Cyanide-bridged FeIII-CuII complexes: Jahn-Teller isomerism and its influence on the magnetic properties
We report here the synthesis and characterization of four dinuclear cyanide-bridged FeIII-CuII complexes, based on a tetra- or a pentadentate bispidine ligand (L1 or L2, respectively; bispidines are 3,7-diazabiyclo[3.3.1]nonane derivatives) coordinated to the CuII center, and a tridentate bipyridine...
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| Main Authors: | , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
August 20, 2012
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| In: |
Inorganic chemistry
Year: 2012, Volume: 51, Issue: 17, Pages: 9357-9368 |
| ISSN: | 1520-510X |
| DOI: | 10.1021/ic301122h |
| Online Access: | Verlag, Volltext: http://dx.doi.org/10.1021/ic301122h Verlag, Volltext: https://doi.org/10.1021/ic301122h 
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| Author Notes: | Mihail Atanasov, Peter Comba, Stefan Helmle |
| Summary: | We report here the synthesis and characterization of four dinuclear cyanide-bridged FeIII-CuII complexes, based on a tetra- or a pentadentate bispidine ligand (L1 or L2, respectively; bispidines are 3,7-diazabiyclo[3.3.1]nonane derivatives) coordinated to the CuII center, and a tridentate bipyridineamide (bpca) coordinated to the low-spin FeIII site, with cyanide groups completing the two coordination spheres, one of them bridging between the two metal ions. The four structurally characterized complexes [{Fe(bpca)(CN)3}{Cu(L1·H2O)}]BF4, [{Fe(bpca)(CN)3}{Cu(L2)}][Fe(bpca)(CN)3]·5H2O, [{Fe(bpca)(CN)3}{Cu(L2·MeOH)}]PF6·MeOH·H2O, and [{Fe(bpca)(CN)3}{Cu(L2)}]PF6·2H2O belong to different structural isomers. The most important differences are structurally and electronically enforced (direction of the pseudo-Jahn-Teller mode) strong or weak interactions of the copper(II) center with the cyanide bridge. The related strength of the magnetic coupling of the two centers is analyzed with a combination of experimental magnetic, electron paramagnetic resonance (EPR), electronic spectroscopic data together with a ligand-field theory- and density functional theory (DFT)-based analysis. |
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| Item Description: | Gesehen am 20.08.2018 Im Titel ist "III" und "II" hochgestellt |
| Physical Description: | Online Resource |
| ISSN: | 1520-510X |
| DOI: | 10.1021/ic301122h |