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Advanced Magnetic Resonance Studies of Tetraphenylporphyrinatoiron(III) Halides

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Abstract

High-Frequency and -Field EPR (HFEPR) studies of Fe(TPP)X (X = F, Cl, Br; I, TPP2−= meso-tetraphenylporphyrinate dianion) and far-IR magnetic spectroscopic (FIRMS) studies of Fe(TPP)Br and Fe(TPP)I have been conducted to probe magnetic intra- and inter-Kramers doublet transitions in these S = 5/2 metalloporphyrin complexes, yielding zero-field splitting (ZFS) and g parameters for the complexes: Fe(TPP)F, D =  +4.67(1) cm−1, E = 0.00(1) cm−1, g⊥ = 1.97(1), g|| = 2.000(5) by HFEPR; Fe(TPP)Cl, D =  +6.458(2) cm−1, E =  +0.015(5) cm−1, E/D = 0.002, g⊥ = 2.004(3), g|| = 2.02(1) by HFEPR; Fe(TPP)Br, D = +9.03(5) cm−1, E =  +0.047(5) cm−1, E/D = 0.005, giso = 1.99(1) by HFEPR and D = +9.05 cm−1, giso = 2.0 by FIRMS; Fe(TPP)I, D =  +13.84 cm−1, E =  +0.07 cm−1, E/D = 0.005, giso = 2.0 by HFEPR and D = +13.95 cm−1, giso = 2.0 by FIRMS (the sign of E was in each case arbitrarily assigned as that of D). These results demonstrate the complementary nature of field- and frequency-domain magnetic resonance experiments in extracting with high accuracy and precision spin Hamiltonian parameters of metal complexes with S > 1/2. The spin Hamiltonian parameters obtained from these experiments have been compared with those obtained from other physical methods such as magnetic susceptibility, magnetic Mössbauer spectroscopy, inelastic neutron scattering (INS), and variable-temperature and -field magnetic circular dichroism (VT-VH MCD) experiments. INS, Mössbauer and MCD give good agreement with the results of HFEPR/FIRMS; the others not as much. The electronic structure of Fe(TPP)X (X = F, Cl, Br, I) was studied earlier by multi-reference ab initio methods to explore the origin of the large and positive D-values, reproducing the trends of D from the experiments. In the current work, a simpler model based on Ligand Field Theory (LFT) is used to explain qualitatively the trend of increasing ZFS from X = F to Cl to Br and to I as the axial ligand. Tetragonally elongated high-spin d5 systems such as Fe(TPP)X exhibit D > 0, but X plays a key role. Spin delocalization onto X means that there is a spin–orbit coupling (SOC) contribution to D from X•, as opposed to none from closed-shell X−. Over the range X = F, Cl, Br, I, X• character increases as does the intrinsic SOC of X• so that D increases correspondingly over this range.

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Acknowledgements

Besides the sources of funding listed below J.K. thanks the HLD for financial support of his sabbatical stay in Dresden. Dr. A. Ozarowski (NHMFL) is acknowledged for his EPR simulation and fit program SPIN as well as help with some simulations. We thank Dr. Rodolphe Clérac, CNRS Centre de Recherche Paul Pascal (CRPP), Pessac, France for helpful comments about magnetometry.

Funding

US National Science Foundation (NSF, CHE-1633870 and CHE-1900296 to Z.-L.X.) and a Shull Wollan Center Graduate Research Fellowship (S.E.S) are acknowledged for partial support of the research. Part of this work was performed at the National High Magnetic Field Laboratory which is supported by NSF Cooperative Agreement No. DMR-1644779 and the State of Florida, and at the Dresden High Magnetic Field Laboratory (HLD) at Helmholtz-Zentrum Dresden-Rossendorf, Germany, member of the European Magnetic Field Laboratory (EMFL). This work was also funded by Deutsche Forschungsgemeinschaft (DFG, Germany) through the projects ZV6/2-2 and the Würzburg-Dresden Cluster of Excellence on Complexity and Topology in Quantum Matter—ct.qmat (EXC 2147, project No. 390858490).

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  1. A. N. Ponomaryov

    Present address: Institute of Radiation Physics, Helmholtz-Zentrum Dresden-Rossendorf, 01328, Dresden, Germany

Authors and Affiliations

  1. Department of Chemistry, University of Tennessee, Knoxville, TN, 37996, USA

    Pagnareach Tin, Shelby E. Stavretis & Zi-Ling Xue

  2. National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL, 32310, USA

    Mykhaylo Ozerov & J. Krzystek

  3. Dresden High Magnetic Field Laboratory (HLD-EMFL) and Würzburg-Dresden Cluster of Excellence ct.qmat, Helmholtz-Zentrum Dresden-Rossendorf, 01328, Dresden, Germany

    A. N. Ponomaryov, S. A. Zvyagin & J. Wosnitza

  4. Institut für Festkörper- und Materialphysik, Technische Universität Dresden, 01062, Dresden, Germany

    J. Wosnitza

  5. Department of Chemistry, National Chung Hsing University, Taichung, 402, Taiwan

    Ching-Chin Chen & Peter P.-Y. Chen

  6. Department of Biological, Physical and Health Sciences, Roosevelt University, Chicago, IL, 60605, USA

    Joshua Telser

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Dedicated to Prof. Dante Gatteschi, Università degli Studi di Firenze, on the occasion of his birthday and in recognition of his contribution to the fields of molecular magnetism and magnetic resonance, and many years of service to the respective communities.

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Tin, P., Stavretis, S.E., Ozerov, M. et al. Advanced Magnetic Resonance Studies of Tetraphenylporphyrinatoiron(III) Halides. Appl Magn Reson 51, 1411–1432 (2020). https://doi.org/10.1007/s00723-020-01236-8

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