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Publications (287)
Combined experimental 57Fe Mössbauer and theoretical DFT study of a series of iron(II)-centered (pseudo)macrobicyclic analogs and homologs was performed. The field strength of the corresponding (pseudo)encapsulating ligand was found to affect both the spin state of a caged iron(II) ion and the electron density at its nucleus. In a row of the iron(I...
A multistep general synthetic strategy towards polytopic carboranyl-containing (semi)clathrochelate metal complexes, based on the template synthesis, transmetallation, amide condensation and 1,3-dipolar cycloaddition reactions, is developed. Their mono(semi)clathrochelate precursors with a single reactive group were obtained using a transmetallatio...
The title cobalt(II) pseudoclathrochelate complexes possess an intermediate trigonal prismatic-trigonal antiprismatic geometry. As follows from PPMS data, they exhibit an SMM behaviour with Orbach relaxation barriers of approximately 90 K. Paramagnetic NMR experiments confirmed a persistence of these magnetic characteristics in solution. Therefore,...
Fast crystallization of the monoclathrochelate cobalt(II) intracomplex [Co(Cl2Gm)3(BAd)2] (where Cl2Gm2- is a dichloroglyoxime dianion and BAd is an adamantylboron capping group, 1), initially obtained by the direct template condensation of the corresponding chelating α-dioximate and cross-linking ligand synthons on the Co2+ ion as a matrix, from b...
Mixed boron,antimony-capped iron(II) tris-dioximate monoclathrochelates and their hybrid phthalocyaninatoclathrochelate derivatives, the molecules of which are decorated with the single N-donor 4-pyridyl group, were obtained using two different approaches, such as ([Formula: see text] a transmetallation (a capping group exchange) reaction of their...
Reaction of the template synthesis of the methylboron‐capped iron(II) tris‐heptoximate clathrochelate on Fe2+ ion as a matrix was found to proceed in the quantitative yield in diluted aqueous‐organic solutions. This complex is intensively colored in the visible range, whereas the initial ligand synthons are optically silent, thus allowing to photom...
Multistep synthetic pathway towards a series of the anisoleboron-capped ribbed-functionalized iron(II) cage complexes was developed. Their hexachloroclathrochelate precursor was obtained by the template condensation of three dichloroglyoximate chelating ligand synthons with two molecules of 4-methoxyphenylboronic acid as a Lewis-acidic cross-linkin...
Tris-pyridineoximate iron, cobalt, and nickel(II) pseudoclathrochelates with apical ferrocenyl substituent were obtained in the reasonable yields (50–70%) in a boiling ethanol by the template condensation of 2-acetylpyridineoxime with ferrocenylboronic acid on the corresponding M ²⁺ ion as a matrix. The composition and structure of new ditopic comp...
Multistep synthetic pathway towards a series of the anisoleboron-capped ribbed-functionalized iron(II) cage complexes was developed. Their hexachloroclathrochelate precursor was obtained by the template condensation of three dichloroglyoximate chelating ligand synthons with two molecules of 4-methoxyphenylboronic acid as a Lewis-acidic cross-linkin...
Binuclear FeII, ZrIV(HfIV)-containing phthalocyaninatoclathrochelates with a terminal reactive formyl group were prepared using three synthetic approaches, (i) the direct template condensation of appropriate chelating and capping ligand synthons on the iron(ii) ion as a matrix, (ii) a transmetallation of the initially obtained macrobicyclic precurs...
Comprehensive Summary
General and straightforward synthetic strategy towards the iron(II) clathrochelates with functionalizing substituents in their apical capping and one of the three chelate ribbed fragments was developed. Their hexachloroclathrochelate precursors were prepared by the direct template condensation of dichloroglyoxime with a suitab...
Hybrid metallo(IV)phthalocyaninate-capped tris-dioximate iron(II) complexes (termed as "phthalocyaninatoclathrochelates") with non-equivalent apical fragments and functionalized with one terminal reactive vinyl group were prepared for the first time using three different synthetic approaches: (i) transmetallation (capping group exchange) of the app...
The interest in functional supramolecular systems for the design of innovative materials and technologies, able to fundamentally change the world, is growing at a high pace. The huge array of publications that appeared in recent years in the global literature calls for systematization of the structural trends inherent in the formation of these syst...
