Unexpected Supramolecular-Induced Redox Switching in Sandwich Gd Bisphthalocyaninate.

The redox state of the phthalocyanine in sandwich lanthanide complexes is crucial for their applications. In this work, we demonstrate that the cation-induced supramolecular assembly of crown-substituted phthalocyanine lanthanide complexes Ln[(15C5)4Pc]2 can be used to control the redox state of the ligand simultaneously with the coordination sphere of the central metal. We achieve unprecedented redox switching of phthalocyanine ligands in a double-decker Gd(III) complex, resulting from the intramolecular inclusion of potassium cations between the decks with simultaneous twisting of the ligands (the skew angle between them decreases from 44.61 to 0.21°). Such a structural change leads to an increase in the deck-to-deck distance and drastically facilitates ligand reduction. This process was shown to be anion-dependent: only potassium salts of weak acids (KOPiv and KOAc) induce intramolecular inclusion of cations with redox switching in contrast to salts of strong acids (KBr, KOPic, KSCN, and KPF6), where such a redox process does not occur. This breakthrough opens new avenues for controlling the electrochromic properties, of phthalocyanines, along with other properties, such as electrical conductivity, optics, etc.

A Family of Hexacopper Phenylsilsesquioxane/Acetate Complexes: Synthesis, Solvent-Controlled Cage Structures, and Catalytic Activity.

Convenient self-assembly synthesis of copper(II) complexes via double (phenylsilsesquioxane and acetate) ligation allows to isolate a family of impressive sandwich-like cage compounds. An intriguing feature of these complexes is the difference in the structure of a pair of silsesquioxane ligands despite identical (Cu6) nuclearity and number (four) of acetate fragments. Formation of particular combination of silsesquioxane ligands (cyclic/cyclic vs condensed/condensed vs cyclic/condensed) was found to be dependent on the synthesis/crystallization media. A combination of Si4-cyclic and Si6-condensed silsesquioxane ligands is a brand new feature of cage metallasilsesquioxanes. A representative Cu6-complex (4) (with cyclic silsesquioxanes) exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. Maximum yield of the products of cyclohexane oxidation attained 30 %. The compound 4 was also tested as catalyst in the Baeyer-Villiger oxidation of cyclohexanone by m-chloroperoxybenzoic acid: maximum yields of 88 % and 100 % of ϵ-caprolactone were achieved upon conventional heating at 50 °C for 4 h and MW irradiation at 70 or 80 °C during 30 min, respectively. It was also possible to obtain the lactone (up to 16 % yield) directly from the cyclohexane via a tandem oxidation/Baeyer-Villiger oxidation reaction using the same oxidant.

Preparation, X-ray Characterization, and Reactivity of the Rod-like and Angular Germanium- and Titanium(IV)-Capped Iron(II) Bis-Clathrochelates and Their Mono- and Bis-Capped (Semi)clathrochelate Precursors.

Transmetalation of the bis{triethylantimony(V)}-capped iron(II) tris-α-dioximate with n-butylboronic acid afforded the mixed antimony, boron cross-linked clathrochelate with single reactive antimony(V)-based apical fragment. This macrobicyclic precursor easily underwent the transmetalation reactions with germanium and titanium(IV) alkoxides to give the rod-like and angular FeII2MIV-trinuclear bis-clathrochelates. Those of the aforementioned diantimony(V)-capped complex with 3- and 4-carboxyphenylboronic acids afforded the monoboron-capped iron(II) semiclathrochelates, undergoing a double-cyclization (macrobicyclization) with germanium- and titanium(IV)-based capping agents. The reactions in the low-temperature range unexpectedly gave the stable 2:1 associates, formed by the bridging of two carboxyl-terminated macrobicyclic molecules of the mixed carboxylboron, triethylantimony-capped iron(II) clathrochelate with a triethylantimony(V)-based linker fragment. The obtained complexes were characterized using elemental analysis, MALDI-TOF, 1H and 13C{1H} NMR and UV-vis spectra, and single-crystal XRD experiments. The encapsulated iron(II) ion in their 3D-molecules is situated almost in the center of its FeN6-coordination polyhedron possessing a truncated trigonal-pyramidal geometry. Fe-N distances fall in the range 1.887(7)-1.945(4) Å characteristic of the low-spin iron(II) complexes. The cross-linking titanium and germanium(IV) ions in the corresponding bis-clathrochelate molecules form the octahedral MIVO6-coordination polyhedra, the MIV-O distances of which vary from 1.946(2) to 1.964(2) Å and from 1.879(7) to 1.907(6) Å, respectively.

