Optical effects of S-oxidation and Mn+ binding in meso-thienyl dipyrrin systems and of stepwise bromination of 4,4-Difluoro-8-(2,5-dibromo-3- thienyl)-4-bora-3a,4a-diaza-s-indacene

Hei Choi Shin, Kibong Kim, June Jeon, Bhupal Meka, Daniela Bucella, Keliang Pang, Snehadrinarayan Khatua, Junseong Lee, David G. Churchill

Research output: Contribution to journalArticle

Abstract

We report 16 novel species and 8 molecular structures in studying how meso-thienyl-substituted dipyrrole oxidation, bromination, and metal ion binding impart optical changes, as monitored by UV-vis absorption/emission spectroscopy. Treatment of 4,4-difluoro-8-(3-benzothienyl)-4-bora-3a,4a-diaza-s- indacene (φF = 0.19) with m-CPBA gives selective S-dioxidation (φF = 0.006). Results of titrations of transition metal- and "scorpionate"-like dipyrrin species varied under room temperature treatment of m-CPBA. Ni-(thienyl-dipyrrin)n (n = 2) degraded significantly in the presence of m-CPBA, whereas related species (M = Cu, Fe, Co; n = 2,3) were inert. meso-Thienyl group properties were revealed through the use of 3,4,4-triphenyl-8-(thienyl)4-bora-3a,4a-diaza-s-indacene; Cu 2+ addition resulted in smooth absorption decreases which were modeled to support 1:1 substrate:M2+ binding; for Hg2+1:2 substrate:M2+ binding was found. Treatment of 4,4-difluoro-8-(2,5- dibromo-3-thienyl)-4-bora-3a,4a-diaza-s-indacene with Br2 gave red-shifted UV-vis absorption band features that grow with increasing dipyrrin bromination. Structures of the di- and tetra-substituted bromination products were obtained.

Original languageEnglish (US)
Pages (from-to)11071-11083
Number of pages13
JournalInorganic Chemistry
Volume47
Issue number23
DOIs
StatePublished - Dec 1 2008

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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