Crystal structures and thermal decomposition mechanism of four lanthanide complexes with halogen-benzoic acid and 1,10-phenanthroline |
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Authors: | JuanFen Wang Hua Li JianJun Zhang Ning Ren KeZhong Wu |
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Institution: | WANG JuanFen 1 , LI Hua 2 , ZHANG JianJun 1 , REN Ning 3 & WU KeZhong 1 1 Experimental Center, Hebei Normal University, Shijiazhuang 050016, China 2 Shijiazhuang College, Shijiazhuang 050035, China 3 Department of Chemistry, Handan College, Handan 056005, China |
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Abstract: | This paper describes syntheses and structure determination of four lanthanide complexes Nd(2-Cl-4-FBA) 3 phen] 2 (1, 2-Cl-4-FBA = 2-chloro-4-fluorobenzoate, phen = 1,10-phenanthroline), Ln(2,5-DClBA) 3 phen] 2 (Ln = Sm(2) and Tb(3), 2,5-DClBA = 2,5-dichlorobenzoate) and Sm(2-Cl-4,5-DFBA) 3 (phen)(H 2 O)] 2 (4, (2-Cl-4,5-DFBA = 2-chloro-4,5-difluorobenzo- ate). The complexes were characterized by elemental analysis, infrared and ultraviolet spectra, and X-ray single-crystal diffraction. In the molecular structures of 1 4, two Ln 3+ ions are linked by four carboxyl groups, with two of them in a bridging bidentate mode and the other two in a bridging-chelating tridentate mode, forming four binuclear molecules. In addition, each Ln 3+ ion is also chelated to one phen molecule and one carboxyl group in the complexes, except each Sm 3+ ion in 4 which is bonded to one carboxyl group by unidentate mode and one H 2 O molecule. There are two different coordination polyhedrons for each Nd 3+ ion in the two similar molecular structures of 1 and they are a distorted monocapped square antiprismatic and a distorted tricapped triangular prism conformation, respectively. The coordination polyhedron for each Ln 3+ ion in 2 4 is a nine-coordinated distorted mono-capped square antiprismatic conformation. The complex 3 exhibits green luminescence under the radiation of UV light. The thermal decomposition behaviors of the complexes have been discussed by simultaneous TG/DSC-FTIR technique. The 3D surface graphs for the FTIR spectra of the evolved gases were recorded and the gaseous products were identified by the typical IR spectra obtained at different temperatures from the 3D surface graphs. Meanwhile, we discussed the nonisothermal kinetics of 1 4 by the integral isoconversional non-linear (NL-INT) method. |
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Keywords: | rare earth complexes thermal decomposition mechanism crystal structures three-dimensional IR accumulation spectra evolved gases TG/DSC-FTIR non-isothermal kinetics |
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