脱氢枞酸芳胺化合物的结构优化及溶致变色行为

Structure Optimization by DFT and Solvatochromism of Series of Dehydroabietic Acid-based Arylamines

采用Gaussian 03程序的密度泛函DFT/B3LYP方法,对两个系列脱氢枞酸芳胺化合物5a^5g(13-(苯基)胺基-脱异丙基脱氢枞酸甲酯(5a)、13-(4-甲氧基苯基)胺基-脱异丙基脱氢枞酸甲酯(5b)、14-(苯基)胺基-脱氢枞酸甲酯(5c)、13-(8-喹啉)胺基-脱异丙基脱氢枞酸甲酯(5d)、13-(α-溴萘)胺基-脱异丙基脱氢枞酸甲酯(5e)、13-(对溴联苯基)胺基-脱异丙基脱氢枞酸甲酯(5f)、13-[N-(4-甲基苯基)]胺基-脱异丙基脱氢枞酸甲酯(5g))和6a^6h(13-[N,N-(4-甲氧基苯基)-苯基]胺基-脱异丙基脱氢枞酸甲酯(6a)、13-[N,N-(对溴联苯)-苯基]胺基-脱异丙基脱氢枞酸甲酯(6b)、13-[N,N-(4-甲基苯基)-苯基]胺基-脱异丙基脱氢枞酸甲酯(6c)、13-(N,N-双苯基)胺基-脱异丙基脱氢枞酸甲酯(6d)、13-[N,N-双(4-甲氧基苯基)]胺基-脱异丙基脱氢枞酸甲酯(6e)、13-[N,N-(α-萘)-苯基]胺基-脱异丙基脱氢枞酸甲酯(6f)、13-[N,N-双(4-甲基苯基)]胺基-脱异丙基脱氢枞酸甲酯(6g)、13-(N,N-联苯-苯基)胺基-脱异丙基脱氢枞酸甲酯(6h))的几何构型进行全优化,并研究了它们在5种不同极性溶剂中的荧光发射光谱,探讨了化合物的结构与其发光性能之间的关系。结果表明:芳环的共轭长度及芳环上取代基的种类均影响其共轭程度,从而影响其荧光性能。二芳胺化合物(5a^5g)和三芳胺化合物(6f、6b和6h)在不同极性溶剂中发射波长发生明显位移,所有化合物在不同极性溶剂中具有不同的荧光发射强度,具备作为荧光分子探针探测分子外部环境极性大小的潜能。

Molecular configuration of compounds 5a-5g（methyl 13-（phenyl） aminodeisopropyldehydroabietate（5a）,Methyl 13-（4-methoxyphenyl） aminodeisopropyldehydroabietate（5b）,methyl 14-（phenyl） aminodehydroabietate（5c）,methyl 13-（8-quinoline） aminodeisopropyldehydroabietate（5d）,methyl 13-（α-naphthalene）aminodeisopropyldehydroabietate（5e）,methyl 13-（ p-bromodiphenyl ） aminodeisopropyldehydroabietate （ 5f ）, methyl 13-（ 4-methylphenyl ） aminodeisopropyldehydroabietate （5g）） and 6a-6h（Methyl 13-[N,N-（4-methoxyphenyl）-phenyl]aminodeisopropyldehydroabietate（6a）,methyl 13-[N,N -（p-bromobiphenyl ）-phenyl ] aminodeisopropyldehydroabietate （ 6b ）, methyl 13-[ N, N-（ 4-methylphenyl ）-phenyl ]＆amp;nbsp;aminodeisopropyldehydroabietate（6c）,methyl 13-（N,N-bis-phenyl） aminodeisopropyldehydroabietate（6d）,methyl 13-[N, N-bis （ 4-methoxyphenyl ）] aminodeisopropyldehydroabietate （ 6e ）, methyl 13-[ N, N- （ α-naphthalene ）-phenyl ] aminodeisopropyldehydroabietate（6f）,methyl 13-[N,N -bis（4-methylphenyl）-phenyl]aminodeisopropyldehydroabietate（6g）, methyl 13-[N,N-biphenyl-phenyl]aminodeisopropyldehydroabietate（6h）） were optimized by DFT/B3LYP using Gaussian 03. Their fluorescent properties in solvents of different polarity were analysed, and the relationship between structures and properties were also discussed. The results show that the conjugated length or substituent groups on aryl rings of compounds have big effect on their conjugated degree, and then affect their fluorescent properties. Compounds 5a -5g, 6f, 6b and 6h have deffrent fluorescent emmision wavelengths and all compounds show defferent fluorescent intensity in defferent polarity solvents. Above properties indicate that these compounds have potential to be used as fluorescent probes in different polarity environment.