Incorporation of Mn(II) and Fe(II) into uranyl carboxyphosphonates

Alsobrook A.N.; Alekseev E.V.; Depmeier W.; Albrecht-Schmitt T.E.

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Incorporation of Mn(II) and Fe(II) into uranyl carboxyphosphonates

机译：Mn（II）和Fe（II）掺入铀酰羧基膦酸酯

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Five heterobimetallic U(VI)/M(II) (M = Mn, Fe) carboxyphosphonates have been synthesized under mild hydrothermal conditions by reacting UO_3, triethyl phosphonoacetate, with either Mn(II) or Fe(II) acetate. The manganese reactions yield Mn_2[(UO_2)_6(PO _3CH_2CO_2)_3O_3(OH)(H _2O)_2]?16H_2O (MnUPAA-1) and [Mn(H _2O)_6][Mn(H_2O)_5Mn_2(UO _2)_5(PO_3CH_2CO_2) _6(H_2O)]?5.75H_2O (MnUPAA-2). The addition of boric acid, which lowers the crystallization temperature, allows for the production of a third product, [Mn(H_2O)_4] _2(UO_2)_3(PO_3CH_2CO _2)_2O_2 (MnUPAA-3). The iron-containing reactions yield [Fe(H_2O)_6][UO_2(PO_3CH _2CO_2)]_2?8H_2O (FeUPAA-1) and [Fe(H_2O)_6][UO_2(PO_3CH _2CO_2)H_2O]_2?4H_2O (FeUPAA-2). Four of these five compounds crystallize in low-symmetry space groups; whereas MnUPAA-1 crystallizes in the cubic space group Im3 and possesses a remarkably complex open-framework structure containing both UO_7 pentagonal bipyramids and UO_8 hexagonal bipyramids. MnUPAA-3 adopts a one-dimensional uranium oxide topology that contains both UO_6 tetragonal bipyramids and UO_7 pentagonal bipyramids. The remaining three compounds solely contain UO_7 pentagonal bipyramids.

机译：通过使UO_3，膦酸三乙酯与乙酸Mn（II）或Fe（II）反应，在温和的水热条件下合成了五种双双金属U（VI）/ M（II）（M = Mn，Fe）羧基膦酸酯。锰反应产生Mn_2 [（UO_2）_6（PO _3CH_2CO_2）_3O_3（OH）（H _2O）_2]？16H_2O（MnUPAA-1）和[Mn（H _2O）_6] [Mn（H_2O）_5Mn_2（UO _2） _5（PO_3CH_2CO_2）_6（H_2O）]→5.75H_2O（MnUPAA-2）。硼酸的添加降低了结晶温度，从而允许生产第三种产物[Mn（H_2O）_4] _2（UO_2）_3（PO_3CH_2CO _2）_2O_2（MnUPAA-3）。含铁反应产生[Fe（H_2O）_6] [UO_2（PO_3CH _2CO_2）] _ 2？8H_2O（FeUPAA-1）和[Fe（H_2O）_6] [UO_2（PO_3CH _2CO_2）H_2O] _2？4H_2O（FeUPAA- 2）。这五种化合物中的四种在低对称空间群中结晶。而MnUPAA-1则在立方空间群Im3中结晶，并具有一个非常复杂的开放框架结构，其中同时包含UO_7五角双锥和UO_8六角双锥。 MnUPAA-3采用一维铀氧化物拓扑结构，其中既包含UO_6四方双锥体，又包含UO_7五方双锥体。其余三种化合物仅包含UO_7五角双锥体。

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《Crystal growth & design》 |2011年第6期|共10页
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Alsobrook A.N.; Alekseev E.V.; Depmeier W.; Albrecht-Schmitt T.E.;
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Incorporation of Mn(II) and Fe(II) into uranyl carboxyphosphonates

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