Реферат: Nucleophilic substitution of the bis-alpha-benzyldioximate clathrochelate precursor with ortho-phenylenediamine hydrochloride in the presence of triethylamine as an organic base under mild conditions afforded the macrobicyclic iron (II) complex with an annelated ribbed quinoxaline fragment. This complex easily underwent oxidation in solution with air oxygen leading to its oxidized macrobicyclic derivative with the quinoid ribbed system. Such cage complex with a heterocyclic fragment annelated to its quasi-aromatic polyazomethine electron-withdrawing macrobicyclic framework possesses pronounced oxidative properties and undergoes both the chemical (with metallic lithium) and electrochemical stepwise reduction to the corresponding radical anion macrobicyclic species, registered by EPR, and, then, to the diamagnetic dianionic clathrochelate complex. Such reductions were found to be accompanied by dramatic changes in coloration from blue-violet to yellow (that is characteristic of the macrobicyclic anion radical) and orange-red (that is characteristic of the clathrochelate dianion); these redox and electrochromic properties were studied using cyclic voltammetry and spectroelectrochemistry in solution and in a thin film. The clathrochelates obtained were characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV-vis, EPR, H-1, B-11, F-19 and C-13{H-1} NMR spectroscopy, and by X-ray diffraction; their FeN6-coordination polyhedra possess a distorted trigonal prismatic-trigonal antiprismatic geometry with the distortion angles of approximately 24 degrees. The Fe-N distances vary from 1.89 to 1.94 angstrom, and the heights h of such polyhedra are 2.33 and 2.36 angstrom, respectively. So, the first clathrochelates with redox-innocent encapsulated metal ion and redox-active macrobicycle ligand systems have been prepared and characterized. For the first time, a quasi-aromatic polyazomethine cage metal complex with an annelated redox-active heterocyclic fragment, having an extended pi-conjugated system, has been shown to undergo a reversible 2-electron reduction accompanied with electrochromism both in solution and as a thin film. (C) 2014 Elsevier B.V. All rights reserved.

Библиографическая ссылка: Burdukov A.B. , Vershinin M.A. , Pervukhina N.V. , Boguslvaskii E.G. , Eltsov I.V. , Shundrin L.A. , Selector S.L. , Shokurov A.V. , Voloshin Y.Z.
Towards the clathrochelate-based electrochromic materials: The case study of the first iron(II) cage complex with an annelated quinoxaline fragment
Inorganic Chemistry Communications. 2014. V.44. P.183-187. DOI: 10.1016/j.inoche.2014.03.032 WOS Scopus РИНЦ

Даты:

Опубликована в печати:

1 июн. 2014 г.

Идентификаторы:

Web of science	WOS:000336772700042
Scopus	2-s2.0-84898605543
РИНЦ	21872165
OpenAlex	W2092166991

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