Multiresponsive luminescent metal-organic framework for cooking oil adulteration detection and gallium(III) sensing.

A new 3D metal-organic framework {[Cd16(tr2btd)10(dcdps)16(H2O)3(EtOH)]∙15DMF}n (MOF 1, tr2btd = 4,7-di(1,2,4-triazol-1-yl)benzo-2,1,3-thiadiazole, H2dcdps = 4,4'-sulfonyldibenzoic acid) was obtained and its luminescent properties were studied. MOF 1 exhibited bright blue-green luminescence with a high quantum yield of 74 % and luminescence quenching response to a toxic natural polyphenol gossypol and luminescence enhancement response to some trivalent metal cations (Fe3+, Cr3+, Al3+ and Ga3+). The limit of gossypol detection was 0.20 µM and the determination was not interfered by the components of the cottonseed oil. The limit of detection of gallium(III) was 1.1 µM. It was demonstrated that MOF 1 may be used for distinguishing between the genuine sunflower oil and oil adulterated by crude cottonseed oil through qualitative luminescent and quantitative visual gossypol determination.

Enhancement of intermolecular aggregation on solvent-influenced strong hydrogen-bonded single crystal.

The intermolecular aggregation between the solvent and organic molecules is covered in the current article. 4,4'-(Buta-1,3-diyne-1,4-diyl)dibenzoic acid (DADBA) was used as an organic molecule and dimethyl sulfoxide (DMSO) as a solvent to create the target compound DADBA-DMSO. The material's hydrogen bonding and intermolecular aggregation were determined by appropriate characterization methods, including single-crystal X-ray diffraction (XRD), Fourier-transform infrared (FTIR), photoluminescence (PL), and cyclic voltammetry (CV) analysis. Each hydrogen of the carboxylic group is coordinated by oxygen from the DMSO molecule in the stiff planar layer packing that makes up the DADBA-DMSO crystal structure.

Fe(III)-Based Phenylsilsesquioxane/Acetylacetonate Complexes: Synthesis, Cage-like Structure, and High Catalytic Activity.

Unprecedented iron-based silsesquioxane/acetylacetonate complexes were synthesized. The intriguing cage-like structure of compounds is alkaline metal-dependent: the Fe2Li2 complex includes condensed Si6-silsesquioxane and four acetylacetonate ligands; the Fe4Na4 complex exhibits two cyclic Si4-silsesquioxane and eight acetylacetonate ligands, while the Fe3K3 complex features two cyclic Si3-silsesquioxane and six acetylacetonate ligands. The latter case is the very first observation of small trimeric silsesquioxane ligands in the composition of cage-like metallasilsesquioxanes. The Fe4Na4-based complex exhibits a record high activity in the oxidation of inert alkanes with peroxides (55% yield of oxygenates in cyclohexane oxidation). It also acts as a catalyst in the cycloaddition of CO2 with epoxides, leading to cyclic carbonates in good yields (58-96%).

4-Oxo-7-fluoro-1,10-phenanthroline-2,9-diamides: Synthesis, Structural Features, Lanthanide Complexes, and Am(III)/Ln(III) Solvent Extraction.

A highly efficient synthetic approach was developed for the synthesis of unsymmetrical 1,10-phenanthroline-2,9-diamides with two different substituents in the fourth and seventh positions of the phenanthroline core. The structures of these ligands were confirmed using various spectral methods including 2D-NMR and X-ray analysis. Quantum chemical calculations supported the presence of tautomeric forms of these ligands. Furthermore, it was discovered that these compounds exhibit polydentate ligand behavior toward lanthanide nitrates. The structural characteristics of the complexes formed between these ligands and lanthanide nitrates were investigated both in the solid state and in solution. To further understand the binding properties of these novel unsymmetrical ligands, the binding constants for potential complexes were quantitatively measured by using UV-vis spectrophotometric titration. This allowed for a comprehensive analysis of the binding affinity and stability of these complexes. Extraction experiments of f-elements were performed for symmetrical and unsymmetrical diamides. Overall, this study presents significant advancement in the synthesis and characterization of unsymmetrical 1,10-phenanthroline-2,9-diamides and provides valuable insights into their potential applications as polydentate ligands for lanthanide nitrates.

