Crystallographic, Photophysical, NMR Spectroscopic and Reactivity Manifestations of the "8-Heteroaryl Effect" in 4,4-Difluoro-8-(C 4H3 X)-4-bora-3 a,4 a-diaza-s-indacene (X = O, S, Se) (BODIPY) Systems

Kibong Kim, Changbum Jo, Shanmugam Easwaramoorthi, Jooyoung Sung, Dong Ho Kim, David G. Churchill

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67 Citations (Scopus)


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 φF. Solution and density functional theory (DFT) results reveal interesting platforms for potential in fluorescent studies for neurology. 2-Heterocyclic species show larger λabs,max/em,max values relative to 3-heterocyclic ones, based on electron withdrawing effects. 10 has the greatest φF 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); λem,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 H 2O2, and uniformly undergo λabs,max red-shifting and lowered φF values as they become brominated with Br2.

Original languageEnglish
Pages (from-to)4881-4894
Number of pages14
JournalInorganic Chemistry
Issue number11
Publication statusPublished - 2010 Jun 7

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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