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

Novel heteroleptic Er( iii ) and Yb( iii ) naphthalocyaninato-phthalocyaninates containing an octa-phenyl or octa-phenoxysubstituted naphthalocyanine deck were synthesised and identified by 1 H NMR, EPR and high resolution MALDI-TOF/TOF mass spectrometry. Direct synthesis of novel homoleptic Yb( iii...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2019-09, Vol.48 (35), p.13413-13422
Main Authors: Dubinina, Tatiana V, Kosov, Anton D, Petrusevich, Elizaveta F, Borisova, Nataliya E, Trigub, Alexander L, Mamin, George V, Gilmutdinov, Ildar F, Masitov, Artem A, Tokarev, Sergey V, Pushkarev, Victor E, Tomilova, Larisa G
Format: Article
Language:English
Subjects:
Absorption spectra
Aromatic compounds
Diamagnetism
Erbium
Ferromagnetism
Magnetic anisotropy
Magnetic properties
Mass spectrometry
NMR
Nuclear magnetic resonance
Parameters
Synthesis
Ytterbium
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Summary:Novel heteroleptic Er( iii ) and Yb( iii ) naphthalocyaninato-phthalocyaninates containing an octa-phenyl or octa-phenoxysubstituted naphthalocyanine deck were synthesised and identified by 1 H 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. Near-IR absorbing sandwich double-decker Er( iii ) and Yb( iii ) complexes, containing naphthalocyanine moiety were obtained. Magnetic parameters were determined and interpreted by EPR and SQUID techniques and supported by theoretical considerations.
ISSN:1477-9226
1477-9234
DOI:10.1039/c9dt03226f