A Family of Cagelike Mn-Silsesquioxane/Bathophenanthroline Complexes: Synthesis, Structure, and Catalytic and Antifungal Activity.

This study reports a novel family of cage manganesesilsesquioxanes prepared via complexation with bathophenanthroline (4,7-diphenyl-1,10-phenanthroline). The resulting Mn4-, Mn6Li2-, and Mn4Na-compounds exhibit several unprecedented cage metallasilsesquioxane structural features, including intriguing self-assembly of silsesquioxane ligands. Complexes were tested in vitro for fungicidal activity against seven classes of phytopathogenic fungi. The representative Mn4Na-complex acts as a catalyst in the cycloaddition of CO2 to epoxides under solvent-free conditions to form cyclic carbonates in good yields.

Experimental and Computational Investigation of the Oxime Bond Stereochemistry in c-Jun N-terminal Kinase 3 Inhibitors 11H-Indeno[1,2-b]quinoxalin-11-one Oxime and Tryptanthrin-6-oxime.

11H-Indeno[1,2-b]quinoxalin-11-one oxime (IQ-1) and tryptanthrin-6-oxime are potent c-Jun N-terminal kinase 3 (JNK-3) inhibitors demonstrating neuroprotective, anti-inflammatory and anti-arthritic activity. However, the stereochemical configuration of the oxime carbon-nitrogen double bond (E- or Z-) in these compounds was so far unknown. In this contribution, we report the results of the determination of the double bond configuration in the solid state by single crystal X-ray diffraction and in solution by 1D and 2D NMR techniques and DFT calculations. It was found that both in the solid state and in solution, IQ-1 adopts the E-configuration stabilized by intermolecular hydrogen bonds, in contrast to previously assumed Z-configuration that could be stabilized only by an intramolecular hydrogen bond.

First 24-Membered Macrocyclic 1,10-Phenanthroline-2,9-Diamides-An Efficient Switch from Acidic to Alkaline Extraction of f-Elements.

A reaction of acyl chlorides derived from 1,10-phenanthroline-2,9-dicarboxylic acids with piperazine allows the preparation of the corresponding 24-membered macrocycles in good yield. The structural and spectral properties of these new macrocyclic ligands were thoroughly investigated, revealing promising coordination properties towards f-elements (Am, Eu). It was shown that the prepared ligands can be used for selective extraction of Am(III) from alkaline-carbonate media in presence of Eu(III) with an SFAm/Eu up to 40. Their extraction efficiency is higher than calixarene-type extraction of the Am(III) and Eu(III) pair. Composition of macrocycle-metal complex with Eu(III) was investigated by luminescence and UV-vis spectroscopy. The possibility of such ligands to form complexes of L:Eu = 1:2 stoichiometry is revealed.

Solvation-Induced Conformational Switching of Trisphthalocyanates for Control of Their Magnetic Properties.

Stabilization of different conformers of sandwich phthalocyaninates by changing the solvation environment has been demonstrated with the examples of new heteroleptic yttrium(III) and terbium(III) triple-decker complexes [(BuO)8Pc]M[(BuO)8Pc]M[(15C5)4Pc] (where M = Y or Tb, [(BuO)8Pc]2- = octa-n-butoxyphthalocyaninato ligand, and [(15C5)4Pc]2- = tetra-15-crown-5-phthalocyaninato ligand). To this end, we have performed a comprehensive crystallographic characterization of two solvates formed by the Y(III) complex with either toluene or dichloromethane. In the solvate with toluene, both pairs of Pc ligands are in staggered conformations, providing both metal cations with a square-antiprismatic environment. In contrast, in the solvate with dichloromethane, only one cation between the BuO- and 15C5-substituted ligands remains in a square-antiprismatic polyhedron, while the pair of BuO-substituted ligands switches to a gauche conformation. In both solvates, the staggered conformations are stabilized by weak interactions of peripheral substituents with solvent molecules. Detailed analysis of the 1H NMR spectra of the isostructural Tb(III) complex in aliphatic and aromatic solvents demonstrates that the stabilization of the corresponding conformations by solvation is also valid in the solution state, resulting in an increase in the axial component of the magnetic susceptibility tensor as the symmetry decreases from staggered to gauche. Thus, solvation-induced conformational switching of lanthanide trisphthalocyaninates can be used as a tool to control their magnetic properties.

