含8-羟基喹啉侧基聚酯及其锌和铝配合物的合成与荧光性质

经多步反应合成3种含8-羟基喹啉侧基聚酯(P7~P9),进一步与无水醋酸锌和六水氯化铝反应,得到6种聚酯锌、铝配合物(P7-Zn~P9-Zn,P7-Al~P9-Al)。 采用元素分析、红外光谱、紫外可见光谱、核磁共振氢谱、凝胶渗透色谱、热重分析仪、差示扫描量热和荧光光谱等技术手段对其结构和性能进行表征。 P7~P9易溶于N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAC)、二甲基亚砜(DMSO)和N-甲基吡咯烷酮(NMP),P7-Zn~P9-Zn和P7-Al~P9-Al部分溶于DMF、DMAC、DMSO和NMP。 P7~P9的质均相对分子质量(M_w)为1.79×10⁴、2.14×10⁴和2.52×10⁴ g/mol,相对分子质量分布指数PDI为1.54、1.64和1.72。 P7~P9的5%失重温度分别为291.6、291.3和284.9 ℃,P7-Zn~P9-Zn、P7-Al~P9-Al的5%失重温度分别为348.7、339.2、334.6、316.1、316.7和316.0 ℃。 P7~P9的玻璃化转变温度(T_g)分别为121.8、106.2和86.4 ℃,聚酯锌、铝配合物的T_g均高于180 ℃。 P7~P9的DMF溶液(5×10^-5 mol/L)在413~418 nm处发紫色荧光,P7-Zn~P9-Zn、P7-Al~P9-Al的DMF溶液(5×10^-5 mol/L)分别在509~513和485~487 nm处发强绿色荧光,固体分别在516~519和492~497 nm处发强绿色荧光。 P7~P9、P7-Zn~P9-Zn和P7-Al~P9-Al的荧光量子产率分别为5.5%~8.4%、21%~28%和23%~29%。

Synthesis and Fluorescent Properties of Polyesters Containing 8-Hydroxyquinoline Side Groups and Their Zn(Ⅱ) and Al(Ⅲ) Complexes

Three kinds of novel polyesters containing 8-hydroxyquinoline side groups(P7~P9) were synthesized, and subsequently their zinc complexes(P7-Zn~P9-Zn) and aluminum complexes(P7-Al~P9-Al) were obtained by reactions with zinc acetate and aluminum chloride, respectively. The structures and properties of polyesters and their metal complexes were characterized by elemental analysis, infrared(IR), ultraviolet-visable spectroscopy(UV-Vis), proton nuclear magnetic resonance(¹H NMR), gel permeation chromatography(GPC), thermogravimetric analysis(TG), differential scanning calorimetry(DSC) and fluorescence spectroscopy. The polyesters obtained are soluble in N,N-dimethyl formamide(DMF), N,N-dimethyl acetamide(DMAC), dimethylsulfoxide(DMSO), and N-methyl pyrrolidone(NMP). Complexes P7-Zn~P9-Zn and P7-Al~P9-Al can be partially dissolved in DMF, DMAC, DMSO and NMP. The M_w and polydispersity index(PDI) of P7~P9 are 1.79×10⁴, 2.14×10⁴ and 2.52×10⁴ g/mol and 1.54, 1.64 and 1.72 , respectively. The 5% mass loss temperatures of P7~P9, P7-Zn~P9-Zn and P7-Al~ P9-Al are 291.6, 291.3, 284.9, 348.7, 339.2, 334.6, 316.1, 316.7 and 316.0 ℃, respectively. The glass transition temperatures(T_g) of P7~P9 are 121.8, 106.2 and 91.3 ℃, respectively, and T_g of their metal complexes are all higher than 180 ℃. Fluorescence emission peaks of P7~P9 in DMF solution appear at 413~418 nm, emitting weak purple light. Fluorescence emission peaks of P7-Zn~P9-Zn and P7-Al~P9-Al in DMF solution emerged at 509~513 and 485~487 nm, respectively, emitting strong green light, Fluorescence emission peaks of P7-Zn~P9-Zn and P7-Al~P9-Al in solid state located at 516~519 and 492~497 nm, respectively, emitting strong green light. The fluorescence quantum yields of P7~P9, P7-Zn~P9-Zn and P7-Al~P9-Al are 5.5%~8.4%, 21%~28% and 23%~29%, respectively.