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Issue 35, 2019
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Sandwich double-decker Er(iii) and Yb(iii) complexes containing naphthalocyanine moiety: synthesis and investigation of the effect of a paramagnetic metal center

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Abstract

Novel heteroleptic Er(III) and Yb(III) naphthalocyaninato-phthalocyaninates containing an octa-phenyl or octa-phenoxysubstituted naphthalocyanine deck were synthesised and identified by 1H NMR, EPR and high resolution MALDI-TOF/TOF mass spectrometry. Direct synthesis of novel homoleptic Yb(III) bis (octa-phenylnaphthalocyaninate) was carried out. Downfield lanthanide induced shifts of the aromatic protons in target compounds were observed compared with the corresponding diamagnetic Lu(III) complexes. In the near-IR absorption spectra, an increase in ionic radius from Lu(III) to Er(III) resulted in a bathochromic shift of the intervalence band up to 1473 nm. This work presents the first experimental EPR study of Yb(III) bis naphthalocyaninate, where a set of magnetic parameters and properties (including spin, magnitude and sign of magnetic anisotropy parameter D, increased splitting in a crystal field, ferromagnetic f–π interaction etc.) were determined and interpreted by both EPR and SQUID techniques and supported by theoretical considerations.

Graphical abstract: Sandwich double-decker Er(iii) and Yb(iii) complexes containing naphthalocyanine moiety: synthesis and investigation of the effect of a paramagnetic metal center

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Article information


Submitted
08 Jul 2019
Accepted
13 Aug 2019
First published
13 Aug 2019

Dalton Trans., 2019,48, 13413-13422
Article type
Paper

Sandwich double-decker Er(III) and Yb(III) complexes containing naphthalocyanine moiety: synthesis and investigation of the effect of a paramagnetic metal center

T. V. Dubinina, A. D. Kosov, E. F. Petrusevich, N. E. Borisova, A. L. Trigub, G. V. Mamin, I. F. Gilmutdinov, A. A. Masitov, S. V. Tokarev, V. E. Pushkarev and L. G. Tomilova, Dalton Trans., 2019, 48, 13413
DOI: 10.1039/C9DT03226F

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