Bis(2,6-pyrazolyl)pyridines as a New Scaffold for Coordination Polymers.

Two coordination polymers, Fe(LOBF3)(CH3COO)(CH3CN)2]n•nCH3CN and [Fe(LO-)2AgNO3BF4•CH3OH]n•1.75nCH3OH•nH2O (LO- = 3,3'-(4-(4-cyanophenyl)pyridine-2,6-diyl)bis(1-(2,6-dichlorophenyl)-1H-pyrazol-5-olate)), were obtained via a PCET-assisted process that uses the hydroxy-pyrazolyl moiety of the ligand and the iron(II) ion as sources of proton and electron, respectively. Our attempts to produce heterometallic compounds under mild conditions of reactant diffusion resulted in the first coordination polymer of 2,6-bis(pyrazol-3-yl)pyridines to retain the core N3(L)MN3(L). Under harsh solvothermal conditions, a hydrogen atom transfer to the tetrafluoroborate anion caused the transformation of the hydroxyl groups into OBF3 in the third coordination polymer of 2,6-bis(pyrazol-3-yl)pyridines. This PCET-assisted approach may be applicable to produce coordination polymers and metal-organic frameworks with the SCO-active core N3(L)MN3(L) formed by pyrazolone- and other hydroxy-pyridine-based ligands.

Combined Structural and Computational Study of the mRubyFT Fluorescent Timer Locked in Its Blue Form.

The mRubyFT is a monomeric genetically encoded fluorescent timer based on the mRuby2 fluorescent protein, which is characterized by the complete maturation of the blue form with the subsequent conversion to the red one. It has higher brightness in mammalian cells and higher photostability compared with other fluorescent timers. A high-resolution structure is a known characteristic of the mRubyFT with the red form chromophore, but structural details of its blue form remain obscure. In order to obtain insight into this, we obtained an S148I variant of the mRubyFT (mRubyFTS148I) with the blocked over time blue form of the chromophore. X-ray data at a 1.8 Å resolution allowed us to propose a chromophore conformation and its interactions with the neighboring residues. The imidazolidinone moiety of the chromophore is completely matured, being a conjugated π-system. The methine bridge is not oxidized in the blue form bringing flexibility to the phenolic moiety that manifests itself in poor electron density. Integration of these data with the results of molecular dynamic simulation disclosed that the OH group of the phenolic moiety forms a hydrogen bond with the side chain of the T163 residue. A detailed comparison of mRubyFTS148I with other available structures of the blue form of fluorescent proteins, Blue102 and mTagBFP, revealed a number of characteristic differences. Molecular dynamic simulations with the combined quantum mechanic/molecular mechanic potentials demonstrated that the blue form exists in two protonation states, anion and zwitterion, both sharing enolate tautomeric forms of the C=C-O- fragment. These two forms have similar excitation energies, as evaluated by calculations. Finally, excited state molecular dynamic simulations showed that excitation of the chromophore in both protonation states leads to the same anionic fluorescent state. The data obtained shed light on the structural features and spectral properties of the blue form of the mRubyFT timer.

Supramolecular hybrids based on Ru(II) porphyrin and octahedral Mo(II) iodide cluster.

The coordination-driven design and synthesis of new stable supramolecular cluster-porphyrin (CP) hybrids based on an A2-type ruthenium porphyrin 5,15-bis[(p-tolyl)porphyrinato(2-)]ruthenium(carbonyl)(aqua) [RuDTolP(CO)H2O] and an octahedral molybdenum(II) iodide cluster with six terminal isonicotinate ligands (Bu4N)2[{Mo6I8}(OOC-C5H4N)6] (PyMoC) are reported. The stepwise supramolecular assembly of the PyMoC "superoctahedron" with RuDTolP(CO)H2O has been studied by 1H NMR and 2D 1H-1H COSY, 1H-15N HMBC and DOSY techniques, as well as by UV-vis spectroscopy and HR-ESI mass spectrometry. The formation of discrete cluster-porphyrin CPn adducts with different numbers of coordinated porphyrins (n = 1-6), including the geometrical isomers of CP2, CP3 and CP4, has been observed. Using a double equivalent amount of RuDTolP(CO)H2O relative to the cluster (C : P ratio 1 : 12) affords a mixture of CP5 and CP6 species in solution, while only the CP6 complex is crystallized from this system. Fine tuning of crystallization conditions leads to the formation of a more complex architecture CP6+2, where the CP6 assembly incorporates two additional porphyrin molecules bound to the cluster core by hydrogen bonds. Thus, the coordination-based supramolecular approach provides new stable cluster-multiporphyrin 3D arrays based on two types of photosensitizers, which can be promising for the design of photoactive materials.

