1507408-70-9Relevant academic research and scientific papers
Regioisomer-dependent endo- and exocyclic coordination of bis-dithiamacrocycles
Siewe, Arlette Deukam,Kim, Ja-Yeon,Kim, Seulgi,Park, In-Hyeok,Lee, Shim Sung
, p. 393 - 398 (2014)
Syntheses of the regioisomers of bis-dithiamacrocycle and the regioisomer-controlled endo- and exocyclic coordination behaviors are reported. Direct bis-cyclization reaction of 1,2,4,5-tetra(bromomethyl)benzene with 3,6-dioxa-1,8-octanedithiol led to a mixture of two bis-dithiamacrocycle regioisomers (ortho-type; o-bis-L and meta-type; m-bis-L) which were separated by recrystallization and column chromatography. When the two isomers were reacted with AgPF6, o-bis-L gave an endocyclic one-dimensional (1-D) coordination polymer {[Ag3(o-bis-L)2(CH 3CN)](PF6)3·2CH3CN} n (1) with a 3:2 (metal-to-ligand) stoichiometry, while m-bis-L afforded an exocoordination-based 1-D polymeric complex {[Ag(m-bis-L)](PF 6)}n (2) with a 2:2 stoichiometry. The observed endo- and exocoordination modes depending on the isomers were discussed in terms of the S···S distances in the bis-dithiamacrocycle isomers. Due to the closer S···S distance in each macrocyclic ring, o-bis-L is suitable for the endocoordination. However, m-bis-L forms an exocyclic complex because the S···S distance between two macrocyclic rings is shorter than that in one macrocyclic ring. NMR experiments also revealed that o-bis-L and m-bis-L form the endo- and the exocyclic complexes, respectively, in solution.
Ligand Isomer Effect on the Formations of Supramolecular Lead(II), Mercury(II), and Copper(II)/Mercury(II) Complexes of Bis-O2S2-Macrocycle
Kim, Seulgi,Siewe, Arlette Deukam,Lee, Eunji,Ju, Huiyeong,Park, In-Hyeok,Jung, Jong Hwa,Habata, Yoichi,Lee, Shim Sung
, p. 2424 - 2431 (2018/04/11)
In addition to ortho-isomer (o-bis-L) and meta-isomer (m-bis-L) of bis-O2S2-macrocycle obtained previously, its para-isomer (p-bis-L) was newly isolated, and the complete isomer series were structurally characterized by single crystal X-ray analysis. In complexations, borderline (Pb2+) and soft (Hg2+ and Cu+) metal salts were employed to investigate the isomer effect on the coordination modes and topologies of the supramolecular complexes. Lead(II) perchlorate afforded an infinite one-dimensional (1-D) coordination polymer {[Pb2(o-bis-L)(μ-ClO4)2(ClO4)2]}n (1) and a discrete complex [Pb2(m-bis-L)(CH3CN)2(H2O)2(ClO4)2](ClO4)2 (2), both of which are based on the endocyclic binuclear complexes mainly due to the oxophilicity of the lead(II) ion. Meanwhile, mercury(II) halides showed an endocyclic dinuclear complex [Hg2(o-bis-L)I2][Hg3I8] (3) and an exocyclic 1-D coordination polymer [Hg3(m-bis-L)Br6]n (4) because the differences of sulfur-to-sulfur separation in the free ligand isomers might induce the different coordination modes. When a mixture of mercury(II) iodide and copper(I) iodide was used in the reaction with m-bis-L, a heterometallic 1-D coordination polymer [Cu2Hg2(m-bis-L)(μ-Cu2I2)(CH3CN)2I6]n (5) was obtained. In 5, exocyclic dicopper(I) complex units are linked by -Hg-Cu2I4-Hg- segments to form an infinite zigzag chain. Consequently, unlike the borderline metal, the soft metal ions show the sulfur-to-sulfur separation dependent coordination modes. These results demonstrate how small differences in the ligand isomers impact their self-assembled coordination products in terms of coordination mode and topological structure including dimensionality.
