Resonance Raman studies of macrocyclic complexes. 2. Antiresonance and selective intensity enhancement in synthetic metal(II) porphyrin analogues

Laurence A. Nafie, Richard W. Pastor, James C. Dabrowiak, William H. Woodruff

Research output: Contribution to journalArticle

44 Citations (Scopus)

Abstract

The resonance Raman spectra are reported for the Mn(II), Cu(II), Ni(II), and Co(II) complexes of the dianonic N 4 macrocyclic ligand 5,7,12,14-tetramethyldibenzo [b,i][1,4,8,11]tetraazacyclotetradecahexenate (L 2-). Raman intensity patterns as a function of excitation frequency covering the argon ion laser emission lines (and the Rhodamine 6G dye laser emission region for Ni IIL) have been constructed. Mn IIL and Cu IIL show a simple one-term frequency dependence with the ligand π → π* transition near 380 nm. Ni IIL shows selective Raman intensity enhancement of low-frequency modes in resonance with a charge transfer band at 585 nm. Incontrast, the resonance behavior near the π → π* transition shows characteristic enhancement of high-frequency ligand modes. In each region a one-term theoretical curve fits the data well. Co IIL shows a strong antiresonance interference effect near 460 nm within a weak charge transfer band on the shoulder of the π → π* transition. This is the first observation of Raman antiresonance involving only allowed electronic transitions. The data are fit with a two-term theoretical expression which demonstrates the origin of the antiresonance behavior. The interpretation of the Raman intensity patterns leads us to assign the 460 nm band in Co IIL and the 585 nm band in Ni IIL to charge transfer transitions and indicates that the 460 nm band is coupled to the ligand π → π* transition while the 585 nm band is not.

Original languageEnglish (US)
Pages (from-to)8007-8014
Number of pages8
JournalJournal of the American Chemical Society
Volume98
Issue number25
StatePublished - 1976

Fingerprint

Synthetic metals
Porphyrins
Metals
Ligands
Charge transfer
Dye Lasers
Dye lasers
Gas Lasers
Argon
Raman scattering
Observation
Ions
Lasers

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Resonance Raman studies of macrocyclic complexes. 2. Antiresonance and selective intensity enhancement in synthetic metal(II) porphyrin analogues. / Nafie, Laurence A.; Pastor, Richard W.; Dabrowiak, James C.; Woodruff, William H.

In: Journal of the American Chemical Society, Vol. 98, No. 25, 1976, p. 8007-8014.

Research output: Contribution to journalArticle

Nafie, Laurence A. ; Pastor, Richard W. ; Dabrowiak, James C. ; Woodruff, William H. / Resonance Raman studies of macrocyclic complexes. 2. Antiresonance and selective intensity enhancement in synthetic metal(II) porphyrin analogues. In: Journal of the American Chemical Society. 1976 ; Vol. 98, No. 25. pp. 8007-8014.
@article{1c1eaa16fb0047c8b9eeda4aabf66969,
title = "Resonance Raman studies of macrocyclic complexes. 2. Antiresonance and selective intensity enhancement in synthetic metal(II) porphyrin analogues",
abstract = "The resonance Raman spectra are reported for the Mn(II), Cu(II), Ni(II), and Co(II) complexes of the dianonic N 4 macrocyclic ligand 5,7,12,14-tetramethyldibenzo [b,i][1,4,8,11]tetraazacyclotetradecahexenate (L 2-). Raman intensity patterns as a function of excitation frequency covering the argon ion laser emission lines (and the Rhodamine 6G dye laser emission region for Ni IIL) have been constructed. Mn IIL and Cu IIL show a simple one-term frequency dependence with the ligand π → π* transition near 380 nm. Ni IIL shows selective Raman intensity enhancement of low-frequency modes in resonance with a charge transfer band at 585 nm. Incontrast, the resonance behavior near the π → π* transition shows characteristic enhancement of high-frequency ligand modes. In each region a one-term theoretical curve fits the data well. Co IIL shows a strong antiresonance interference effect near 460 nm within a weak charge transfer band on the shoulder of the π → π* transition. This is the first observation of Raman antiresonance involving only allowed electronic transitions. The data are fit with a two-term theoretical expression which demonstrates the origin of the antiresonance behavior. The interpretation of the Raman intensity patterns leads us to assign the 460 nm band in Co IIL and the 585 nm band in Ni IIL to charge transfer transitions and indicates that the 460 nm band is coupled to the ligand π → π* transition while the 585 nm band is not.",
author = "Nafie, {Laurence A.} and Pastor, {Richard W.} and Dabrowiak, {James C.} and Woodruff, {William H.}",
year = "1976",
language = "English (US)",
volume = "98",
pages = "8007--8014",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "25",

