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
Synthesis, Spatial Configuration and Spectral Properties of Donor-Acceptor Molecules with Dehydroabietic Acid Triarylamine as Donors
TAN Guan-ni1, GAO Hong1,2*, SONG Jie3, SHANG Shi-bin1,2, SONG Zhan-qian1,2
1. 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
2. Research Institute of Forestry New Technology, Chinese Academy of Forestry, Beijing 100091, China
3. Department of Chemistry and Biochemistry, University of Michigan-Flint, Flint, MI 48502, USA
Abstract：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.
檀贯妮，高 宏，宋 杰，商士斌，宋湛谦. 脱氢枞酸基D-A型分子的合成、空间构型及光谱性能[J]. 光谱学与光谱分析, 2019, 39(07): 2083-2090.
TAN Guan-ni, GAO Hong, SONG Jie, SHANG Shi-bin, SONG Zhan-qian. Synthesis, Spatial Configuration and Spectral Properties of Donor-Acceptor Molecules with Dehydroabietic Acid Triarylamine as Donors. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2019, 39(07): 2083-2090.
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