Supramolecular inter-ionic charge-transfer complexes between derivatives of pyridinium-4-oxime cations and hexacyanoferrate(ii) anions†,New Journal of Chemistry

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Supramolecular inter-ionic charge-transfer complexes between derivatives of pyridinium-4-oxime cations and hexacyanoferrate(ii) anions†
New Journal of Chemistry ( IF 2.7 ) Pub Date : 2018-09-05 00:00:00 , DOI: 10.1039/c8nj03066a
Blaženka Foretić _{1,

2,

3,

4,

5} , Robert Vianello _{5,

6,

7,

8,

9} , Dubravka Matković-Čalogović _{3,

5,

10,

11,

12} , Dijana Jadreško _{5,

9,

13} , Igor Picek _{1,

2,

3,

4,

5}

Affiliation

Mono- and bis-pyridinium-4-oxime compounds are introduced as new electron acceptors for the formation of colored, supramolecular, inter-ionic charge-transfer complexes with hexacyanoferrate(II) as a donor. The structure and properties of the formed complexes are characterized by a combination of experimental and computational studies. In water, the electron-donor/acceptor dyads exhibit a characteristic charge-transfer band in the visible spectral region whose energy is closely related to the acceptor's electron affinity, LUMO orbital energy and one-electron reduction potential. Such influence of the acceptor's electrochemical nature is revealed through varying the group attached to the N atom of the pyridinium-4-oxime moiety. The color, composition and spectroscopic analysis of the complexes in the solid state provide insights into binding of the cationic and anionic counterparts and the role of lattice water. Crystal structures are reported for two mono-pyridinium-4-oxime/hexacyanoferrate(II) complexes, characterized in solution by UV/Vis and ¹H-NMR spectroscopy. Comparison of the solid-state structures and the aqueous-phase dyads reveals the nature of the charge-transfer interactions involving conjugated pyridinium-4-oximes as electron acceptors.

中文翻译：

吡啶鎓-4-肟阳离子与六氰合铁酸酯（ii）阴离子之间的超分子离子间电荷转移络合物†

单吡啶和双吡啶-4-肟化合物被引入作为新的电子受体，与六氰合铁酸酯形成有色，超分子，离子间电荷转移络合物（II）作为捐赠者。形成的复合物的结构和性质通过实验研究和计算研究相结合来表征。在水中，电子给体/受体二重体在可见光谱区域显示出特征性的电荷转移带，其能量与受体的电子亲和力，LUMO轨道能和单电子还原电势密切相关。通过改变连接到吡啶鎓-4-肟部分的N原子上的基团，揭示了受体的电化学性质的这种影响。固态配合物的颜色，组成和光谱分析为洞悉阳离子和阴离子对应物的结合以及晶格水的作用提供了见识。报道了两种4-吡啶肟/六氰基高铁酸盐的晶体结构（II）配合物，其溶液通过UV / Vis和¹ H-NMR光谱表征。固态结构和水相二元化合物的比较揭示了涉及共轭吡啶鎓-4-肟作为电子受体的电荷转移相互作用的性质。

更新日期：2018-09-05

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