Multistep synthesis and X-ray structures of carboxyl-terminated hybrid iron(II) phthalocyaninatoclathrochelates and their postsynthetic transformation into polytopic carboranyl-containing derivatives.

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 transmetallation of the triethylantimony-capped macrobicyclic precursor. The thus obtained carboxyl-terminated iron(II) semiclathrochelate underwent a macrobicyclization with zirconium(IV) phthalocyaninate to form the corresponding phthalocyaninatoclathrochelate. The direct one-pot template condensation of the suitable chelating and cross-linking ligand synthons on the Fe2+ ion as a matrix was also used for its preparation. Further amide condensation of the aforementioned semiclathrochelate and hybrid complexes with propargylamine in the presence of carbonyldiimidazole gave the (pseudo)cage derivatives with a terminal CC bond. Their "click" reaction with an appropriate carboranylmethyl azide afforded the ditopic carboranosemiclathrochelates and the tritopic carboranyl-containing phthalocyaninatoclathrochelates with a flexible spacer fragment between their polyhedral entities. The obtained new complexes were characterized using elemental analysis, MALDI-TOF mass spectrometry, multinuclear NMR, and UV-vis spectroscopy, and by single crystal X-ray diffraction experiments. Their FeN6-coordination polyhedra show a truncated trigonal-pyramidal geometry, while the cross-linking heptacoordinate Zr4+ or Hf4+ cations in the hybrid compounds form the MIVN4O3-coordination polyhedra with the geometry of a capped trigonal prism.

Hybrid Silsesquioxane/Benzoate Cu7-Complexes: Synthesis, Unique Cage Structure, and Catalytic Activity.

A series of phenylsilsesquioxane-benzoate heptacopper complexes 1-3 were synthesized and characterized by X-ray crystallography. Two parallel routes of toluene spontaneous oxidation (into benzyl alcohol and benzoate) assisted the formation of the cagelike structure 1. A unique multi-ligation of copper ions (from (i) silsesquioxane, (ii) benzoate, (iii) benzyl alcohol, (iv) pyridine, (v) dimethyl-formamide and (vi) water ligands) was found in 1. Directed self-assembly using benzoic acid as a reactant afforded complexes 2-3 with the same main structural features as for 1, namely heptanuclear core coordinated by (i) two distorted pentameric cyclic silsesquioxane and (ii) four benzoate ligands, but featuring other solvate surroundings. Complex 3 was evaluated as a catalyst for the oxidation of alkanes to alkyl hydroperoxides and alcohols to ketones with hydrogen peroxide and tert-butyl hydroperoxide, respectively, at 50 °C in acetonitrile. The maximum yield of cyclohexane oxidation products as high as 32% was attained. The oxidation reaction results in a mixture of cyclohexyl hydroperoxide, cyclohexanol, and cyclohexanone. Upon the addition of triphenylphosphine, the cyclohexyl hydroperoxide is completely converted to cyclohexanol. The specific regio- and chemoselectivity in the oxidation of n-heptane and methylcyclohexane, respectively, indicate the involvement of of hydroxyl radicals. Complex 3 exhibits a high activity in the oxidation of alcohols.

Pyridine Carboxamides Based on Sulfobetaines: Design, Reactivity, and Biological Activity.

The synthesis of the products of the 1,3-propanesultone ring opening during its interaction with amides of pyridinecarboxylic acids has been carried out. The dependence of the yield of the reaction products on the position (ortho-, meta-, para-) of the substituent in the heteroaromatic fragment and temperature condition was revealed. In contrast to the meta- and para-substituted substrates, the reaction involving ortho-derivatives at the boiling point of methanol unexpectedly led to the formation of a salt. On the basis of spectroscopic, X-Ray, and quantum-chemical calculation data, a model of the transition-state, as well as a mechanism for this alkylation reaction of pyridine carboxamides with sultone were proposed in order to explain the higher yields obtained with the nicotinamide and its N-methyl analog compared to ortho or meta parents. Based on the analysis of ESP maps, the positions of the binding sites of reagents with a potential complexing agent in space were determined. The in silico evaluation of possible biological activity showed that the synthetized compounds revealed some promising pharmacological effects and low acute toxicity.

