Dynamic chiral-at-metal stability of tetrakis(d/l-hfc)Ln(III) complexes capped with an alkali metal cation in solution

CORC > 厦门大学 > 化学化工－已发表论文

	Dynamic chiral-at-metal stability of tetrakis(d/l-hfc)Ln(III) complexes capped with an alkali metal cation in solution
	Lin, Yiji ; Zou, Fang ; Wan, Shigang ; Ouyang, Jie ; Lin, Lirong ; Zhang, Hui ; Zhang H(章慧)
刊名	http://dx.doi.org/10.1039/c2dt30431g
	2012
关键词	TRIPLE-HELICAL COMPLEXES CIRCULARLY-POLARIZED LUMINESCENCE COORDINATION CHEMISTRY LANTHANIDE COMPLEXES ENANTIOMERIC DIFFERENTIATION CHIROPTICAL PROPERTIES MOLECULAR RECOGNITION EU(III) COMPLEXES CRYSTAL-STRUCTURE NMR-SPECTROSCOPY
英文摘要	NSFC [20973136, 20773098]; NSF of Fujian Province [2010J01048]; Chiral tetrakis(beta-diketonate) Ln(III) complexes Delta-[NaLa(d-hfc)(4)(CH3CN)] (1) and Delta-[NaLa(l-hfc)(4) (CH3CN)] (2) (d/l-hfc(-) = 3-heptafluo-robutylryl-(+)/(-)-camphorate) are a pair of enantiomers and crystallize in the same Sohncke space group (P2(1)2(1)2(1)) with dodecahedral (DD) geometry. Typically positive and negative exciton splitting patterns around 320 nm were observed in the solid-state circular dichroism (CD) spectra of complexes 1 and 2, which indicate that their shell configurational chiralities are. and., respectively. The apparent bisignate couplets in the solid-state CD spectra of [CsLn(d-hfc)(4)(H2O)] [Ln = La (3), Yb (5)] and [CsLn(l-hfc)(4)(H2O)] [Ln = La (4), Yb (6)] show that they are a pair of enantiomers and their absolute configurations are denoted. and., respectively. The crystallographic data of 5 reveals that its coordination polyhedron is the square antiprism (SAP) geometry and it undergoes a phase transition from triclinic (alpha phase, P1) to monoclinic (beta phase, C2) upon cooling. The difference between the two phases is brought about by the temperature dependent behaviour of the coordination water molecules, but this did not affect the configurational chirality of the Delta-SAP-[Yb(d-hfc)(4)](-) moiety. Furthermore, time-dependent CD, UV-vis and F-19 NMR were applied to study the solution behavior of these complexes. It was found that the chiral-at-metal stability of the three pairs of complexes is different and affected by both the Ln(3+) and M+ ion size. The results show that the Cs+ cation can retain the metal center chirality and stablize the structures of [Ln(d/l-hfc)(4)](-) or the dissociated tris(d/l-hfc) Ln(III) species in solution for a longer time than that of the Na+ cation, and it is important that the Cs+ ion successfully lock the configurational chirality around the Yb3+ center of the complex species in solution. This is reasoned by the short Cs+center dot center dot center dot FC, Cs+center dot center dot center dot O-Yb and Cs+center dot center dot center dot Yb3+ interactions observed in the crystal structure of alpha-5 and further confirmed by the chiral self-assembly of 5 or 6 from [Yb(H2O)(d/l-hfc)(3)] induced by CsI in a CHCl3 solution.
语种	英语
内容类型	期刊论文
源URL	[http://dspace.xmu.edu.cn/handle/2288/63096]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Lin, Yiji,Zou, Fang,Wan, Shigang,et al. Dynamic chiral-at-metal stability of tetrakis(d/l-hfc)Ln(III) complexes capped with an alkali metal cation in solution[J]. http://dx.doi.org/10.1039/c2dt30431g,2012.
APA	Lin, Yiji.,Zou, Fang.,Wan, Shigang.,Ouyang, Jie.,Lin, Lirong.,...&章慧.(2012).Dynamic chiral-at-metal stability of tetrakis(d/l-hfc)Ln(III) complexes capped with an alkali metal cation in solution.http://dx.doi.org/10.1039/c2dt30431g.
MLA	Lin, Yiji,et al."Dynamic chiral-at-metal stability of tetrakis(d/l-hfc)Ln(III) complexes capped with an alkali metal cation in solution".http://dx.doi.org/10.1039/c2dt30431g (2012).