First quadruple-glycine bridging mono-lanthanide-substituted borotungstate hybrids. Issue 41 (26th September 2016)

• Record Type: Journal Article
• Authors: Liu, Jiancai; Yu, Jing; Han, Qing; Wen, Yue; Chen, Lijuan; Zhao, Junwei
• Is Part Of: Dalton transactions. Volume 45:Issue 41(2016)
• Page Start: 16471
• Page End: 16484
• Publication Date: 2016-09-26
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c6dt03148j
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : A class of novel organic–inorganic hybrid quadruple-glycine lanthanide-substituted Keggin-type borotungstates have been synthesized and characterized. Abstract : A class of novel organic–inorganic hybrid lanthanide (Ln)-substituted Keggin-type borotungstates K4 Na4 H4 [Ln2 (gly)4 (α-BW11 O39 )2 ]·23H2 O [Ln = Ce 3+ (1 ), Pr 3+ (2 ), Nd 3+ (3 ), Sm 3+ (4 ), Eu 3+ (5 ), Tm 3+ (6 ); gly = glycine] have been synthesized from the reaction of K8 [BW11 O39 H]·13H2 O, NaAc·6H2 O and Ln(NO3 )3 ·6H2 O by employing gly ligands as structure-stabilizing agents in the conventional aqueous solution system and structurally characterized by elemental analyses, IR spectroscopy, thermogravimetric (TG) analyses, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The common prominent structural feature of isomorphic1–6 is that all of them consist of two mono-Ln-substituted Keggin [Ln(α-BW11 O39 )] 6− fragments linked by four gly ligands, furnishing an intriguing dimeric assembly of the quadruple-gly-connective mono-Ln-substituted borotungstate, in which each carboxylic oxygen atom from gly ligands is bound to Ln 3+ cations in the μ2 -O or μ3 -O mode. To the best of our knowledge, 1–6 represent the first examples of inorganic–organic hybrid Ln-substituted borotungstates functionalized by quadruple amino acid bridges. The solid-state photoluminescence properties of3–5 have been determined at ambient temperature and the photoluminescence emission spectra exhibit the characteristic emission bands derived from Ln 3+ centers. The thermostability of1–6 has been studied and the thermal decomposition procedure of3 has been comprehensively investigated with the assistance of variable-temperature PXRD patterns and variable-temperature IR spectra. Furthermore, magnetic susceptibility measurements of1, 2 and4 have been conducted.