Effect of Extended π Conjugation on the Spectroscopic and Electrochemical Properties of Boron Difluoride Formazanate Complexes
Effect of Extended π Conjugation on the Spectroscopic and Electrochemical Properties of Boron Difluoride Formazanate Complexes
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DOI：
10.1021/acs.joc.5b00620
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发表时间：
2015-05-15
影响因子：
3.6
通讯作者：
Gilroy, Joe B.
中科院分区：
文献类型：
--
作者：
Barbon, Stephanie M.;Staroverov, Viktor N.;Gilroy, Joe B.
通过系统比较苯基和萘基取代的衍生物，研究了扩展π共轭对二氟化硼（BF2）甲氮酸盐配合物光谱和电化学性质的影响。所描述的每种 BF2 配合物均通过 H-1、C-13、B-11 和 F-19 NAIR 光谱、循环伏安法、红外光谱、紫外-可见吸收和发射光谱以及质谱进行表征。 X 射线晶体学和电子结构计算用于合理化观察到的趋势，包括直接比较 3-氰基-、3-硝基-和 3-苯基-取代的 BF2 甲氮酸盐络合物。在所有情况下，随着π共轭的系统扩展（通过用萘基取代苯基），最大吸收和发射的波长发生红移，荧光量子产率增加（高达10倍），并且甲氮酸盐配合物电化学转化为其自由基阴离子和双阴离子形式发生在较低的负电势（更容易减少）下。
The effect of extended pi conjugation on the spectroscopic and electrochemical properties of boron difluoride (BF2) formazanate complexes was studied by the systematic comparison of phenyl- and naphthyl-substituted derivatives. Each of the BF2 complexes described was characterized by H-1, C-13, B-11, and F-19 NAIR spectroscopy, cyclic voltammetry, infrared spectroscopy, UV-vis absorption and emission spectroscopy, and mass spectrometry. X-ray crystallography and electronic structure calculations were used to rationalize the trends observed, including direct comparison of 3-cyano-, 3-nitro-, and 3-phenyl-substituted BF2 formazanate complexes. In all cases, the wavelengths of maximum absorption and emission were red-shifted as pi conjugation was systematically extended (by replacing phenyl with naphthyl), fluorescence quantum yields increased (up to 10-fold), and electrochemical conversion of the formazanate complexes to their radical anion and dianion forms occurred at less negative potentials (easier to reduce).