Crystallographic, Photophysical, NMR Spectroscopic and Reactivity Manifestations of the "8-Heteroaryl Effect" in 4,4-Difluoro-8-(C4H3X)-4-bora-3a,4a-diaza-s-indacene (X=O, S, Se) (BODIPY) Systems
Crystallographic, Photophysical, NMR Spectroscopic and Reactivity Manifestations of the "8-Heteroaryl Effect" in 4,4-Difluoro-8-(C4H3X)-4-bora-3a,4a-diaza-s-indacene (X=O, S, Se) (BODIPY) Systems
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DOI：
10.1021/ic902467h
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发表时间：
2010-06-07
影响因子：
4.6
通讯作者：
Churchill, David G.
中科院分区：
文献类型：
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作者：
Kim, Kibong;Jo, Changbum;Churchill, David G.
我们合成了三个新的，但密切相关的，杂环内消旋取代（BODIPY）荧光团4，4-二氟-8-（C4 H3 X）-4-硼-3a，4a-二氮杂-s-引达省，并对其进行了全面表征（X=O，2-/3-呋喃基（7/10）; Se，2-硒烯基（9））通过使用2-D NMR（COSY，HSQC和HMBC），单晶X射线衍射，质谱，元素分析，紫外-可见光谱和荧光衰减寿命，用于与先前报道的噻吩类物质进行比较（X = S，2-/3-噻吩基（8/11））。具体地，7-11在形式上通过硫族元素（O、S或Se）或硫族元素布置而不同。固态比较揭示了来自细微结构差异的主要影响，这使得人们能够深入了解荧光晶体工程。对于2-杂原子取代，分子量的增加（7 < 8 < 9）与增加的晶胞体积、C4 H3 X基团的更大正交性和（F-Phi）的较低值相关。溶液和密度泛函理论（DFT）结果揭示了神经学荧光研究潜力的有趣平台。2-基于吸电子效应，杂环物种相对于3-杂环物种显示出更大的λ（abs，max/em，max）值。10具有最大的Phi（F）值（0.25，甲苯）。发现荧光寿命为2.60（7），0.74（8），0.27（9），4.26（10）和1.86 ns（11）; λ（em，max）衰减研究了8。杂环的差异也会导致不同的吡咯NMR光谱位移。这些化合物抗分解，如从用H2 O2滴定所见，并且当它们被Br-2溴化时均匀地经历λ（abs，max）红移和降低的Phi（F）值。
We have synthesized and fully characterized three novel, yet closely related, heterocyclically meso-substituted (BODIPY) fluorophores 4,4-difluoro-8-(C4H3X)-4-bora-3a,4a-diaza-s-indacene (X=O, 2-/3-furyl (7/10); Se, 2-selenenyl (9)) through the use of 2-D NMR (COSY, HSQC, and HMBC), single crystal X-ray diffraction, mass spectrometry, elemental analysis, UV-vis spectroscopy, and fluorescent decay lifetimes, for comparison to the previously reported thienyl species (X = S, 2-/3-thienyl (8/11)). Specifically, 7-11 differ formally by chalcogen (O, S, or Se) or chalcogen placement. Solid state comparisons reveal major effects stemming from subtle structural differences which allows for insights into fluorescent crystal engineering. For the 2-heteroatom substitution, an increase in molecular weight (7 < 8 < 9) correlates with an increasing unit cell-volume, a greater orthogonality for the C4H3X group, and a lower value for (F-Phi, Solution and density functional theory (DFT) results reveal interesting platforms for potential in fluorescent studies for neurology. 2-Heterocyclic species show larger lambda(abs,max/em,max) values relative to 3-heterocyclic ones, based on electron withdrawing effects. 10 has the greatest Phi(F) value herein (0.25, toluene). Fluorescence lifetimes were found to be 2.60 (7), 0.74 (8), 0.27 (9), 4.26 (10), and 1.86 ns (11); lambda(em,max) decay was studied for 8. Heterocyclic differences give rise to somewhat different pyrrolic NMR spectroscopic shifts as well. These compounds resist decomposition as seen from titrations with H2O2, and uniformly undergo lambda(abs,max) red-shifting and lowered Phi(F) values as they become brominated with Br-2.