}

TY - JOUR

T1 - Resonance Raman studies of macrocyclic complexes. 2. Antiresonance and selective intensity enhancement in synthetic metal(II) porphyrin analogues

AU - Nafie, Laurence A.

AU - Pastor, Richard W.

AU - Dabrowiak, James C.

AU - Woodruff, William H.

PY - 1976

Y1 - 1976

N2 - The resonance Raman spectra are reported for the Mn(II), Cu(II), Ni(II), and Co(II) complexes of the dianonic N 4 macrocyclic ligand 5,7,12,14-tetramethyldibenzo [b,i][1,4,8,11]tetraazacyclotetradecahexenate (L 2-). Raman intensity patterns as a function of excitation frequency covering the argon ion laser emission lines (and the Rhodamine 6G dye laser emission region for Ni IIL) have been constructed. Mn IIL and Cu IIL show a simple one-term frequency dependence with the ligand π → π* transition near 380 nm. Ni IIL shows selective Raman intensity enhancement of low-frequency modes in resonance with a charge transfer band at 585 nm. Incontrast, the resonance behavior near the π → π* transition shows characteristic enhancement of high-frequency ligand modes. In each region a one-term theoretical curve fits the data well. Co IIL shows a strong antiresonance interference effect near 460 nm within a weak charge transfer band on the shoulder of the π → π* transition. This is the first observation of Raman antiresonance involving only allowed electronic transitions. The data are fit with a two-term theoretical expression which demonstrates the origin of the antiresonance behavior. The interpretation of the Raman intensity patterns leads us to assign the 460 nm band in Co IIL and the 585 nm band in Ni IIL to charge transfer transitions and indicates that the 460 nm band is coupled to the ligand π → π* transition while the 585 nm band is not.

AB - The resonance Raman spectra are reported for the Mn(II), Cu(II), Ni(II), and Co(II) complexes of the dianonic N 4 macrocyclic ligand 5,7,12,14-tetramethyldibenzo [b,i][1,4,8,11]tetraazacyclotetradecahexenate (L 2-). Raman intensity patterns as a function of excitation frequency covering the argon ion laser emission lines (and the Rhodamine 6G dye laser emission region for Ni IIL) have been constructed. Mn IIL and Cu IIL show a simple one-term frequency dependence with the ligand π → π* transition near 380 nm. Ni IIL shows selective Raman intensity enhancement of low-frequency modes in resonance with a charge transfer band at 585 nm. Incontrast, the resonance behavior near the π → π* transition shows characteristic enhancement of high-frequency ligand modes. In each region a one-term theoretical curve fits the data well. Co IIL shows a strong antiresonance interference effect near 460 nm within a weak charge transfer band on the shoulder of the π → π* transition. This is the first observation of Raman antiresonance involving only allowed electronic transitions. The data are fit with a two-term theoretical expression which demonstrates the origin of the antiresonance behavior. The interpretation of the Raman intensity patterns leads us to assign the 460 nm band in Co IIL and the 585 nm band in Ni IIL to charge transfer transitions and indicates that the 460 nm band is coupled to the ligand π → π* transition while the 585 nm band is not.

UR - http://www.scopus.com/inward/record.url?scp=0017301860&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0017301860&partnerID=8YFLogxK

M3 - Article

VL - 98

SP - 8007

EP - 8014

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 25

ER -