1,3,5,7-四甲基氟硼二吡咯甲川的合成、晶体结构及密度泛函理论研究

摘要

1,3,5,7-tetramethyl-3a,4a-diaza-s-indacene p-toluenesulfonate (T1) was synthesized by solvent-free method using 2,4-dimethylpyrrole,triethyl orthoformate and p-toluenesulfonic acid.1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (F1) was synthesized by solvent-free method using T1,boron trifluoride diethyl ether and triethylamine.The structures of compounds have been characterized by 1H NMR and single-crystal Xray diffraction.The results show that T1 belongs to monoclinic system,space group P21/c with a=0.777 3(3) nm,b=1.518 5(5)nm,c=1.612 2(5) nm,β=91.923(12)°,V=1.901 9(11) nm3,Z=4 and that F1 belongs to monoclinic system,space group P21 with a=0.775 02(1) nm,b=1.444 20(3) nm,c=1.174 35(2) nm,β=107.779 5(9)°,V=1.251 65(4) nm3,Z=4.In four different solvent,the UV-Vis spectrum of T1,the UV-Vis and steady-state fluorescence spectra of F1 were determined.The possible derived way of T1 and F1 were investigated by the density functional calculation and the front orbital theory.%以2,4-二甲基吡咯、原甲酸三乙酯以及对甲苯磺酸为原料,无溶剂下合成了1,3,5,7-四甲基对甲苯磺酸二吡咯甲川(T1);以T1、三氟化硼乙醚以及三乙胺为原料,无溶剂下合成了1,3,5,7-四甲基氟硼二吡咯甲川(F1).利用1H NMR和X射线单晶衍射对其进行了表征.结果表明:T1属于单斜晶系,P21/c空间群,晶胞参数为a=0.777 3(3) nm,b=1.518 5(5) nm,c=1.612 2(5) nm,β=91.923(12)°,V=1.901 9(11) nm3,Z=4;F1属于单斜晶系,P21空间群,晶胞参数为a=0.775 02(1) nm,b=1.444 20(3) nm,c=1.174 35(2) nm,β=107.779 5(9)°,V=1.251 65(4) nm3,Z=4.在4种不同溶剂中,测定了T1的紫外可见光谱、F1的紫外可见光谱和稳态荧光光谱.将密度泛函计算与前线轨道理论相结合,研究了T1和F1可能的衍生方式.