Magnetic circular dichroism spectroscopy of cobalt tetraphenyltetraacenaphthoporphyrin

John Mack; Yoshiaki Asano; Nagao Kobayashi; Martin J. Stillman

doi:10.1016/j.jinorgbio.2007.10.031

Magnetic circular dichroism spectroscopy of cobalt tetraphenyltetraacenaphthoporphyrin

John Mack, Yoshiaki Asano, Nagao Kobayashi, Martin J. Stillman

Research output: Contribution to journal › Article › peer-review

15 Citations (Scopus)

Abstract

The first MCD spectral data for an open shell first row transition metal complex of tetraphenyltetraacenaphthoporphyrin (TPTANP) are reported. The B (or Soret) band of cobalt tetraphenyltetraacenaphthoporphyrin (Co^IITPTANP(-2)) exhibits an anomalous negative Faraday A₁ term as was reported previously in the case of ZnTPTANP, while a positive A₁ term is observed for the Q band. INDO/1 geometry optimizations predict that the TPTANP ligand is saddled due to steric hindrance at the ligand periphery to a slightly lesser extent than is the case with ZnTPTANP. The Q and B bands of CoTPTANP arising from the π-system are blue shifted relative to those of ZnTPTANP, based on the "hypso" effect reported previously for planar porphyrin complexes of d^6-9 transition metals.

Original language	English
Pages (from-to)	472-479
Number of pages	8
Journal	Journal of Inorganic Biochemistry
Volume	102
Issue number	3
DOIs	https://doi.org/10.1016/j.jinorgbio.2007.10.031
Publication status	Published - 2008 Mar

Keywords

Co(II)
DFT calculations
Magnetic circular dichroism spectroscopy
Non-planar porphyrin
Red-shifted Q band

ASJC Scopus subject areas

Biochemistry
Inorganic Chemistry

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10.1016/j.jinorgbio.2007.10.031

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title = "Magnetic circular dichroism spectroscopy of cobalt tetraphenyltetraacenaphthoporphyrin",

abstract = "The first MCD spectral data for an open shell first row transition metal complex of tetraphenyltetraacenaphthoporphyrin (TPTANP) are reported. The B (or Soret) band of cobalt tetraphenyltetraacenaphthoporphyrin (CoIITPTANP(-2)) exhibits an anomalous negative Faraday A1 term as was reported previously in the case of ZnTPTANP, while a positive A1 term is observed for the Q band. INDO/1 geometry optimizations predict that the TPTANP ligand is saddled due to steric hindrance at the ligand periphery to a slightly lesser extent than is the case with ZnTPTANP. The Q and B bands of CoTPTANP arising from the π-system are blue shifted relative to those of ZnTPTANP, based on the {"}hypso{"} effect reported previously for planar porphyrin complexes of d6-9 transition metals.",

keywords = "Co(II), DFT calculations, Magnetic circular dichroism spectroscopy, Non-planar porphyrin, Red-shifted Q band",

author = "John Mack and Yoshiaki Asano and Nagao Kobayashi and Stillman, {Martin J.}",

note = "Funding Information: We thank NSERC of Canada for Operating and Equipment grants (to MJS) and support from Fujitsu America Inc. in providing the CAChe Workstation software. MJS is a member of the Centre for Chemical Physics at UWO. This research was partially supported by the Ministry of Education, Science, Sports and Culture, with a Grant-in-Aid for the COE project, Giant Molecules and Complex Systems, 2006 and a Grant-in-Aid for Exploratory Research (No. 19655045) (to NK).",

year = "2008",

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doi = "10.1016/j.jinorgbio.2007.10.031",

language = "English",

volume = "102",

pages = "472--479",

journal = "Journal of Inorganic Biochemistry",

issn = "0162-0134",

publisher = "Elsevier Inc.",

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TY - JOUR

T1 - Magnetic circular dichroism spectroscopy of cobalt tetraphenyltetraacenaphthoporphyrin

AU - Mack, John

AU - Asano, Yoshiaki

AU - Kobayashi, Nagao

AU - Stillman, Martin J.

N1 - Funding Information: We thank NSERC of Canada for Operating and Equipment grants (to MJS) and support from Fujitsu America Inc. in providing the CAChe Workstation software. MJS is a member of the Centre for Chemical Physics at UWO. This research was partially supported by the Ministry of Education, Science, Sports and Culture, with a Grant-in-Aid for the COE project, Giant Molecules and Complex Systems, 2006 and a Grant-in-Aid for Exploratory Research (No. 19655045) (to NK).

PY - 2008/3

Y1 - 2008/3

N2 - The first MCD spectral data for an open shell first row transition metal complex of tetraphenyltetraacenaphthoporphyrin (TPTANP) are reported. The B (or Soret) band of cobalt tetraphenyltetraacenaphthoporphyrin (CoIITPTANP(-2)) exhibits an anomalous negative Faraday A1 term as was reported previously in the case of ZnTPTANP, while a positive A1 term is observed for the Q band. INDO/1 geometry optimizations predict that the TPTANP ligand is saddled due to steric hindrance at the ligand periphery to a slightly lesser extent than is the case with ZnTPTANP. The Q and B bands of CoTPTANP arising from the π-system are blue shifted relative to those of ZnTPTANP, based on the "hypso" effect reported previously for planar porphyrin complexes of d6-9 transition metals.

AB - The first MCD spectral data for an open shell first row transition metal complex of tetraphenyltetraacenaphthoporphyrin (TPTANP) are reported. The B (or Soret) band of cobalt tetraphenyltetraacenaphthoporphyrin (CoIITPTANP(-2)) exhibits an anomalous negative Faraday A1 term as was reported previously in the case of ZnTPTANP, while a positive A1 term is observed for the Q band. INDO/1 geometry optimizations predict that the TPTANP ligand is saddled due to steric hindrance at the ligand periphery to a slightly lesser extent than is the case with ZnTPTANP. The Q and B bands of CoTPTANP arising from the π-system are blue shifted relative to those of ZnTPTANP, based on the "hypso" effect reported previously for planar porphyrin complexes of d6-9 transition metals.

KW - Co(II)

KW - DFT calculations

KW - Magnetic circular dichroism spectroscopy

KW - Non-planar porphyrin

KW - Red-shifted Q band

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