Polynuclear Complexes of Ligands Containing in Situ Formed Oxazinane and Oxazolidine Rings with Appended Alkoxyl and Phenol Groups

doi:10.1021/cg300096n

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	Polynuclear Complexes of Ligands Containing in Situ Formed Oxazinane and Oxazolidine Rings with Appended Alkoxyl and Phenol Groups
	Ding, Caixia 1,2; Zeng, Fanhua 1,2,3; Ni, Jia 4; Wang, Bingwu 5; Xie, Yongshu 1,2
刊名	CRYSTAL GROWTH & DESIGN
	2012-04-01
卷号	12 期号:4 页码:2089-2096
ISSN号	1528-7483
DOI	10.1021/cg300096n
英文摘要	In situ formation of ligands is an efficient approach to synthesizing novel complexes with unique coordinating moieties. Oxazolidines and oxazinanes are 1,3-N,O-containing five-membered and six-membered heterocycles, respectively. Metal complexes of Ligands derived from these two heterocycles are rather rare. In this work, we designed and synthesized a novel multihydoxy ligand, 2((2,3-dihydroxypropylamino)methyl)phenol (H3L1). It contains both aminoethanol and aminopropanol units, which may be employed to react with aldehydes to afford oxazolidines and oxazinanes, respectively. Thus, H3L1 was reacted with metal salts in the absence cr presence of aldehydes to afford complexes [Cu(HL1)](2) (1), [CuL2](4)center dot 4CH(3)OH (2) [Zn5Na2(L-3)(4)(DMSO)(2.65)(DMF)(1.35)]-DMF (3), and [Ni(HL4)](2) (4). Complex 1 is a dialkoxo-bridged binuclear Cu(II) complex. The coordination moieties are linked by intermolecular C-H center dot center dot center dot O hydrogen bonds to afford a 1D double-chain supramolecular structure. Interestingly, in complexes 2-4, H3L1 has been reacted with formaldehyde, salicylaldehyde, and 2,6-diformyl-4-cresol to afford novel ligands H2L2, H3L3, and H3L4, respectively. The combination of in situ formed oxazinane or oxazolidine rings with appended alkoxyl and phenol functionalities in these ligands has been demonstrated to form a rich diversity of coordination structures. Thus, 2 is a tetranuclear Cu(II) complex with a face-sharing double defective cubane core structure. In this complex, (L-2)(2-) ligands coordinate in two different bridging modes with the Harris notations of 3.1(1)2(12)2(13)1(1) and 3.1(1)3(123)1(1)1(1), respectively. Complex 3 has an interesting heptanuclear Zn5Na2 core structure. A central Zn(II) is coordinated with four alkoxo O atoms from four (L-3)(3-) ligands. Each of the O atom further bridges another Zn(II) atom, resulting in a Zn-5 moiety, which is then connected to two Na+ by phenoxo O bridges, finally affording the Zn5Na2 core. The bridging mode of (L-3)(3-) can be designated as 4.2(12)2(13)1(1)3(124)1(1). And Complex 4 is a binuclear Ni(II) complex containing di-mu(2)-phenoxo bridges. The coordination moieties are linked by intermolecular C-H center dot center dot center dot pi, C-H center dot center dot center dot O, and pi center dot center dot center dot pi interactions to afford a two-dimensional supramolecular network. These results indicate that the combination of in situ formed oxazinane and oxazolidine rings with appended phenol and alkoxyl functionalities is an efficient approach to developing novel ligands and complexes with a rich structural diversity. Variable temperature magnetic data measurements revealed that medium antiferromagnetic interaction exists between the Cu(II) centers in complex 1 with a -2J value of 278 cm(-1). And in complex 4, weak antiferromagnetic coupling occurs between the Ni(II) centers, with a -2J value of 9.36 cm(-1).
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000302336900048
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/49721]
专题	中国科学院化学研究所
通讯作者	Xie, Yongshu
作者单位	1.E China Univ Sci & Technol, Key Lab Adv Mat, Shanghai 200237, Peoples R China 2.E China Univ Sci & Technol, Inst Fine Chem, Shanghai 200237, Peoples R China 3.Xiangnan Univ, Dept Chem & Life Sci, Chenzhou 423000, Peoples R China 4.Shantou Univ, Dept Chem, Shantou 515063, Peoples R China 5.Peking Univ, Coll Chem & Mol Engn, State Key Lab Rare Earth Mat Chem & Applicat, Beijing Natl Lab Mol Sci, Beijing 100871, Peoples R China
推荐引用方式 GB/T 7714	Ding, Caixia,Zeng, Fanhua,Ni, Jia,et al. Polynuclear Complexes of Ligands Containing in Situ Formed Oxazinane and Oxazolidine Rings with Appended Alkoxyl and Phenol Groups[J]. CRYSTAL GROWTH & DESIGN,2012,12(4):2089-2096.
APA	Ding, Caixia,Zeng, Fanhua,Ni, Jia,Wang, Bingwu,&Xie, Yongshu.(2012).Polynuclear Complexes of Ligands Containing in Situ Formed Oxazinane and Oxazolidine Rings with Appended Alkoxyl and Phenol Groups.CRYSTAL GROWTH & DESIGN,12(4),2089-2096.
MLA	Ding, Caixia,et al."Polynuclear Complexes of Ligands Containing in Situ Formed Oxazinane and Oxazolidine Rings with Appended Alkoxyl and Phenol Groups".CRYSTAL GROWTH & DESIGN 12.4(2012):2089-2096.