Hydrogen-bonded assemblies of two-electron reduced mixed-valence [XMo12O40] (X = P and Si) with p-phenylenediamines.
Hydrogen-bonded assemblies of two-electron reduced mixed-valence [XMo12O40] (X = P and Si) with p-phenylenediamines.
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DOI：
10.1021/ic200683e
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发表时间：
2011-06
影响因子：
4.6
通讯作者：
T. Akutagawa;F. Kudo;R. Tsunashima;S. Noro;L. Cronin;Takayoshi Nakamura
中科院分区：
文献类型：
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作者：
T. Akutagawa;F. Kudo;R. Tsunashima;S. Noro;L. Cronin;Takayoshi Nakamura
通过对苯二胺（PPD）和2，3，5，6-四甲基-PPD（TMPPD）（供体）和H（+）（3）[PMo（12）O（40）]（3-）或H（+）（4）[SiMo（12）O（40）]（4-）（受体）在CH（3）CN中的溶液。[PMo（12）O（40）]（5-）和[SiMo（12）O（40）]（6-）团簇的氧化还原状态由氧化还原滴定和电子吸收测量确定。在（HPPD（+））（3）（H（+））（2）[PMo（12）O（40）]（5-）（CH（3）CN）（3-6）（1）中，单质子化HPPD（+）之间的N-H ~ O氢键相互作用（或双质子化的H2 PPD（2+））和[PMo（12）O（40）]（5-）形成风车状组装体，并形成具有交叉-截面积为0.065 nm（2），并且这些被CH（3）CN分子填充。此外，通过将1的单晶浸入H（2）O、CH（3）OH和C（2）H（5）OH溶剂中来除去盐1中的CH（3）CN分子。在化合物（HTMPPD（+））（6）[SiMo（12）O（40）]（6-）（CH（3）CN）（6）（2）中，单质子化的HTMPPD（+）分子与[SiMo（12）O（40）]（6-）之间通过N-H ~ O氢键相互作用形成了“土星环”式的组装体。每个Saturn环通过HTMPPD（+）的氢键和π堆积相互作用排列成六边形排列阵列，而存在于盐2中的CH（3）CN溶剂仅存在于零维孤立腔中。
Hydrogen-bonded assemblies of the two-electron reduced mixed-valence Keggin clusters [PMo(12)O(40)](5-) and [SiMo(12)O(40)](6-) were obtained by the one-pot electron-transfer reactions between p-phenylenediamine (PPD) or 2,3,5,6-tetramethyl-PPD (TMPPD) (donors) and H(+)(3)[PMo(12)O(40)](3-) or H(+)(4)[SiMo(12)O(40)](4-) (acceptors) in CH(3)CN. The redox states of the [PMo(12)O(40)](5-) and [SiMo(12)O(40)](6-) clusters were confirmed by the redox titrations and electronic absorption measurements. In (HPPD(+))(3)(H(+))(2)[PMo(12)O(40)](5-)(CH(3)CN)(3-6) (1), the N-H ~ O hydrogen-bonded interactions between the monoprotonated HPPD(+) (or diprotonated H2PPD(2+)) and the [PMo(12)O(40)](5-) resulted in a windmill-like assembly and hydrophilic one-dimensional channels are formed with a cross-sectional area of 0.065 nm(2), and these are filled by the CH(3)CN molecules. Also, the CH(3)CN molecules in salt 1 were removed by immersing the single crystals of 1 into H(2)O, CH(3)OH, and C(2)H(5)OH solvents. In the compound, (HTMPPD(+))(6)[SiMo(12)O(40)](6-)(CH(3)CN)(6) (2), the N-H ~ O hydrogen-bonded interactions between the monoprotonated HTMPPD(+) molecules and the [SiMo(12)O(40)](6-) formed a "Saturn-ring"-like assembly. Each Saturn-ring was arranged into an hexagonally packed array via hydrogen-bonded and π-stacking interactions of HTMPPD(+), while the CH(3)CN solvent present in salt 2 are only found in the zero-dimensional isolated cavities.