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  Magnetic circular dichroism spectroscopy of weakly exchange coupled transition metal dimers: A model study

Piligkos, S., Slep, L. D., Weyhermüller, T., Chaudhuri, P., Bill, E., & Neese, F. (2009). Magnetic circular dichroism spectroscopy of weakly exchange coupled transition metal dimers: A model study. Coordination Chemistry Reviews, 253(19-20), 2352-2362. doi:10.1016/j.ccr.2008.10.014.

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 Creators:
Piligkos, Stergios1, 2, Author           
Slep, Leonardo D.1, 3, Author           
Weyhermüller, Thomas1, Author           
Chaudhuri, Phalguni1, Author           
Bill, Eckhard1, Author           
Neese, Frank1, 4, Author           
Affiliations:
1Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023881              
2Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen, Denmark, ou_persistent22              
3Departamento de Quimica Inorganica, Analitica y Quimica Fisica, INQUIMAE, Facultad de Ciencias Exactas y Naturales Universidad de Buenos Aires, Pabellon 2, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina, ou_persistent22              
4Universität Bonn, Institut für Physikalische und Theoretische Chemie, Wegelerstr. 12, D-53115 Bonn, Germany, ou_persistent22              

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 Abstract: A detailed study of the magnetic circular dichroism (MCD) spectra of weakly exchange coupled transition metal heterodimers is reported. The systems consist of three isostructural complexes of the type [LM(III)(PyA)3M(II)](ClO4)2 where L represents 1,4,7-trimethyl-1,4,7-triazacyclonanane and PyA is the monoanion of pyridine-2-aldoxime. The trivalent metal ion M(III) is either diamagnetic Ga(III) or paramagnetic Cr(III) (SCr = 3/2). The divalent metal ion M(II) is either diamagnetic Zn(II) or paramagnetic Ni(II) (SNi = 1). The three systems 1 (CrZn), 2 (GaNi) and 3 (CrNi) have been structurally and magnetically characterized through magnetic susceptibility measurements. For 1 the zero-field splitting is D = 0.6 cm−1 while for 2 the value D = 3.5 cm−1 was found. These values have been fixed in analyzing 3 which was found to be characterized by an antiferromagnetic interaction of JCrNi = −8.4 cm−1 (H = −2JSASB). These values served as benchmarks in the MCD analysis. The zero-field splitting of 1 and 2 was qualitatively recovered using a multi-wavelength analysis of the variable-temperature variable-field (VTVH) MCD data. The observed ligand field bands were assigned to individual d3 and d8 multiplets. Using an extension of an earlier developed theory of the nonlinear MCD response, the stunningly complex multiwavelength VTVH-MCD curves of 3 could be quantitatively reproduced with only the relative transition polarizations as input into the fitting procedure. Interestingly, the MCD bands of the minority spin Ni(II) ligand field bands were observed to change sign relative to the parent complex 2. This behavior has been analyzed. The present work hence provides a benchmark study for the application of MCD spectroscopy to weakly interacting transition metal dimers.

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Language(s): eng - English
 Dates: 2008-08-112008-10-302009-10-01
 Publication Status: Published in print
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1016/j.ccr.2008.10.014
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Title: Coordination Chemistry Reviews
  Abbreviation : Coord. Chem. Rev.
Source Genre: Journal
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Publ. Info: Amsterdam : Elsevier
Pages: - Volume / Issue: 253 (19-20) Sequence Number: - Start / End Page: 2352 - 2362 Identifier: ISSN: 0010-8545
CoNE: https://pure.mpg.de/cone/journals/resource/954925393339