The reaction of Mn(BF4 )2 ⋅x H2 O with (Pr4 N)2 TCNQF4 (TCNQF4 =2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) in a mixture of CH3 OH/CH2 Cl2 gives a 2:3 stoichiometric complex of (Pr4 N)2 [Mn2 (TCNQF4 )3 (CH3 OH)2 ] (1). If the solvent system used for the crystallisation of 1 is changed to CH3 OH/DMF, then a different product, [Mn(TCNQF4 )(DMF)2 ]⋅(CH3 OH)2 (2), is obtained. The use of Li2 TCNQF4 instead of (Pr4 N)2 TCNQF4 leads to the generation of [Mn2 (TCNQF4 )2 (DMF)4 ]⋅3 DMF (3). An unexpected mixed oxidation state network with a composition of [MnII 4 MnIII 16 O10 (OH)6 (OCH3 )24 (TCNQF4 )2 ](NO3 )2 ⋅24 CH3 OH (4), is formed if Mn(NO3 )2 ⋅x H2 O is used in place of Mn(BF4 )2 ⋅x H2 O in the reaction that leads to the formation of 3. Compounds 1-3 have been characterised by X-ray crystallography; FTIR, Raman and UV/Vis spectroscopy; and electrochemistry. Compound 4 has only been analysed by X-ray crystallography and vibrational spectroscopy (Raman, FTIR), owing to rapid deterioration of the compound upon exposure to air. These results indicate that relatively minor changes in reaction conditions have the potential to yield products with vastly different structures. Compound 1 adopts an anionic 2D network with unusual π-stacked dimers of the TCNQF4 2- dianion, whereas 2 and 3 are composed of similar neutral sheets of [Mn(TCNQF4 )(DMF)2 ]. Interestingly, the solvent has a significant influence on the stacking of the sheets in the structures of 2 and 3. In compound 4, clusters with a composition of [MnII 4 MnIII 16 O10 (OH)6 (OCH3 )24 (CH3 OH)4 ]6+ serve as eight-connecting nodes, whereas TCNQF4 2- ligands act as four-connecting nodes in a 3D network that has the same topology as fluorite. Compound 3 exhibits an exceptionally high super-catalytic activity for the electron-transfer reaction between ferricyanide and thiosulfate ions in aqueous media.

中文翻译：

---

锰基TCNQF4配合物中溶剂，阳离子和阴离子引起的结构变化：合成，晶体结构，电化学及其催化性能。

Mn（BF4）2⋅xH2 O与（Pr4 N）2 TCNQF4（TCNQF4 = 2,3,5,6-四氟-7,7,8,8-四氰基喹二甲烷）在CH3 OH / CH2的混合物中的反应Cl 2产生（Pr 4 N）2 [Mn 2（TCNQF 4）3（CH 3 OH）2]（1）的2：3化学计量的络合物。如果将用于1结晶的溶剂体系更改为CH3 OH / DMF，则会得到另一种产物[Mn（TCNQF4）（DMF）2]·（CH3 OH）2（2）。使用Li2 TCNQF4代替（Pr4 N）2 TCNQF4会生成[Mn2（TCNQF4）2（DMF）4]⋅3DMF（3）。如果Mn（NO3）2⋅会形成具有[MnII 4 MnIII 16 O10（OH）6（OCH3）24（TCNQF4）2]（NO3）2⋅24CH3 OH（4）组成的意外混合氧化态网络。在导致形成3的反应中，使用x H2 O代替Mn（BF4）2⋅xH2O。FTIR，拉曼光谱和紫外/可见光谱；和电化学。由于化合物4暴露在空气中会迅速变质，因此仅通过X射线晶体学和振动光谱法（拉曼光谱，FTIR）对化合物4进行了分析。这些结果表明，反应条件的相对较小的变化有可能产生具有截然不同的结构的产物。化合物1采用的阴离子2D网络具有TCNQF4 2-二价阴离子的不寻常的π堆叠二聚体，而化合物2和3由[Mn（TCNQF4）（DMF）2]的相似中性片组成。有趣的是，溶剂对2和3结构中的片材堆叠具有显着影响。在化合物4中，组成为[MnII 4 MnIII 16 O10（OH）6（OCH3）24（CH3 OH）4的簇） ] 6+充当八个连接节点，而TCNQF4 2-配体充当3D网络中的四个连接节点，该网络具有与萤石相同的拓扑结构。化合物3对水性介质中铁氰化物和硫代硫酸根离子之间的电子转移反应表现出极高的超催化活性。