Ru（L2）3]和[-Ru（L3）3]，并进行了表征。这些Ru（Ⅱ）配合物在溶液中具有π→π＊跃迁吸收峰和金属到配体的电荷转移跃迁（MLCT）吸收峰，其发光峰位约为590nm左右。将Ru（Ⅱ）配合物掺杂到聚甲基丙烯酸甲酯（PMMA）中得到相应的温敏漆。Ru（Ⅱ）配合物在PMMA膜中的吸收峰精细结构消失，且在长波方向663nm附近有新的发射峰，表明Ru（Ⅱ）配合物在PMMA膜中有聚集。温度升高后，Ru（Ⅱ）配合物在PMMA膜中的发射峰强度逐渐减弱。分别计算了在30-60℃和60-90℃区间内非辐射活化能Enr和温度灵敏度ST。结果表明，具有苯基取代的咪唑[4，5-f]-1，10-邻菲罗啉配体的[-Ru（L1）3]配合物，比咪唑[4，5-f]-1，10-邻菲罗啉Ru（Ⅱ）配合物[-Ru（L2）3]及烷基取代基的咪唑[4，5-f]-1，10-邻菲罗啉Ru（Ⅱ）配合物[Ru（L3）3]具有更高的温度灵敏度。

Three imidazo[-4,5-f2-1,10-phenanthroline derivatives L1-L3, with different substitutes, and their Ru（ Ⅱ ） complexes have been synthesized and characterized. These Ru（ Ⅱ ） complexes show characteristic π→π＊transition and metal-ligand charge transfer （MLCT） transition absorptions, and emission maximums at 590 nm. The Ru （Ⅱ ） complexes have been doped into the Poly （methyl methacrylate） （PMMA） and obtained thetemperature sensitive paint. In PMMA film, the fined structure of the absorption spectra of the Ru （ Ⅱ ） complexes disappeared, and a new emission peak at the longer wavelength （663 nm） appeared, indicating theaggregation of Ru（ Ⅱ ） complexes. The emission intensity of the Ru（ Ⅱ ） complexes in PMMA film decreases gradually with increase of the temperature. The activation energy of non-radiative process （Enr） temperaturesensitivity （ST） of compounds are calculated in the range of 30 60 ℃and 60 90 ℃, respectively. The results indicate that [Ru（L1 ）3 ] with phenyl substituted imidazo[-4,5-f]-1, 10-phenanthroline has relatively higher STthan [Ru（L2）3] with imidazo[4,5-f]-1, 10-phenanthroline and [Ru（L3 ）3 ] with alkyl substituted imidazo[4,5 f]-1, 10-phenanthroline.