TY - JOUR
T1 - α-Substituted Bis(octabutoxyphthalocyaninato)Terbium(III) Double-Decker Complexes
T2 - Preparation and Study of Protonation by NMR and DFT
AU - Damjanović, Marko
AU - Horie, Yusuke
AU - Morita, Takaumi
AU - Horii, Yoji
AU - Katoh, Keiichi
AU - Yamashita, Masahiro
AU - Enders, Markus
N1 - Publisher Copyright:
© 2015 American Chemical Society.
Copyright:
Copyright 2015 Elsevier B.V., All rights reserved.
PY - 2015/12/9
Y1 - 2015/12/9
N2 - Synthesis of the anionic, α-substituted, bis(phthalocyaninato)TbIII complex [Tb(α-obPc)2]- ([1]-) (obPc = α-octabutoxyphthalocyaninato) leads to the isolation of its protonated form [1H]0. This complex was characterized by X-ray diffraction (XRD), mass spectroscopy (MS), infrared (IR) and ultraviolet-visible-near-infrared (UV-vis-NIR) spectroscopy. Crystal structure analysis did not allow localization of the additional proton, which is probably attached to the meso-N atom or isoindole-N atom of the phthalocyaninato ligand. [1H]0 can easily be deprotonated or protonated, giving the corresponding anionic and cationic complexes. The three compounds [1H]0, [1]-, and [1HH]+ were studied by a combination of paramagnetic NMR experiments (1H, 13C, variable-temperature measurements, two-dimensional nuclear magnetic resonance and DFT calculations (done on YIII analogues with octamethoxyphthalocyaninato ligands), for the purpose of elucidating the positions of the acidic protons and for understanding the structural changes of the coordination environment of the Tb ion induced by protonation.
AB - Synthesis of the anionic, α-substituted, bis(phthalocyaninato)TbIII complex [Tb(α-obPc)2]- ([1]-) (obPc = α-octabutoxyphthalocyaninato) leads to the isolation of its protonated form [1H]0. This complex was characterized by X-ray diffraction (XRD), mass spectroscopy (MS), infrared (IR) and ultraviolet-visible-near-infrared (UV-vis-NIR) spectroscopy. Crystal structure analysis did not allow localization of the additional proton, which is probably attached to the meso-N atom or isoindole-N atom of the phthalocyaninato ligand. [1H]0 can easily be deprotonated or protonated, giving the corresponding anionic and cationic complexes. The three compounds [1H]0, [1]-, and [1HH]+ were studied by a combination of paramagnetic NMR experiments (1H, 13C, variable-temperature measurements, two-dimensional nuclear magnetic resonance and DFT calculations (done on YIII analogues with octamethoxyphthalocyaninato ligands), for the purpose of elucidating the positions of the acidic protons and for understanding the structural changes of the coordination environment of the Tb ion induced by protonation.
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U2 - 10.1021/acs.inorgchem.5b02391
DO - 10.1021/acs.inorgchem.5b02391
M3 - Article
AN - SCOPUS:84951294481
VL - 54
SP - 11986
EP - 11992
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 24
ER -