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Issue 9, 2017
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Novel bis(phthalocyaninato) rare earth complexes with the bulky and strong electron-donating dibutylamino groups: synthesis, spectroscopy, and SMM properties

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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 effects 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 the corresponding metal free ligand in a 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 yields, with their sandwich double-decker nature revealed on the basis of their 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 a blocking temperature of 25 K and a spin reversal energy barrier of 752 ± 8 K, representing the sole example of sandwich-type tetrapyrrole lanthanide-based SMMs reported thus far with a 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.

Graphical abstract: Novel bis(phthalocyaninato) rare earth complexes with the bulky and strong electron-donating dibutylamino groups: synthesis, spectroscopy, and SMM properties

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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., 2017,4, 1465-1471
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    Novel bis(phthalocyaninato) rare earth complexes with the bulky and strong electron-donating dibutylamino groups: synthesis, spectroscopy, and SMM properties

    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, 4, 1465
    DOI: 10.1039/C7QI00332C

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