Aggregation of tetranuclear Mn building blocks with alkali ion. Syntheses, crystal structures and chemical behaviors of monomer, dimer and polymer containing Mn4(mu(3)-O)(2) (8+) units
文献类型:期刊论文
作者 | D. G. Huang ; X. F. Zhang ; C. B. Ma ; H. Chen ; C. N. Chen ; Q. T. Liu ; C. X. Zhang ; D. Z. Liao ; L. C. Li |
刊名 | Dalton Transactions
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出版日期 | 2007 |
期号 | 6页码:680-688 |
关键词 | photosynthetic water oxidation manganese carboxylate complexes sodium-centered polyhedra oxygen-evolving center high-spin molecules dual-mode epr photosystem-ii formate dihydrate potential relevance angstrom resolution |
ISSN号 | 1477-9226 |
中文摘要 | Aggregation of tetranuclear Mn4O2 building blocks with alkali ion was studied. Several Mn( III) complexes containing [ Mn4O2(AcO)(7)( pyz)(2)](-) ( pyz = pyrazinate) anion(s) were obtained from an assembly system containing Mn(II), MnO4-, HOAc and Hpyz ( Napyz or Kpyz). These [ Mn4O2](8+) complexes have monomeric ( 1 and 2), dimeric ( 4 and 5) and one- dimensional chain ( 3) structures of which alkali metal ion connects the Mn ions of adjacent [ Mn4O2](8+) units through mu(1,1)-and mu(1,3)- carboxylate bridges. Complexes 2 or 3 were converted into [ Mn12O12(AcO)(16)( H2O)(4)] in EtOH solution in the presence of HOAc. However, in MeOH solution, a coordination polymer [ Mn-2( HCOO)(4)( H2O)(4)](n) was obtained accompanying the oxidation of MeOH to become HCHO and HCOOH. Tracing the H-1 NMR spectra of 2 or 3 in CD3OD, the disappearance of the resonance signals in 3 h indicated the decomposition of the [ Mn4O2](8+) cores. Complex 2 exhibits its proton NMR signals in CDCl3 which are similar to those of its pic analogue but accompany downfield shift to various extents for all the corresponding signals. Variable-temperature magnetic susceptibilities of complexes 2 - 5 in the range 5 - 300 K were recorded and were fitted for an Mn4O2 butterfly core, giving the fitting parameters J(bb) =-2.67 to -3.76 cm(-1) and J(wb) =-1.16 to -3.14 cm(-1). Small J values indicate weak antiferromagnetic coupling interactions of the Mn( III) sites and the spin ground states are considered as S-T = 0 based on the J(bb)/J(wb) ratio approximate to 1 for these complexes. The ESR spectra were recorded for complex 2 in dual-mode at liquid-helium temperatures and no obvious signal could be found. The addition of p-cresol gives rise to the reduction of the [ Mn4O2](8+), resulting in observable signals. |
语种 | 英语 |
公开日期 | 2013-04-01 |
源URL | [http://ir.fjirsm.ac.cn/handle/350002/6301] ![]() |
专题 | 福建物质结构研究所_中科院福建物质结构研究所_期刊论文 |
推荐引用方式 GB/T 7714 | D. G. Huang,X. F. Zhang,C. B. Ma,et al. Aggregation of tetranuclear Mn building blocks with alkali ion. Syntheses, crystal structures and chemical behaviors of monomer, dimer and polymer containing Mn4(mu(3)-O)(2) (8+) units[J]. Dalton Transactions,2007(6):680-688. |
APA | D. G. Huang.,X. F. Zhang.,C. B. Ma.,H. Chen.,C. N. Chen.,...&L. C. Li.(2007).Aggregation of tetranuclear Mn building blocks with alkali ion. Syntheses, crystal structures and chemical behaviors of monomer, dimer and polymer containing Mn4(mu(3)-O)(2) (8+) units.Dalton Transactions(6),680-688. |
MLA | D. G. Huang,et al."Aggregation of tetranuclear Mn building blocks with alkali ion. Syntheses, crystal structures and chemical behaviors of monomer, dimer and polymer containing Mn4(mu(3)-O)(2) (8+) units".Dalton Transactions .6(2007):680-688. |
入库方式: OAI收割
来源:福建物质结构研究所
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