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

Synthesis,Crystal Structure and Density Functional Theoretical Study of 1,3,5,7-Tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene

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/n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)nm^3,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。

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 X-ray 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/n 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.