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Heptacoordinated W(IV) Cyanido Supramolecular Complex Trapped by Photolysis of a [W(CN)6(bpy)]2–/Zn2+ System
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2020-11-13 , DOI: 10.1021/acs.cgd.0c00966
Maciej Hodorowicz 1 , Janusz Szklarzewicz 1 , Mariusz Radoń 1 , Anna Jurowska 1
Affiliation  

The synthesis and single-crystal X-ray structure of the supramolecular complex {[Zn]1.5[Zn(H2O)][W(CN)5(OH)2][W(CN)5(OH)(H2O)]} (1) are reported. We found that photolysis of PPh4[W(CN)6(bpy)] in the presence of Zn(NO3)2 aq results in formation of a porous supramolecular network (channels with a volume of 44.1% of the unit cell volume) with all cyanido ligands involved in W–CN–Zn bridges. Complex 1 crystallizes in the Pmn space group with a cell volume of 20560.7 Å3 with three Zn and two W distinct coordination spheres. All water coordinated to Zn is directed into holes of 8.27 Å in diameter in porous 1. The presence of Zn cations during the photolysis results in isolation and structural characterization of unique seven-coordinate complex ions, [W(CN)5(OH)2]3– and [W(CN)5(OH)(H2O)]2–, which were earlier only postulated as the photolysis intermediates. Quantum chemical calculations for isolated [W(CN)5(OH)2]3– and [W(CN)5(OH)(H2O)]2– ions show that their ideal pentagonal bipyramid geometries around W(IV) atoms are stable only in the crystal phase due to interactions with Zn2+ cations. The energy difference between the most stable distorted pentagonal bipyramid and that found in the crystal structure is predicted to be only 4 or 11 kcal/mol for each ion, respectively. The tungsten and zinc sites present in the crystal lattice of 1 pose different acidic properties for their aqua ligands with theoretically estimated pKa values of ca. 7 and 8, respectively.

中文翻译:

[W(CN)6(bpy)] 2- / Zn 2+系统的光解捕集的七配位的W(IV)氰基超分子复合物

超分子配合物{[Zn] 1.5 [Zn(H 2 O)] [W(CN)5(OH)2 ] [W(CN)5(OH)(H 2)的合成和单晶X射线结构O)]}(1)被报告。我们发现在Zn(NO 32 aq存在下PPh 4 [W(CN)6(bpy)]的光解导致形成多孔超分子网络(通道的体积为单位细胞体积的44.1%) W-CN-Zn桥中涉及的所有氰基配体。复杂1个结晶在PM 3 Ñ空间群20560.7埃的细胞体积3具有三个Zn和两个W不同的配位球。所有与Zn配位的水被引导到多孔1中直径为8.27Å的孔中。在光解过程中锌阳离子的存在导致独特的七配位复合离子[W(CN)5(OH)2 ] 3–和[W(CN)5(OH)(H 2 O)的分离和结构表征] 2–,以前仅假定为光解中间体。分离的[W(CN)5(OH)2 ] 3–和[W(CN)5(OH)(H 2 O)] 2–的量子化学计算离子表明,由于与Zn 2+阳离子的相互作用,它们在W(IV)原子周围的理想五边形双锥体几何形状仅在晶相中稳定。对于每个离子,最稳定的扭曲五角形双锥体与晶体结构中发现的能量差分别仅为4或11 kcal / mol。存在于1晶格中的钨和锌位点对其水族配体具有不同的酸性,理论上估计的p K a值为ca。分别为7和8。
更新日期:2020-12-02
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