Towards the clathrochelate-based electrochromic materials: The case study of the first iron(II) cage complex with an annelated quinoxaline fragment

Electrophilic Addition of Polyaromatic o-Quinones to an Iron(II) Diaminoclathrochelate Leading to the Macrobicyclic Iron(II) tris-Dioximates with Extended Annulated Ribbed Substituents

“…The absence of proper isosbestic points can be explained by the low concentration of the initial complex comparable with that of the trace contaminants remaining in the solvent. The spectrum of the reduced macrobicyclic derivative of FeBd 2 ((Phen))Gm)(BF) 2 is quite similar to that of the anion-radical derivative of the quinoxaline-containing clathrochelate analog, [5] thus suggesting chemical one-electron ligand-centered reduction of FeBd 2 ((Phen)Gm)(BF) 2 .…”

“…[1][2][3][4] Recently we described an iron(II) clathrochelate with annulated ribbed quinoxaline fragment that exhibited the reversible ligand-centered redox transformations coupled with electrochromism. [5] Its annulated azaheterocyclic moiety has been constructed using nucleophilic substitution of the reactive chlorine atoms in a dichloroclathrochelate precursor FeBd 2 (Cl 2 Gm)(BF) 2 (where Bd 2-and Cl 2 Gm 2-are α-benzildioxime and dichloroglyoxime dianions) (Scheme 1).…”

Synthesis, X-Ray Structure and (Spectro)electrochemical Study of an Electrochromic Iron(II) Chlathrochelate with Tuned Redox Properties

“…[23] This approach is based on nucleophilic substitution of the reactive chlorine atoms of the dichloroclathrochelate precursor FeBd 2 (Cl 2 Gm)(BF) 2 with 4,5-dimethyl-1,2-phenylenediamine in the presence of triethylamine as organic base followed by in situ oxidation of the amine macrobicyclic intermediate FeBd 2 H} NMR spectra. The molecular structure of this complex was studied both in solid state and in solution using single-crystal X-ray diffraction and various NMR techniques, respectively.…”

“…[17][18][19][20][21][22] Another pathway of transformations of these cage metal complexes is based on the ligand-centered processes, such as chemical or electrochemical redox reactions of heterocyclic ribbed fragments, annulated to the quasiaromatic macrobicyclic framework. Recently [23] we reported the synthesis and reactivity of an iron(II) clathrochelate FeBd 2 (QnGm) (BF) 2 (where Bd 2-and Gm are a-benzildioxime dianion and glyoxime residue, respectively) carrying an annulated ribbed quinoxaline (Qn) fragment. This complex revealed the reversible, ligand-centered, chemical (electrochemical) redox transformations coupled with electrochromism.…”

The Role of Oxygen in Electrochemical Reduction of Double-Decker Phthalocyaninates of Lanthanides

“…Apparently, this process leads to formation of the compounds of studied phthalocyaninates with dissolved oxygen, as a result of decomposition of which reduced forms of phthalocyaninates that do not contain oxygen are generated at potentials below -1.2 V. It is interesting to note that analogous role of the dissolved oxygen in electrochemical processes was observed by us for solutions of the compounds of another classiron(II) clathrochelates. [40] The results obtained should be considered upon investigation of the electrochemical processes occurring in the Langmuir-Blodgett films of the studied compounds. Single-layered films were obtained under conditions described in the experimental section.…”