Kinetics and thermodynamics of the template synthesis and of the acidic decomposition of the methylboron-capped iron(II) tris-1,2-dioximates—the clathrochelate derivatives of six (nioxime)- and eight (octoxime)-membered alicyclic ligand synthons—were compared. In the case of a macrobicyclic iron(II) tris-nioximate, the plausible pathway of its form...
A synthetic strategy for obtaining structurally flexible hybrid iron(II) carboranoclatrochelates functionalized with biorelevant groups, based on a combination of a 1,3-dipolar cycloaddition reaction with nucleophilic substitution of an appropriate chloroclathrochelate precursor, was developed. In its first stage, a stepwise substitution of the dic...
Two most common synthetic approaches (i.e. the esterification and 1,3-dipolar cycloaddition reactions) to a function-alization of the reactive three-dimensional molecular platforms, allowing to obtain the fluorescently labelled iron(II) clathrochelates and, therefore, to study their localization and accumulation in cancer cells, were compared. Beca...
The fluorescein-tagged iron( ii ) clathrochelate was synthesized for the first time and its accumulation in A2780 cancer cells was studied.
The in situ spectroelectrochemical cyclic voltammetric studies of the antimony-monocapped nickel(II) and iron(II) tris-pyridineoximates with a labile triethylantimony cross-linking group and Zr(IV)/Hf(IV) phthalocyaninate complexes were performed in order to understand the nature of the redox events in the molecules of heterodinuclear zirconium(IV)...
Hydrogen-evolving cathodes were prepared using a series of iron(ii) clathrochelates bearing various number of terminal phenanthrenyl groups via physisorption on carbon paper and employed in the polymer electrolyte membrane water electrolysis cells instead of typically used platinum. In situ electrochemical activation of the cathodes was carried out...
Recognition of elements of protein tertiary structure is crucial for biotechnological and biomedical tasks; this makes the development of optical sensors for certain protein surface elements important. Herein, we demonstrated the ability of iron(II) clathrochelates (1–3) functionalized with mono-, di- and hexa-carboxyalkylsulfide to induce selectiv...
It is generally accepted that transition metal (pseudo)clathrochelates, a unique class of coordination compounds are easily obtained by a simple template condensation of appropriate oximes, boronic acids and metal salts. Our X‐ray diffraction study of single crystals unexpectedly found in the reaction mixtures of different pseudoclathrochelates, ho...
Hexaphenanthrene iron, cobalt and ruthenium(II) macrobicyclic complexes, the molecules of which have been designed for their efficient immobilization on carbon materials, such as activated carbon (AC), reduced graphene oxide (RGO) and carbon paper (CP), were tested as the cathode electro(pre)catalysts for hydrogen production in a PEM MEA water elec...
Boron-cross-linked cobalt(II) pseudoclathrochelate was obtained by the template reaction of 2-acetylpyrazoloxime, phenylboronic acid, and a new DMF cobalt(II) solvato complex with a decachloro-closo-decaborate dianion. As confirmed by single-crystal X-ray diffraction, this complex crystallizes with two symmetry-independent cobalt(II) pseudoclathroc...
Successful using of cage metal complexes (clathrochelates) and the functional hybrid materials based on them as promising electro- and (pre)catalysts for hydrogen and syngas production is highlighted in this microreview. The designed polyaromatic-terminated iron, cobalt and ruthenium clathrochelates, adsorbed on carbon materials, were found to be t...
The Fe, Co and Ru clathrochelates bearing terminal polar groups were immobilized as the precursors of single atom catalysts on a surface of highly porous ceramic material used as the support. The obtained materials, which were evaluated for a syngas production from CH4 based on its partial oxidation and dry reforming reactions, did not catalyze the...
First pseudomacrobicyclic phthalocyaninate-capped cobalt(III) tris-pyridineoximates were obtained in moderate yields (40–49 %) by the direct template condensation of 2-acetylpyridineoxime with zirconium(IV) and hafnium(IV)phthalocyaninates on the cobalt ion as a matrix. These complexes were thoroughly characterized using elemental analysis, MALDI-T...
Monopropargylamine iron(II) tris‐dioximate was easily prepared in a high yield using nucleophilic substitution of its monochloroclathrochelate precursor with propargylamine as a primary aliphatic amine N‐nucleophile in acetonitrile as a solvent. This complex with terminal C≡C group underwent a 1,3‐dipolar cycloaddition “click”‐reaction with ortho‐c...
