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首页> 外文期刊>Chemistry: A European journal >Effect of bulkiness on reversible substitution reaction at Mn~(II) center with concomitant movement of the lattice DMF: Observation through single-crystal to single-crystal fashion
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Effect of bulkiness on reversible substitution reaction at Mn~(II) center with concomitant movement of the lattice DMF: Observation through single-crystal to single-crystal fashion

机译：体积对Mn〜（II）中心可逆取代反应及晶格DMF伴随运动的影响：单晶至单晶的观察

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摘要

The porous coordination polymer ({[Mn(L)H_2O](H _2O)_(1.5)(dmf)}n, 1) (DMF = N,N-dimethylformamide) exhibits variety of substitution reactions along with movement of lattice DMF molecule depending upon bulkiness of the external guest molecules. If pyridine or 4-picoline is used as a guest, both lattice and coordinated solvent molecules are simultaneously substituted (complexes 6 and 7, respectively). If a bulky guest like aniline is used, a partial substitution at the metal centers and full substitution at the channels takes place (complex 8). If the guest is 2-picoline (by varying the position of bulky methyl group with respect to donor N atom), one Mn~(II) center is substituted by 2-picoline, whereas the remaining center is substituted by a DMF molecule that migrates from the channel to the metal center (complex 9). Here, the lattice solvent molecules are substituted by 2-picoline molecules. For the case of other bulky guests like benzonitrile or 2,6-lutidine, both the metal centers are substituted by two DMF molecules, again migrating from the channel, and the lattice solvent molecules are substituted by these guest molecules (complex 10 and 11, respectively). A preferential substitution of pyridine over benzonitrile (complex 12) at the metal centers is observed only when the molar ratio of PhCN:Py is 95:5 or less. For the case of an aliphatic dimethylaminoacetonitrile guest, the metal centers remain unsubstituted (complex 13); rather substitutions of the lattice solvents by the guest molecules take place. All these phenomena are observed through single crystal to single crystal (SC-SC) phenomena.
机译：多孔配位聚合物（{[Mn（L）H_2O]（H _2O）_（1.5）（dmf）} n，1）（DMF = N，N-二甲基甲酰胺）随着晶格DMF分子的移动表现出多种取代反应取决于外部客体分子的体积。如果使用吡啶或4-甲基吡啶作为客体，则同时取代晶格和配位溶剂分子（分别为配合物6和7）。如果使用笨重的客体（如苯胺），则会在金属中心进行部分置换，并在通道处进行完全置换（络合物8）。如果客人是2-甲基吡啶（通过改变相对于施主N原子的大分子甲基的位置），则一个Mn〜（II）中心被2-甲基吡啶取代，而其余的中心被迁移的DMF分子取代从通道到金属中心（复合体9）。在此，晶格溶剂分子被2-甲基吡啶分子取代。对于其他笨重的客体，例如苄腈或2,6-二甲基吡啶，两个金属中心均被两个DMF分子取代，再次从通道中迁移出来，而晶格溶剂分子被这些客体分子取代（复合物10和11，分别）。仅当PhCN：Py的摩尔比为95：5或更小时，才观察到吡啶优先于金属中心上的苄腈（配合物12）取代。对于脂族二甲基氨基乙腈客体，金属中心保持未取代状态（配合物13）;相反，晶格溶剂被客体分子取代。通过单晶到单晶（SC-SC）现象可以观察到所有这些现象。

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