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Novel Bis(phthalocyaninato) Rare Earth Complexes with the Bulky and Strong Electron-donating Dibutylamino Groups. Synthesis, Spectroscopy, and SMM Property

Abstract

Strong electron-donating dialkylamino groups were incoporated onto the phthalocyanine ligand in bis(phthalocyaninato) rare earth complexes for the first time to investigate their effect on the spectroscopic properties, electrochemistry, and electronic structure. The bis[2,3,9,10,16,17,23,24-octakis(dibutylamino)phthalocyaninate] rare earth complexes M{Pc[N(C4H9)2]8}2 {Pc[N(C4H9)2]8 = 2,3,9,10,16,17,23,24-octakis(dibutylamino)phthalocyanine, M = Y, Tb} (1, 2) were isolated from the condensation reaction of corresponding metal free ligand in refluxing mixture of n-octanol/1,2,4-trichrolobenzene (TCB) (1:5) in the presence of M(acac)3·nH2O (M = Y, Tb) in relatively good yield, with their sandwich double-decker nature revealed on the basis of mass, 1H NMR, electronic absorption, IR, and EPR spectroscopic results in addition to elemental analysis. Their electrochemistry was investigated by cyclic voltammetry (CV). In particular, magnetic studies reveal the typical slow relaxation of the terbium double-decker, indicating its typical single-ion magnet (SIM) nature with the blocking temperature 25 K and spin reversal energy barrier of 752±8 K, representing the sole example of SMMs reported thus far with blocking temperature over 20 K. Theoretical calculations disclose the effect of the bulky and strong electron-donating peripheral dialkylamino groups, which create a square-antiprismatic coordination geometry and intensified coordination field strength for the central terbium ion, resulting in the excellent magnetic performance of this terbium double-decker SIM.

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Publication details

The article was received on 13 Jun 2017, accepted on 08 Jul 2017 and first published on 10 Jul 2017


Article type: Research Article
DOI: 10.1039/C7QI00332C
Citation: Inorg. Chem. Front., 2017, Accepted Manuscript
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    Novel Bis(phthalocyaninato) Rare Earth Complexes with the Bulky and Strong Electron-donating Dibutylamino Groups. Synthesis, Spectroscopy, and SMM Property

    Y. Chen, F. Ma, X. Chen, B. Dong, K. Wang, S. Jiang, C. Wang, X. Chen, D. Qi, H. Sun, B. Wang, S. Gao and J. Jiang, Inorg. Chem. Front., 2017, Accepted Manuscript , DOI: 10.1039/C7QI00332C

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