新颖的5,15-二(4-(5-乙酰基硫戊氧基)苯基)卟啉化合物的结构和性质的密度泛函理论计算  

Structures and properties of novel 5,15-di[4-(5-acetylsulfanylpentyloxy) phenyl]porphyrin derivatives:Density functional theory calculations

作　　者：朱轶飞[1,2] 齐冬冬[1] 张丽娟[1] 万亮[1] 张跃兴[1] 姜建壮[1] 

机构地区：[1]北京科技大学化学系,北京100083 [2]河北北方学院化学系,张家口075000

出　　处：《中国科学：化学》2010年第11期1631-1641,共11页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(20931001);北京市自然科学基金;国家博士后科学基金的资助

摘　　要：通过密度泛函理论计算比较性地研究了5,15-二(4-(5-乙酰基硫戊氧基)苯基)自由卟啉及其锌配合物的分子结构、电荷性质、分子轨道、电子吸收光谱和红外光谱.这类化合物具有在卟啉相对的两个中位的苯环上连有5-乙酰基硫戊氧基的新颖结构.模拟得到的这两个化合物的分子结构和电子吸收光谱以及红外光谱都与实验测得的符合得很好.通过与未取代的自由卟啉和卟啉锌的结构和性质进行比较,研究了中位取代基、极性溶剂和中心金属取代对此类卟啉化合物结构和性质的影响规律.对化合物的电子吸收光谱中的电子跃迁本质进行了归属,并通过基于正则坐标分析产生的动画对红外光谱的振动模式进行了指认.目前的工作将对理解此类新颖卟啉化合物的结构和性质以及取代基和溶剂效应提供很大的帮助.Density functional theory（DFT） calculations have been carried out in order to compare the molecular structures,atomic charges,molecular orbitals,electronic absorption spectra,and infrared（IR） spectra of the metal-free 5,15-di[4-（5-acetylsulfanylpentyloxy） phenyl]porphyrin H2[DPP（OC5H10SCOCH3） 2]（1）（DPP=5,15-diphenylporphyrin） and its zinc complex Zn[DPP（OC5H10SCOCH3） 2]（2） ,which exhibit novel structures with two 5-acetylsulfanylpentyloxy side chains at the para-positions of opposite meso-attached phenyl groups.The calculated molecular structure and electronic absorption and IR spectra of 1 and 2 are consistent with the experimental results. The influence of meso-substitution,polar solvents,and central metal substitution on the structure and properties of porphyrin derivatives has been investigated by comparing the corresponding data for 1 and 2 with the help of data for the unsubstituted porphyrin derivatives,namely the metal-free porphyrin H2Por（3） and the porphyrinato-zinc compound（4） .The identities of the main transitions in the electronic absorption spectra of 1 and 2 are assigned and the vibrational modes in their IR spectra are identified with the assistance of animated pictures produced based on normal coordinates.The theoretical work presented here will be helpful in increasing our understanding of the structure and spectroscopic properties,as well as substitution and solvent effects,for these novel porphyrin compounds.

关 键 词：卟啉 取代效应 电子吸收光谱 红外光谱 密度泛函理论 

分 类 号：O626[理学—有机化学]