Cage metal complexes iron(II) clathrochelates, which are inherently CD silent, were discovered to demonstrate intensive output in induced circular dichroism (ICD) spectra upon their assembly to albumins. With the aim to design clathrochelates as protein-sensitive CD reporters, the approach for the functionalization of one chelate a-dioximate fragme...
The detailed cyclic voltammetry (CV) study of the
iron(II) clathrochelates with one, two or six terminal
(poly)aromatic group(s) (Scheme, [1]) in a wide range
of scan rate of the potential using glassy carbon (GC)
and Pt working electrodes was performed. Their CVs
contain the single one-electron quasireversible Fe2+/+
reduction wave in the cathodic...
We performed an attempt to obtain newmonoribbed-difunctionalized clathrochelate iron(II) complexes with propargylamine- orpropargylamide-terminated ribbed substituents as the prospective macrobicyclic precursors oftheir Sonogashira reactions. However, we observed an uncommon low chemical stability ofthese propargylamine and propargylamide cage comp...
Clathrochelate complexes are the class of compounds that has shown a range of
biologically active properties. Various studies show that nature of terminal ribbed functional
groups is playing key role in its activity. In our recent study [1] we discovered that
clathrochelate molecules bearing aryl carboxygroups form supramolecular complexes with
ser...
Here we report a new trigonal prismatic cobalt(II) complex that behaves as a single molecule magnet. The obtained zero‐field splitting, which is also directly accessed by THz‐EPR spectroscopy (−102.5 cm−1), results in a large magnetization reversal barrier U of 205 cm−1. Its effective value, however, is much lower (101 cm−1) even though there is pr...
An ability of inherently achiral macrobicyclic metal complexes iron(ii) clathrochelates to acquire an induced CD (ICD) output in the visible spectral range upon interaction with bovine serum albumin (BSA) was recently discovered. In the present work, the CD-reporting properties of iron(ii) clathrochelates to proteins and the thermodynamic parameter...
Earlier, the hybrid binuclear metallophthalocyaninate-capped iron and nickel(II) tris-pyridineoximates have been prepared using a two-step synthetic procedure via transmetalation reaction of their labile triethylantimony-capped precursors. We elaborated new efficient synthetic pathway to the preparation of the titled complexes. This synthetic appro...
Transition metal clathrochelates are promising electrocatalysts of the hydrogen evolution reaction, for example at the cathodes of
water electrolysers. Their electrochemical activity can be maximized by forming monolayers on a surface of electrode materials of
large specific area, such as carbon powders or fibers. Surface functionalization via phys...
Tris-glyoximate and tris-dichloroglyoximate iron(II) clathrochelates with apical pyridyl groups were obtained through one-pot template condensation of the corresponding α-dioxime with 3- or 4-pyridylboronic acids on the iron(II) ion as a matrix under vigorous reaction conditions using the boiling CF3COOH as a solvent. The initially formed mixtures...
Zero-field splitting (ZFS) of three high-spin Co(I) ( S = 1) clathrochelate complexes was determined by frequency-domain Fourier-transform THz-EPR (FD-FT THz-EPR). The following axial and rhombic ZFS values ( D and E, respectively) were determined: [N( n-Bu)4]CoI(GmCl2)3(BPh)2 (1, D/ hc = +16.43(1) cm-1, E/ hc = 0.0(1) cm-1), [P(Me2N)4]CoI(GmCl2)3(...
Previously it’s been reported about biological activity of clatrochelates af iron (II) , hoverer, mechanism if its activity is still unknown. In order to comprehend the mechanism of iron (II) clatrochelates accumulation in cell it was desided to selectivly modify one of the clatrochelate’s edges with fluorescent fragment.
The iron(II) clathrochelates with one, two or six terminal (poly)aromatic group(s) (Scheme) have been designed [1] for their effective physical adsorption on carbonaceous substrates as the precatalysts of hydrogen evolution reaction. The quantitative data about their physical adsorption on activated carbon (AC) and reduced graphene oxide (RGO) were...
