Interaction of Dichloride Iron(II) Clathrochelate with Dimercaptomaleodinitrile: Synthesis of the Precursor Monoribbed-Functionalized Phthalocyaninoclathrochelates and the Unexpected Formation of a New Thiophene-Containing Heterocyclic System in the Ribbed Chelate Fragment of the Clathrochelate Framework

Abstract

Clathrochelate iron(II) FeBd 2(S2C2(CN)2Gm)(BF)2 tris-dioximate with a ribbed vic-dinitrile fragment was synthesized as a precursor of the monoribbed-functionalized hybrid phthalocyaninoclathrochelates by nucleophilic substitution of the vic-dichloride FeBd2(Cl2Gm)(BF)2 clathrochelate (1) with the potassium salt of dimercaptomaleodinitrile. Reaction of nitromethane with this salt was followed by the condensation of the reaction products with 1 to yield the clathrochelate with an annulated previously unknown thiazinothiophene heterocyclic system in the ribbed fragment. Both complexes were characterized on the basis of elemental analysis; MALDI-TOF mass spectrometry; IR, UV-vis, (57)Fe Mössbauer, and NMR spectroscopies; and X-ray crystallography.

Single molecular switch based on thiol tethered iron(II)clathrochelate on gold

“…The optimized structure of the IC matched with crystal studies [15,16]. The HOMO-LUMO gap of thiol tethered IC was determined from both the UV-vis spectra and DFT calculations is approximately 2.7 eV.…”

“…This is due to the fact that an encapsulated and coordinatively saturated metal ion is isolated from environmental factors. The size of a three-dimensional ligand cavity may be controlled by changing the nature of the capping and chelating fragments of the macropolycyclic framework and donor atoms (groups) that are optimal for stabilization of a desired electronic configuration of this ion [15,16].…”

The first example of the alkoxy-containing iron(ii) tris-dioximate clathrochelate: synthesis, structure, and properties

“…The molec ular structure of complex 2 (Fig. 1) is characteristic of the iron(II) tris dioximate clathrochelates 1, 22 : the FeN 6 co ordination polyhedron of the encapsulated iron(II) ion has a distorted trigonal prismatic (TP) geometry with the distortion angle ϕ = 26.2° (for an ideal TP ϕ = 0°, and for a trigonal antiprism (TAP) ϕ = 60°). The Fe-N bond distances in the coordination polyhedron are appro ximately 1.90 Å (Table 1), and the height of this polyhe dron is 2.32 Å.…”

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

“…These fragments of a quasiaromatic macrobicyclic polyazomethine framework have been functionalized using well-known "classical" organic reactions, such as N,O,S,C,P-nucleophilic substitution, [1][2][3] free-radical substitution [4,5] and electrophilic addition to the diamine iron(II) clathrochelate. [6,7] These reactions allowed obtaining the different types of mono-, di-and triribbedfunctionalized cage complexes with pendant and annulated substitutents, thus paving the way to new types of molecular switches, [8] wires, [9,10] light-and redox-driven molecular machines [11][12][13] and clathrochelate-based electrocatalysts for hydrogen evolution reaction. [14][15][16] The rigidity of their polyazomethine macrobicyclic ligands imposes a strong limitation on the size of the encapsulated metal ion.…”