Assembly of Silver(I) Complexes of Isomeric NS2-Macrocycles Displaying Cyclic Oligomer, Helix, and Zigzag Structures

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• 作者：Sunhong Park ; Leonard F. Lindoy ; Shim Sung Lee
• 刊名：Crystal Growth & Design
• 出版年：2012
• 出版时间：March 7, 2012
• 年：2012
• 卷：12
• 期：3
• 页码：1320-1329
• 全文大小：577K
• 年卷期：v.12,no.3(March 7, 2012)
• ISSN：1528-7505

文摘

An isomeric series of NS₂-macrocycles, incorporating ortho- (o-L), meta- (m-L), and para-xylyl (p-L) groups in their backbones between the sulfur donors, have been synthesized. A comparative investigation of the coordination behavior of these macrocyclic ligands with silver(I) salts is reported. The X-ray structures of six complexes (1鈥?b>6) were determined, and a variety of structural types that range from cyclic oligomers to zigzag or helical chains is shown to occur. Reactions of o-L with silver nitrate and perchlorate afforded three complexes with different topologies: the cyclic hexamer [Ag₆(o-L)₆](NO₃)₆路0.5DMF路7H₂O (1), the cyclic hexamer with two terminal complex units [Ag₈(o-L)₈](ClO₄)₈ (2), and a one-dimensional (1D) zigzag coordination polymer of type {[Ag₂(o-L)₂](ClO₄)₂路2CH₃CN路CHCl₃}_n (3). Reaction of m-L with silver(I) perchlorate gave the 1D zigzag coordination polymer, {[Ag(m-L)]ClO₄路CH₂Cl₂}_n (4). Reaction of p-L with silver perchlorate yielded a crystalline product whose X-ray analysis confirmed it to be a mixture of two different species: the discrete helical complex {[Ag₃(p-L)₃](ClO₄)₃}_n (5) and the cyclic tetramer [Ag₄(p-L)₄(ClO₄)₄]路3DMF (6). The influence of macrocyclic ring flexibility and sulfur donor atom spacing on the topologies adopted by the respective complexes is discussed.