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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >TTF salts of optically pure cobalt pyridine amidates; Detection of soluble assemblies with stoichiometry corresponding to the solid state
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TTF salts of optically pure cobalt pyridine amidates; Detection of soluble assemblies with stoichiometry corresponding to the solid state

机译：光学纯的吡啶吡啶鎓钴酸盐的TTF盐;以化学计量法检测与固态对应的可溶性装配

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摘要

Optically pure anionic complexes of pyridinecarboxamide ligands, N ~2, N~6-bis((R)-α-methylbenzyl)pyridine-2, 6-dicarboxamide H_2(R, R-L~1) and N~2, N ~6-bis((S)-1-methoxypropan-2-yl)pyridine-2, 6-dicarboxamide H _2(S, S-L~2) have been synthesised and fully characterised. The complexes: (18-crown-6)K[Co~(III)(R, R-L~1)_2], (18-crown-6)K[Fe~(III)(R, R-L~1)_2] and K[Co ~(III)(S, S-L~2)_2]·3H_2O show interesting extended structures from 0D discrete units through 1D zigzag chains to 2D honeycomb layers. The complex anions were used in the synthesis of radical cation salts with tetrathiafulvalene (TTF). The salts (TTF)[Co ~(III)(R, R-L~1)_2] and (TTF)[Co~(III)(S, S- L~2)_2]·EtOAc were characterised by single crystal X-ray diffraction and conductivity measurements. Both compounds comprise mono-oxidised TTF molecules and exhibit similar layered structures with no direct TTF stacking but in which phenyl substituents from the complex anion or co-crystallised ethyl acetate alternate with TTF~+ units. Solution spectroscopic and cyclic voltammetric evidence points to the formation of soluble assemblies between TTF~+ and the counterion which correspond to the stoichiometry observed by crystallography and other methods in the solid state.
机译：吡啶甲酰胺配体，N〜2，N〜6-双（（R）-α-甲基苄基）吡啶-2、6-二甲酰胺H_2（R，RL〜1）和N〜2，N〜6-的光学纯阴离子络合物已合成并完全表征了双（（S）-1-甲氧基丙烷-2-基）吡啶-2，6-二甲酰胺H _2（S，SL〜2）。配合物：（18-冠-6）K [Co〜（III）（R，RL〜1）_2]，（18-冠-6）K [Fe〜（III）（R，RL〜1）_2] K [Co〜（III）（S，SL〜2）_2]·3H_2O显示出有趣的扩展结构，从0D离散单元到1D之字形链到2D蜂窝层。络合阴离子用于与四硫富瓦烯（TTF）合成自由基阳离子盐。盐（TTF）[Co〜（III）（R，RL〜1）_2]和（TTF）[Co〜（III）（S，S-L〜2）_2]·EtOAc用单晶X-射线衍射和电导率测量。两种化合物都包含单氧化的TTF分子，并显示相似的层状结构，没有直接的TTF堆积，但是其中来自复合阴离子或共结晶乙酸乙酯的苯基取代基与TTF +单元交替出现。溶液光谱法和循环伏安法的证据表明，TTF +和抗衡离子之间形成了可溶的组装，这对应于通过晶体学和其他方法观察到的固态化学计量。

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