锌卟啉-蒽醌-2-磺酸酯轴向配位性能研究
|
摘要
本文以三种锌卟啉-蒽醌-2-磺酸酯为主体化合物,利用紫外-可见光谱法研究主体化合物与客体咪唑、吡啶、N-甲基咪唑进行的轴向配位反应,结果表明:①对于同一主体,客体的配位能力为:N-甲基咪唑>咪唑>吡啶;②对于同一客体,主体的配位能力是5-(苯基-4-(蒽醌-2-磺酸酯))-10,15,20-三(4-氯苯基)卟啉锌>5-(苯基-4-(蒽醌-2-磺酸酯))-10,15,20-三苯基卟啉锌>5-(苯基-4-(蒽醌-2-磺酸酯))-10,15,20-三(4-甲氧基苯基)卟啉锌;③实验结果经计算表明主客体之间以摩尔比1∶1配位,随着温度的升高反应的平衡常数逐渐减小,焓变Δ_rH_m~Θ<0,反应是放热反应。
In this paper,three porphyrin-anthraquinone-2-sulfonate Zinc complexes were used as the hosts.The axial coordination reactions between the hosts and the guests imidazole,pyridine and N-methylimidazole were studied by Uv-Vis spectroscopy.The results showed that:①the coordination ability of the same guest was N-methylimidazole>imidazole>pyridine;②for the same guest,the coordination ability of the host was 5-[4-(anthraquinone-2-sulfonyloxy)phenyl]-10,15,20-tri(4-chlorophenyl)porphyrin Zinc>5-[4-(anthraquinone-2-sulfonyloxy)phenyl]-10,15,20-triphenylporphyrin Zinc>5-[4-(anthraquinone-2-sulfonyloxy)phenyl]-10,15,20-tri(4-methoxyphenyl)porphyrin Zinc;③the molar ratio of the coordination reaction was 1∶1.The equilibrium constants of the reaction decreased gradually with the increase of temperature,and the coordination reactions were exothermic.
In this paper,three porphyrin-anthraquinone-2-sulfonate Zinc complexes were used as the hosts.The axial coordination reactions between the hosts and the guests imidazole,pyridine and N-methylimidazole were studied by Uv-Vis spectroscopy.The results showed that:①the coordination ability of the same guest was N-methylimidazole>imidazole>pyridine;②for the same guest,the coordination ability of the host was 5-[4-(anthraquinone-2-sulfonyloxy)phenyl]-10,15,20-tri(4-chlorophenyl)porphyrin Zinc>5-[4-(anthraquinone-2-sulfonyloxy)phenyl]-10,15,20-triphenylporphyrin Zinc>5-[4-(anthraquinone-2-sulfonyloxy)phenyl]-10,15,20-tri(4-methoxyphenyl)porphyrin Zinc;③the molar ratio of the coordination reaction was 1∶1.The equilibrium constants of the reaction decreased gradually with the increase of temperature,and the coordination reactions were exothermic.
引文
[1]Yang S B,Sun B,Ou Z P,et al.β-nitro-substituted free-base,iron(III)and manganese(III)tetraarylporphyrins:synthesis,electrochemistry and effect of the NO2 substituent on spectra and redox potentials in non-aqueous mdia[J].Porphyrins Phthalocyanines,2013,17:857-869.
[2]侯月平,陈雪雁,房媛媛,等.取代锰卟啉的轴向配位反应及平衡常数的测定[J].理化检验(化学分册),2017,08,933-937.
[3]Sun B,Ou Z,Yang S,et al.Synthesis and electrochemistry of β-pyrrole nitrosubstituted cobalt(II)porphyrins.The effect of the NO2 group on redox potentials,the electron transfer mechanism and catalytic reduction of molecular oxygen in acidic media[J].Dalton Trans,2014,43,10809-10815.
[4]宋熙熙,金鑫,宗乾收,等.卟啉衍生物与功能性蛋白作用的光谱学性质研究[J].应用化工,2015,44(9):1674-1676.
[5]李全文,郭江宁.阳离子卟啉与牛血清白蛋白相互作用的光谱研究[J].分子科学学报,2014,30(4):345-353.
[6]李济婷,胡炳成,余传明,等.吡啶基二噻吩乙烯轴向配位锰(Ⅱ)-卟啉化合物的合成及性质[J].应用化学,2017,04,402-407.
[7]彭晓霞,新型卟啉-蒽醌化合物的合成及其荧光性能的研究[D].硕士,20030501.
[8]王树军,彭玉苓,刘光仙.尾式锌卟啉轴向配位反应的光谱性质[J].化学通报,2013,76(4):375-380.
[9]王树军.光谱法研究硝基苯基卟啉锌与咪唑类的轴向配位效应[J].应用化学,2010(06):721-726.
[10]沙秋月,袁雪梅,王小雨,等.Meso位单取代卟啉及其配合物的合成、表征和光谱性质[J].无机化学学报,2016,32(7):1239-1302.
[11]李晨,李剑峰,段武彪,等.一种新型尾式卟啉的合成及其光电性质研究[J].发光学报,2016,37(2):158-164.
[12]王湘利,汪华华,张蕾,等.新型羧酸卟啉锌配合物与人血清蛋白的作用[J].光谱学与光谱分析,2016,36(9):2894-2900.
[13]Frisch M J,Trucks G W,Schlegel H B,et al.Gaussian 09,Gaussian,Inc.,Pittsburgh,PA 2009.
[2]侯月平,陈雪雁,房媛媛,等.取代锰卟啉的轴向配位反应及平衡常数的测定[J].理化检验(化学分册),2017,08,933-937.
[3]Sun B,Ou Z,Yang S,et al.Synthesis and electrochemistry of β-pyrrole nitrosubstituted cobalt(II)porphyrins.The effect of the NO2 group on redox potentials,the electron transfer mechanism and catalytic reduction of molecular oxygen in acidic media[J].Dalton Trans,2014,43,10809-10815.
[4]宋熙熙,金鑫,宗乾收,等.卟啉衍生物与功能性蛋白作用的光谱学性质研究[J].应用化工,2015,44(9):1674-1676.
[5]李全文,郭江宁.阳离子卟啉与牛血清白蛋白相互作用的光谱研究[J].分子科学学报,2014,30(4):345-353.
[6]李济婷,胡炳成,余传明,等.吡啶基二噻吩乙烯轴向配位锰(Ⅱ)-卟啉化合物的合成及性质[J].应用化学,2017,04,402-407.
[7]彭晓霞,新型卟啉-蒽醌化合物的合成及其荧光性能的研究[D].硕士,20030501.
[8]王树军,彭玉苓,刘光仙.尾式锌卟啉轴向配位反应的光谱性质[J].化学通报,2013,76(4):375-380.
[9]王树军.光谱法研究硝基苯基卟啉锌与咪唑类的轴向配位效应[J].应用化学,2010(06):721-726.
[10]沙秋月,袁雪梅,王小雨,等.Meso位单取代卟啉及其配合物的合成、表征和光谱性质[J].无机化学学报,2016,32(7):1239-1302.
[11]李晨,李剑峰,段武彪,等.一种新型尾式卟啉的合成及其光电性质研究[J].发光学报,2016,37(2):158-164.
[12]王湘利,汪华华,张蕾,等.新型羧酸卟啉锌配合物与人血清蛋白的作用[J].光谱学与光谱分析,2016,36(9):2894-2900.
[13]Frisch M J,Trucks G W,Schlegel H B,et al.Gaussian 09,Gaussian,Inc.,Pittsburgh,PA 2009.