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 language | English |
|---|---|
| Pages (from-to) | 8956-8963 |
| Number of pages | 8 |
| Journal | Inorganic Chemistry |
| Volume | 57 |
| Issue number | 15 |
| DOIs | |
| Publication status | Published - 2018 Aug 6 |
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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 journal › Article
}
TY - JOUR
T1 - Synthesis, Structural, Spectral, and Electrochemical Studies of Selenabenziporphyrin and Its Pd(II) Complex
AU - Kumar, Sunit
AU - Thorat, Kishor G.
AU - Lee, Way Zen
AU - Ravikanth, Mangalampalli
PY - 2018/8/6
Y1 - 2018/8/6
N2 - 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.
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.
UR - http://www.scopus.com/inward/record.url?scp=85051193843&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85051193843&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.8b00914
DO - 10.1021/acs.inorgchem.8b00914
M3 - Article
AN - SCOPUS:85051193843
VL - 57
SP - 8956
EP - 8963
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 15
ER -