An attempt to prepare a hybrid clusteroclathrochelate by nucleophilic substitution of iron(II) dichloroclathrochelate by substitution of its chlorine atoms with the [Fe2(μ-S)2(CO)6]2– cluster dianion as a nucleophilic agent generated in situ by the reduction of Fe2(μ-S2)(CO)6 with lithium triethylborohydride unexpectedly gave the macrobicyclic comp...
A series of the iron and cobalt(II) mono- and bis-clathrochelates was in vitro tested in the transcription system of Taq DNA polymerase (DNAP), based on polymerase chain reaction. All these complexes were found to be micromolar transcription inhibitors, but only several clathrochelates with terminal biorelevant groups are inhibitors with IC50 in a...
Variable-temperature NMR spectroscopy has recently emerged as a new alternative to the magnetometry methods for studying single molecule magnets. Its use is based on an accurate determination of magnetic susceptibility tensor anisotropy Δχ, which is not always achievable due to some contact contribution to NMR chemical shifts and possible conformat...
Робота присвячена модифікації бензо-9-краун-3-ефірів а також синетзу нових краун-вмісних клатрохелатів заліза (II)
A new approach for performing Suzuki–Miyaura and Sonogashira reactions of iron(II) dihalogenoclathrochelates, optimizing their reaction conditions (such as temperature, solvent and a palladium-containing catalyst) and the nature of other reagents (such as arylboron components) is elaborated. These palladium-catalyzed reactions are very sensitive to...
The detailed cyclic voltammetry (CV) study of the iron(II) clathrochelates with one, two or six terminal (poly)aromatic group(s) in a wide range of scan rate of the potential using glassy carbon (GC) and Pt working electrodes was performed. Their CVs contain the single one-electron quasireversible Fe2þ/þ reduction wave in the cathodic potential ran...
The first synthesized and X-ray structurally characterized “classical” iron(I) dioximate showed an unrivaled stability towards strong acids; thus, calling for a reassessment of the origins of the electrocatalytic activity of...
An ability of the ribbed-functionalized iron(II) clathrochelates to induce a CD output in interactions with a protein, covalent bonding or supramolecular interactions with a low-molecular-weight chiral inductor, was discovered. The interactions of CD inactive, carboxyl-terminated iron(II) clathrochelates with serum albumin induced their molecular a...
New iron( ii ) di- and tetrahalogenoclathrochelates with apical functionalizing substituents were prepared and characterized.
A potential long-range electronic coupling between two apical ferrocenyl substituents in the clathrochelate molecule FeDm3(BFc)2 (where Dm2– is dimethylglyoximate dianion) was studied using the electrochemical and the spectroelec-trochemical methods with a low ion-pairing ability TBAF {(NBu4)(B(C6F5)4)} electrolyte. Experimental data are suggestive...
Transition metal clathrochelates form a family of the compounds of great practical interest for the hydrogen evolution reaction in acidic electrolytes. When adequately immobilized on the surface of appropriate carbonaceous substrates, they can find application at the cathode of polymer electrolyte membrane water electrolysis cells. The physisorptio...
Four hybrid binuclear metal phthalocyaninate-capped iron(II) and nickel(II) tris-pyridineoximates have been studied both in solutions and the fluoroplastic thin films by UV-Vis absorption technique. The studied polymer-immobilized cage metal complexes form the H-type dimers within the polymer matrix.
All six constitutional isomers of dimethoxy-terminated clathrochelate FeBd2((CH3OOCC6H4S)2Gm)(BF)2 (where Bd2– is α-benzildioxime dianion, Gm is glyoxime residue and BF is fluoroboron capping group) were obtained under mild reaction conditions by nucleophilic substitution of their dichloroclathrochelate precursor with the corresponding carboxypheny...
Self-assembly of monohexadecylboron-capped zinc, cobalt, iron and manganese(II) tris-pyrazoloximate pseudoclathrochelates was performed using one-pot template condensation of 2-acetylpyrazole oxime with n-hexadecylboronic acid as a capping Lewis-acidic agent on the corresponding metal ion as a matrix. Hydrogen atoms of three terminal pyrazolyl NH g...
The study tackles one of the challenges in developing platinum-free molecular electrocatalysts for hydrogen evolution, which is to seek for new possibilities to ensure large turnover numbers by stabilizing electrocatalytic intermediates. These species are often much more reactive than the initial electrocatalysts, and if not properly stabilized by...