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1H MNR, 13C MNR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Gaussian 09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200～250 nm区间, 三个化合物均在二氯甲烷中有较大位移, 在300～350 nm区间, 在甲醇中位移较大, 而在250～300 nm区间, 最大吸收波长差别不大; 在同一溶剂中, 它们在300～350 nm区间的最大吸收波长差别较大, 化合物c较a红移26 nm。 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, 表明它们有明显的溶致变色行为, 具有作为分子探针探测外部环境极性大小的潜能。

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/B3LYP 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 absorption wavelengths have big shift in methanol, and they have almost the same wavelengths in five solvents in 250～300 nm range. In the same solvent, their maximum absorption wavelengths in 300～350 nm range differ greatly, and compound c has a big red-shift (26 nm) from a. Combining with the structural optimization datas, it shows that the conjugated degree of compounds has a great effect on the fluorescence emission spectra and the UV absorption spectra, however, coplanarity affects the fluorescence emission spectra of compounds significantly. The differences in fluorescence emission spectra and UV absorption spectra of compounds a, b and c in different polar solvents indicate that three compounds have significant solvatochromism effect, which means they have potential to be used as fluorescent probes in different polar environment.