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Homotrinuclear lanthanide(III) arrays: Assembly of and conversion from mononuclear and dinuclear units

TitleHomotrinuclear lanthanide(III) arrays: Assembly of and conversion from mononuclear and dinuclear units
Publication TypeJournal Article
Year of Publication2000
AuthorsSetyawati, IA, Liu, S, Rettig, SJ, Orvig, C
JournalInorganic Chemistry
Volume39
Pagination496-507
Date PublishedFeb
Type of ArticleArticle
ISBN Number0020-1669
KeywordsAMINE PHENOL LIGANDS, ANTIBODY, COORDINATION, CRYSTAL-STRUCTURE, GADOLINIUM, IONS, METAL-COMPLEXES, MOLECULAR-STRUCTURE, SAMARIUM(III), Schiff-base
Abstract

The reactions of potentially hexadentate H(2)bbpen (N,N’-bis(2-hydroxybenzyl)-N,N’-bis(2-pyridylmethyl)ethylenediamine, H(2)L1), H-2(Cl)bbpen (N,N’-bis(5-chloro-2-hydroxybenzyl)-N,N’-bis(2-pyridylmethyl)ethylene-di amine. H(2)L2), and H-2(Br)bbpen (N,N’-bis(5-bromo-2-hydroxybenzyl)-N,N’-bis(2-pyridylmethyl)ethylenediam ine H(2)L3) with Ln(III) ions in the presence of a base in methanol resulted in three types of complexes: neutral mononuclear ([LnL(NO3)]), monocationic dinuclear ([Ln(2)Ln(2)(NO3)](+)), and monocationic trinuclear ([Ln(3)L(2)(X)(n)-(CH3OH)](+)) when X = bridging (CH3COO-) and bidentate ligands (NO3-, CH3COO-, ClO4-) and n is 4. The formation of a complex depends on the bose (hydroxide or acetate) and the size of the respective Ln(III) ion. All complexes were characterized by infrared spectroscopy, mass spectrometry, and elemental analyses; in some cases, X-ray diffraction studies were also performed. The structures of the neutral mononuclear [Yb(L1)(NO3)], dinuclear [Pr-2(L1)(2)(NO3)(H2O)]NO3.CH3OH and [Gd-2(L1)(2)(NO3)]NO3.CH3OH.3H(2)O, and trinuclear [Gd-3(L3)(2)(CH3- COO)(4)(CH3OH)]ClO4.5CH(3)OH and [Sm-3(L1)(2)(CH3COO)(2)(NO3)(2)(CH3OH)]NO3.CH3OH.3.65H(2)O were solved by X-ray crystallography. The [LnL(NO3)] or [Ln(2)L(2)(NO3)](+) complexes could be converted to [Ln(3)L(2)(X)(n)(CH3-OH)](+) complexes by the addition of 1 equiv of a Ln(III) salt and 2-3 equiv of sodium acetate in methanol. The trinuclear complexes were found to be the most stable of the three types, which was evident from the presence of the intact monocationic high molecular weight parent peaks ([Ln(3)L(2)(X)(n)](+)) in the mass spectra of all the trinuclear complexes and from the ease of conversion from the mononuclear or dinuclear to the trinuclear species. The incompatibility of the ligand denticity with the coordination requirements of the Ln(III) ions was proven to be a useful tool in the construction of multinuclear Ln(III) metal ion arrays.

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