脱氢枞酸基D-A型分子的合成、空间构型及光谱性能  

Synthesis, Spatial Configuration and Spectral Properties of Donor-Acceptor Molecules with Dehydroabietic Acid Triarylamine as Donors

作　　者：檀贯妮 高宏[1,2] 宋杰 商士斌[1,2] 宋湛谦 TAN Guan-ni;GAO Hong;SONG Jie;SHANG Shi-bin;SONG Zhan-qian(Institute of Chemical Industry of Forest Products,Chinese Academy Forestry/National Engineering Lab for Biomass Chemical Utilization/Key and Open Lab of Forest Chemical Engineering,SFA/Key Lab of Biomass Energy and Material,Nanjing 210042,China;Research Institute of Forestry New Technology,Chinese Academy of Forestry,Beijing 100091,China)

机构地区：[1]中国林业科学研究院林产化学工业研究所、生物质化学利用国家工程实验室、国家林业局林产化学工程重点开放性实验室、江苏省生物质能源与材料重点实验室,江苏南京210042 [2]中国林业科学研究院林业新技术研究所,北京100091 [3]Department of Chemistry and Biochemistry,University of Michigan-Flint,Flint,MI 48502,USA

出　　处：《光谱学与光谱分析》2019年第7期2083-2090,共8页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(31670576)资助

摘　　要：对三苯胺进行溴代和C-N偶联反应合成4-萘基三苯胺(a),对脱氢枞酸进行酯化、溴代、硝化、还原和C-N偶联反应合成13-[N,N-(4-萘基苯基)-苯基]胺基-脱异丙基脱氢枞酸甲酯(b)及13-[N,N-双(4-萘基苯基)]胺基-脱异丙基脱氢枞酸甲酯(c)两个化合物,通过1HMNR,13CMNR及MS对化合物的结构进行表征。为了研究化合物结构与光谱性能之间的关系,首先利用Gaussian09程序采用密度泛函DFT/B3LYP方法,对三个化合物的空间构型进行全优化,得到它们的键长、键角和二面角,对比发现脱氢枞酸骨架和萘环的引入会影响化合物的共平面性,而萘环的引入会增大化合物的共轭程度。光谱性能方面,研究了三种化合物在甲醇、二氧六环、四氢呋喃、二氯甲烷和环己烷这5种极性逐渐减小的溶剂中的荧光发射光谱和紫外吸收光谱。结果表明,在荧光光谱中,化合物a,b和c在不同极性溶剂中最大荧光发射波长均有不同程度位移,在甲醇中最大,在环己烷中最小,但是位移并非随着极性的增大而只发生红移,在二氯甲烷、四氢呋喃和二氧六环3种极性依次增大的溶剂中,a,b,c的荧光发射波长均随着溶剂极性的增大而发生较大程度的蓝移;在同一溶剂中,化合物b和c相对于a的荧光发射波长依次发生红移,c的红移程度与b差距不大。紫外吸收光谱中,三个化合物在不同极性溶剂中的最大吸收波长也有差异,在200~250nm区间,三个化合物均在二氯甲烷中有较大位移,在300~350nm区间,在甲醇中位移较大,而在250~300nm区间,最大吸收波长差别不大;在同一溶剂中,它们在300~350nm区间的最大吸收波长差别较大,化合物c较a红移26nm。结合结构优化所得数据可以证明,化合物的共轭程度对荧光发射光谱和紫外吸收光谱均有影响,而共平面性对荧光发射光谱影响较大。化合物a,b和c在不同极性溶剂中荧光发射光谱和紫外吸收光谱的较大变化,表�Three compounds 4-naphthyltriphenylamine(a), methyl 13-[N,N-(4-naphthylphenyl)-phenyl]aminodeisopropyldehydroabietate(b) and methyl 13-[N,N-Bis(4-naphthylphenyl)]aminodeisopropyldehydroabietate(c) were synthesized by esterification, bromine reaction, nitration reaction, reduction reaction and C-N coupling reaction using triphenylamine and dehydroabietic acid respectively. Their structures were characterized by 1H MNR, 13C MNR, and MS. In order to study the relationship between structures and spectral properties of compounds, molecular configuration of compounds were optimized by DFT/B3 LYP using Gaussian 09, then their bond lengths, bond angles, and dihedral angles were obtained and compared. The results show that the introduction of dehydroabietic acid skeletons and naphthalene rings affect the coplanarity and the introduction of naphthalene rings increase their conjugated degree. Their fluorescence emission spectra and UV absorption spectra in five solvents with decreasing polarity, such as methanol, dioxane, THF, dichloromethane and cyclohexane were also studied. The results show that the maximum fluorescence emission wavelengths of compounds differ greatly in different polar solvents. The fluorescence emission wavelength is the largest in methanol, and which is the smallest in cyclohexane, however, the fluorescence emission wavelengths are not increase with increasing polarity, the fluorescence emission wavelengths of compounds have large degree of blue-shift in dichloromethane, THF and dioxane with increasing polarity. In the same solvent, the maximum fluorescence emission wavelengths of compounds b and c were red-shift relative to compound a, the red-shift degree of compound c was similar to that of compound b. In UV absorption spectra, the maximum absorption wavelengths of compounds a, b and c in different polar solvents are also different. In 200~250 nm range, their maximum absorption wavelengths have big shift in dichloromethane from which is in other four solvents, but in 300~350 nm range, their maximum

关 键 词：脱氢枞酸三芳胺 D-A结构 合成 空间构型 光谱性能 

分 类 号：TQ351[化学工程]