Synthesis, Self-Assembly in Crystalline Phase and Anti-Tumor Activity of 2-(2-/4-Hydroxybenzylidene)thiazolo[3,2-a]pyrimidines.

A series of new thiazolo[3,2-a]pyrimidines different by aryl substituents in 2 and 5 positions are synthesized and characterized in solution as well as in the crystalline phase using 1H and 13C NMR-, IR-spectroscopies, mass-spectrometry methods, and single crystal X-ray diffraction (SCXRD). The SCXRD study revealed the role of intermolecular H-bonding in the formation of supramolecular architectures (racemic monomers, centrosymmetric racematic dimers, or homochiral 1D chains) of obtained thiazolo[3,2-a]pyrimidines derivatives depending on solvents (aprotic DMSO or protic EtOH) used upon the crystallization process. Moreover, the in vitro study of cytotoxicity toward different tumor cells showed their high or moderate efficiency with moderate cytotoxicity against normal liver cells which allows to consider the obtained thiazolo[3,2-a]pyrimidine derivatives as promising candidates for application as antitumor agents.

Novel Type of Tetranitrosyl Iron Salt: Synthesis, Structure and Antibacterial Activity of Complex [FeL'2(NO)2][FeL'L"(NO)2] with L'-thiobenzamide and L"-thiosulfate.

In this work a new donor of nitric oxide (NO) with antibacterial properties, namely nitrosyl iron complex of [Fe(C6H5C-SNH2)2(NO)2][Fe(C6H5C-SNH2)(S2O3)(NO)2] composition (complex I), has been synthesized and studied. Complex I was produced by the reduction of the aqueous solution of [Fe2(S2O3)2(NO)2]2- dianion by the thiosulfate, with the further treatment of the mixture by the acidified alcohol solution of thiobenzamide. Based on the structural study of I (X-ray analysis, quantum chemical calculations by NBO and QTAIM methods in the frame of DFT), the data were obtained on the presence of the NO…NO interactions, which stabilize the DNIC dimer in the solid phase. The conformation properties, electronic structure and free energies of complex I hydration were studied using B3LYP functional and the set of 6-31 + G(d,p) basis functions. The effect of an aquatic surrounding was taken into account in the frame of a polarized continuous model (PCM). The NO-donating activity of complex I was studied by the amperometry method using an "amiNO-700" sensor electrode of the "inNO Nitric Oxide Measuring System". The antibacterial activity of I was studied on gram-negative (Escherichia coli) and gram-positive (Micrococcus luteus) bacteria. Cytotoxicity was studied using Vero cells. Complex I was found to exhibit antibacterial activity comparable to that of antibiotics, and moderate toxicity to Vero cells.

A Novel Family of Cage-like (CuLi, CuNa, CuK)-phenylsilsesquioxane Complexes with 8-Hydroxyquinoline Ligands: Synthesis, Structure, and Catalytic Activity.

The first examples of metallasilsesquioxane complexes, including ligands of the 8-hydroxyquinoline family 1-9, were synthesized, and their structures were established by single crystal X-ray diffraction using synchrotron radiation. Compounds 1-9 tend to form a type of sandwich-like cage of Cu4M2 nuclearity (M = Li, Na, K). Each complex includes two cisoid pentameric silsesquioxane ligands and two 8-hydroxyquinoline ligands. The latter coordinates the copper ions and corresponding alkaline metal ions (via the deprotonated oxygen site). A characteristic (size) of the alkaline metal ion and a variation of characteristics of nitrogen ligands (8-hydroxyquinoline vs. 5-chloro-8-hydroxyquinoline vs. 5,7-dibromo-8-hydroxyquinoline vs. 5,7-diiodo-8-hydroxyquinoline) are highly influential for the formation of the supramolecular structure of the complexes 3a, 5, and 7-9. The Cu6Na2-based compound 2 exhibits high catalytic activity towards the oxidation of (i) hydrocarbons by H2O2 activated with HNO3, and (ii) alcohols by tert-butyl hydroperoxide. Studies of kinetics and their selectivity has led us to conclude that it is the hydroxyl radicals that play a crucial role in this process.