Hydrolytic synthesis and structural characterization of lanthanide hydroxide clusters supported by nicotinic acid

Xiang Jian Kong, La Sheng Long, Lan Sun Zheng, Ruiyao Wang, Zhiping Zheng

Research output: Contribution to journalArticle

58 Citations (Scopus)

Abstract

Polynuclear lanthanide hydroxide complexes featuring the cubane-like [Ln 43-OH) 4] 8+ [Ln ) Eu(III), Gd(III)] cluster core have been synthesized by controlled hydrolysis of the lanthanide ions using nicotinic acid as the ancillary ligand. The synthetic procedure has been found to significantly influence the nature of the resulting cluster species. In a one-pot synthesis, adjusting the pH of the reaction mixture containing Ln(ClO 4) 3 and nicotinic acid afforded tetranuclear complexes of the general formula [Ln 43- OH) 4(Hnic) 5(H 2O) 12](ClO 4) 8 with the [Ln 43-OH) 4] 8+ (Ln ) Eu, Gd) cluster core encapsulated by zwitterionic nicotinate ligands. In stark contrast, mixing aqueous solutions of Ln(ClO 4) 3 and nicotinic acid whose pH had been preadjusted produced assemblies composed of two of the cubanelike cluster cores that are related by a crystallographic inversion center and are doubly bridged by nicotinate ligands using both the carboxylate group and pyridyl N atom for coordination. The influences of pH conditions and synthetic procedures on the identity of the resulting cluster species are discussed, so is the structural relevance of the low-pH complexes to their cluster analogues obtained under higher-pH conditions.

Original languageEnglish (US)
Pages (from-to)3268-3273
Number of pages6
JournalInorganic Chemistry
Volume48
Issue number7
DOIs
StatePublished - 2009

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nicotinic acid
Lanthanoid Series Elements
Niacin
hydroxides
synthesis
Ligands
ligands
cubane
Hydrolysis
assemblies
carboxylates
hydrolysis
hydroxide ion
Ions
adjusting
Atoms
analogs
inversions
aqueous solutions
atoms

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Hydrolytic synthesis and structural characterization of lanthanide hydroxide clusters supported by nicotinic acid. / Kong, Xiang Jian; Long, La Sheng; Zheng, Lan Sun; Wang, Ruiyao; Zheng, Zhiping.

In: Inorganic Chemistry, Vol. 48, No. 7, 2009, p. 3268-3273.

Research output: Contribution to journalArticle

Kong, Xiang Jian ; Long, La Sheng ; Zheng, Lan Sun ; Wang, Ruiyao ; Zheng, Zhiping. / Hydrolytic synthesis and structural characterization of lanthanide hydroxide clusters supported by nicotinic acid. In: Inorganic Chemistry. 2009 ; Vol. 48, No. 7. pp. 3268-3273.
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AB - Polynuclear lanthanide hydroxide complexes featuring the cubane-like [Ln 4(μ 3-OH) 4] 8+ [Ln ) Eu(III), Gd(III)] cluster core have been synthesized by controlled hydrolysis of the lanthanide ions using nicotinic acid as the ancillary ligand. The synthetic procedure has been found to significantly influence the nature of the resulting cluster species. In a one-pot synthesis, adjusting the pH of the reaction mixture containing Ln(ClO 4) 3 and nicotinic acid afforded tetranuclear complexes of the general formula [Ln 4(μ 3- OH) 4(Hnic) 5(H 2O) 12](ClO 4) 8 with the [Ln 4(μ 3-OH) 4] 8+ (Ln ) Eu, Gd) cluster core encapsulated by zwitterionic nicotinate ligands. In stark contrast, mixing aqueous solutions of Ln(ClO 4) 3 and nicotinic acid whose pH had been preadjusted produced assemblies composed of two of the cubanelike cluster cores that are related by a crystallographic inversion center and are doubly bridged by nicotinate ligands using both the carboxylate group and pyridyl N atom for coordination. The influences of pH conditions and synthetic procedures on the identity of the resulting cluster species are discussed, so is the structural relevance of the low-pH complexes to their cluster analogues obtained under higher-pH conditions.

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