NDLI: Fixation of carbon dioxide by macrocyclic lanthanide(III) complexes under neutral conditions producing self-assembled trimeric carbonato-bridged compounds with $μ

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Dutta, Supriya Biswas, Papu Flörke, Ulrich Bag, Pradip Nag, Kamalaksha Maji, Swarup Kumar
Description	Author Affiliation: Bag P ( Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Kolkata, 700032, India.)
Abstract	A series of mononuclear lanthanide(III) complexes $[Ln(LH_{2})(H_{2}O)_{3}Cl](ClO_{4})_{2}$ (Ln = La, Nd, Sm, Eu, Gd, Tb, Lu) of the tetraiminodiphenolate macrocyclic ligand $(LH_{2})$ in 95:5 (v/v) methanol–water solution fix atmospheric carbon dioxide to produce the carbonato-bridged trinuclear complexes $[\{Ln(LH_{2})(H_{2}O)Cl\}_{3}(μ_{3}-CO_{3})](ClO_{4})_{4}·nH_{2}O.$ Under similar conditions, the mononuclear $Y^{III}$ complex forms the dimeric compound $[\{Y(LH_{2})(H_{2}O)Cl\}(μ_{2}-CO_{3})\{Y(LH_{2})(H_{2}O)_{2}\}](ClO_{4})_{3}·4H_{2}O.$ These complexes have been characterized by their IR and NMR $(^{1}H,$ $^{13}C)$ spectra. The X-ray crystal structures have been determined for the trinuclear carbonato-bridged compounds of $Nd^{III},$ $Gd^{III}$ and $Tb^{III}$ and the dinuclear compound of $Y^{III}.$ In all cases, each of the metal centers are 8-coordinate involving two imine nitrogens and two phenolate oxygens of the macrocyclic ligand $(LH_{2})$ whose two other imines are protonated and intramolecularly hydrogen-bonded with the phenolate oxygens. The oxygen atoms of the carbonate anion in the trinuclear complexes are bonded to the metal ions in tris-bidentate $μ_{3}-η^{2}:η^{2}:η^{2}$ fashion, while they are in bis-bidentate $μ_{2}-η^{2}:η^{2}$ mode in the $Y^{III}$ complex. The magnetic properties of the $Gd^{III}$ complex have been studied over the temperature range 2 to 300 K and the magnetic susceptibility data indicate a very weak antiferromagnetic exchange interaction (J = −0.042 $cm^{−1})$ between the $Gd^{III}$ centers (S = 7/2) in the metal triangle through the carbonate bridge. The luminescence spectral behaviors of the complexes of $Sm^{III},$ $Eu^{III},$ and $Tb^{III}$ have been studied. The ligand $LH_{2}$ acts as a sensitizer for the metal ions in an acetonitrile–toluene glassy matrix (at 77 K) and luminescence intensities of the complexes decrease in the order $Eu^{3+}$ > $Sm^{3+}$ > $Tb^{3+}.$
ISSN	14779226
Issue Number	12
Journal	Dalton Trans.
Volume Number	41
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2012-03-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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