Syntheses, crystal structures and luminescence properties of lanthanide coordination polymers involving in situ C–S bond cleavage of (4-pyridylthio)acetic acid

• Published in: Inorganic chemistry communications 2007-07, Vol.10 (7), p.829-832
• Main Authors: He, Yong-Ke, Han, Zheng-Bo, Ma, Yi, Zhang, Xiang-Dong
• Format: Article
• Language: English
• Subjects: Coordination polymers; Crystal structure; Luminescent properties; Synthesis
• ISSN: 1387-7003; 1879-0259
• DOI: 10.1016/j.inoche.2007.04.018

The treatment of the (4-pyridylthio) acetic acid and lanthanide nitrates under hydrothermal conditions leads to generate the two-dimensional lanthanide coordination polymers involving in situ C–S bond cleavage and (4-pyridylthio) acetic acid was transformed into 4-pyridinethiolate and oxalate. Lanthanide coordination polymers with the formula [Ln 2(C 2O 4) 3(H 2O) 6] n ( 1) (Ln = Nd, 1) and [Ln 2(C 2O 4) 3(pythioH) 2(H 2O) 2] n (Ln = Eu 2; Dy 3; Er 4) pythio = 4-pyridinethiolate) were synthesized by treating Ln III nitrates with (4-pyridylthio)acetic acid under hydrothermal conditions. Single-crystal X-ray diffraction studies indicate that these lanthanide coordination polymers consist of extended oxalate-bridged two-dimensional layer structure. Interestingly, in situ C–S bond cleavage occurred and (4-pyridylthio)acetic acid was transformed into 4-pyridinethiolate and oxalate. The complexes 2 and 3 display strong fluorescent emission in the solid state at room temperature.