Gold and Silver Chains Supported by Linear Hexaphosphine Ligands
Gold and Silver Chains Supported by Linear Hexaphosphine Ligands
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线性六膦配体支持的金链和银链
DOI：
10.1002/asia.201500876
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
T.
中科院分区：
文献类型：
--
作者：
Tanse;T.; Chikanishi;M.; Morita;K.; Nakamae;K.; Kure;B.; Nakajima;T.
合成了一种新的线性六膦化合物，即rac-cis，cis，trans-bis {[（diphenylphosphinomethyl）phenylphosphinomethyl]phenylphosphino}methane（P6），并通过转化为相应的硫化膦得到了证实。亚甲基桥连的线性六膦容易组装柔性金（I）和银（I）六核链，[M6（μ-P6）2]X6（X6=（OTf）6，M=Au（1），Ag（2）; X6= Cl 2（PF 6）4，M=Au（3））。六膦还支持四银（I）配合物[Ag 4（μ-P6）2]（OTf）4（4），其通过AgOTf处理容易地转化为3，揭示了两个P6排列的剧烈变化。六角金（I）链的吸收（~ 410 nm）和发射（540-580 nm）分别从金属中心的1 [5dσ*→6pσ]和3 [5dσ*→6pσ]激发态显著红移。 新的线性六膦可能是一个有用的工具，构建线性金属簇作为亚纳米积木。
A new linear hexaphosphine,rac‐cis,cis,trans‐ bis{[(diphenylphosphinomethyl)phenylphosphinomethyl]phenylphosphino}methane (P6), was synthesized and isolated as a pure isomer, confirmed by transforming to the corresponding phosphine sulfide. The methylene‐bridged linear hexaphosphine readily organized flexible gold(I) and silver(I) hexanuclear chains, [M6(μ‐P6)2]X6(X6=(OTf)6, M=Au (1), Ag (2); X6=Cl2(PF6)4, M=Au (3)). The hexaphosphine also supported a tetrasilver(I) complex [Ag4(μ‐P6)2](OTf)4(4), which was readily transformed by treatment with AgOTf into3, revealing a drastic alternation of the twoP6arrangement. The hexagold(I) chains exhibited a considerably red‐shifted absorption (∼410 nm) and emission (540–580 nm) to1[5dσ*→6pσ] and from3[5dσ*→6pσ] excited states of the metal centers, respectively. The new linear hexaphosphine could be a useful tool to construct linear metal clusters as subnano building blocks.