Synthesis, Structural, Spectral, and Electrochemical Studies of Selenabenziporphyrin and Its Pd(II) Complex

Sunit Kumar, Kishor G. Thorat, Way Zen Lee, Mangalampalli Ravikanth

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Abstract

A new nonaromatic selenabenziporphyrin was synthesized by (3 + 1) condensation of m-benzitripyrrane and 2,5-bis[(p-tolyl)hydroxymethyl] selenophene under mild trifluoroacetic acid-catalyzed reaction conditions. The selenabenziporphyrin was characterized by high-resolution mass spectrometry, one- and two-dimensional NMR spectroscopy, and X-ray crystallography. The crystal structure revealed that the macrocycle was planar with moderately tilted m-phenylene ring and that the phenylene ring completely blocks the macrocyclic π-delocalization. The selenabenziporphyrin exhibits one broad absorption band at 645 nm along with one sharp band at 415 nm, and electrochemical studies revealed that the macrocycle was electron-deficient. The selenabenziporphyrin readily forms organometallic Pd(II) complex when treated with PdCl2 in CH3CN/CHCl3 at reflux followed by recrystallization. The X-ray structure revealed that the Pd(II) ion was coordinated with two pyrrole "N"s, selenophene "Se", and m-phenylene ring "C" in square-planar fashion, and the complex retained its nonaromatic nature. The Pd(II) complex exhibits ill-defined absorption bands, and it was more electron-deficient than free-base selenabenziporphyrin macrocycle. Time-dependent density functional theory studies supported the experimental observations.

Original languageEnglish
Pages (from-to)8956-8963
Number of pages8
JournalInorganic Chemistry
Volume57
Issue number15
DOIs
Publication statusPublished - 2018 Aug 6

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Absorption spectra
Electrons
Trifluoroacetic Acid
Pyrroles
rings
X ray crystallography
X Ray Crystallography
Organometallics
synthesis
Nuclear magnetic resonance spectroscopy
Density functional theory
absorption spectra
Mass spectrometry
Condensation
Mass Spectrometry
Magnetic Resonance Spectroscopy
Crystal structure
X-Rays
pyrroles
Ions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Synthesis, Structural, Spectral, and Electrochemical Studies of Selenabenziporphyrin and Its Pd(II) Complex. / Kumar, Sunit; Thorat, Kishor G.; Lee, Way Zen; Ravikanth, Mangalampalli.

In: Inorganic Chemistry, Vol. 57, No. 15, 06.08.2018, p. 8956-8963.

Research output: Contribution to journalArticle

Kumar, Sunit ; Thorat, Kishor G. ; Lee, Way Zen ; Ravikanth, Mangalampalli. / Synthesis, Structural, Spectral, and Electrochemical Studies of Selenabenziporphyrin and Its Pd(II) Complex. In: Inorganic Chemistry. 2018 ; Vol. 57, No. 15. pp. 8956-8963.
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AB - A new nonaromatic selenabenziporphyrin was synthesized by (3 + 1) condensation of m-benzitripyrrane and 2,5-bis[(p-tolyl)hydroxymethyl] selenophene under mild trifluoroacetic acid-catalyzed reaction conditions. The selenabenziporphyrin was characterized by high-resolution mass spectrometry, one- and two-dimensional NMR spectroscopy, and X-ray crystallography. The crystal structure revealed that the macrocycle was planar with moderately tilted m-phenylene ring and that the phenylene ring completely blocks the macrocyclic π-delocalization. The selenabenziporphyrin exhibits one broad absorption band at 645 nm along with one sharp band at 415 nm, and electrochemical studies revealed that the macrocycle was electron-deficient. The selenabenziporphyrin readily forms organometallic Pd(II) complex when treated with PdCl2 in CH3CN/CHCl3 at reflux followed by recrystallization. The X-ray structure revealed that the Pd(II) ion was coordinated with two pyrrole "N"s, selenophene "Se", and m-phenylene ring "C" in square-planar fashion, and the complex retained its nonaromatic nature. The Pd(II) complex exhibits ill-defined absorption bands, and it was more electron-deficient than free-base selenabenziporphyrin macrocycle. Time-dependent density functional theory studies supported the experimental observations.

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