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 Buccella, 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

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bromination
Oxidation
oxidation
Emission spectroscopy
Substrates
Titration
Absorption spectroscopy
titration
Molecular structure
Transition metals
Metal ions
Absorption spectra
metal ions
ions
molecular structure
transition metals
absorption spectra
room temperature
products
spectroscopy

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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

In: Inorganic Chemistry, Vol. 47, No. 23, 01.12.2008, p. 11071-11083.

Research output: Contribution to journalArticle

Shin, Hei Choi ; Kim, Kibong ; Jeon, June ; Meka, Bhupal ; Buccella, Daniela ; Pang, Keliang ; Khatua, Snehadrinarayan ; Lee, Junseong ; Churchill, David G. / 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. In: Inorganic Chemistry. 2008 ; Vol. 47, No. 23. pp. 11071-11083.
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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.",
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T1 - 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

AU - Shin, Hei Choi

AU - Kim, Kibong

AU - Jeon, June

AU - Meka, Bhupal

AU - Buccella, Daniela

AU - Pang, Keliang

AU - Khatua, Snehadrinarayan

AU - Lee, Junseong

AU - Churchill, David G.

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AB - 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.

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