N-methyl and N-glycyl glycine derivatives - namely (trimethylammonium)acetate (N,N,N-trimethylglycine, betaine, Bet), N,N-dimethylglycine (Dmg), N-methylglycine (sarcosine, Sar), and glycylglycylglycine (GlyGlyGly) - as naturally occurring glycine metabolites, were employed as stabilizing ligands for silver(I) ions, leading to the formation of water-soluble polymeric coordination compounds: {[Ag(HSar)(NO3)]}n (AgSar), {[Ag(HDmg)(NO3)]}n (AgDmg), {[Ag3(HBet)2(NO3)3]}n (AgBet), and [Ag(HGlyGlyGly)(NO3)] (AgGlyGlyGly). The composition and structures of the resulting complexes were unambiguously confirmed using attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR), elemental analysis, thermogravimetric analysis (TGA), and single-crystal X-ray diffraction (SC-XRD). Speciation and stability studies in relevant test and growth media were conducted using a novel multi-technique approach combining potentiometric titrations, electrochemical measurements, 1H NMR and UV-Vis spectroscopy and were additionally supported by theoretical calculations. From a biological evaluation standpoint, all complexes demonstrated significantly enhanced antistaphylococcal activity (including S. aureus L12) compared to silver(I) nitrate (AgNO3), with AgBet and AgGlyGlyGly exhibiting approximately 10-fold, and AgSar and AgDmg approximately 5-fold, increased efficacy. Moreover, AgBet and AgGlyGlyGly were nearly twice as active as silver(I) sulfadiazine (AgSD), a clinically used but poorly water-soluble antimicrobial agent. Remarkably, AgBet and AgGlyGlyGly also showed unusual potent antifungal activity, being 10- to 100-fold more effective than both AgNO3 and AgSD against Rhizopus oryzae, the causative agent of mucormycosis. In cytotoxicity assays, AgSar exhibited the greatest selectivity and sensitivity, being over three times higher than cisplatin (cisPt), against the human breast adenocarcinoma cell line MDA-MB-231. New approaches from the perspectives of structure-activity relationships and bioavailability of the novel silver(I) complexes were explored through human serum albumin (HSA) binding studies and molecular docking calculations, as well as experimental and computational evaluations of lipophilicity and additional Lipinski parameters. Furthermore, the silver(I) complexes' action mechanism was assessed via β-galactosidase inhibition and PCR amplification inhibition in E. coli, intracellular reactive oxygen species (ROS) production, their effects on cell cycle progression and binding to ctDNA.

The first structurally characterized vanadium(IV) mandelato complexes [V2O2(S-mand)2(bpy)2]center dot H2O center dot CH3CN (11), [V2O2(R-mand)(S-mand)(bpy)2]center dot 4H2O (12), [V2O2(S-mand)2(phen)2]center dot 2CH3CN (13), [V2O2(R-mand)(S-mand) (phen)2]center dot 2CH3CN (14) (mand2- - mandelato ligand, bpy - 2,2 '-bipyridine, phen - 1,10-phenanthroline) have been prepared by the reduction of NMe4VO3 by an excess of mandelic acid in the presence of bpy (phen) and in CH3CN/ H2O (1/1 vol. ratio) solvent. The single crystal X-ray diffraction studies of the complexes revealed the presence of molecular complexes with alkoxy oxygen atoms of mandelato ligands acting as bridging atoms linking the vanadium atoms and distorted octahedral coordination environment around vanadium atoms. The compounds were further characterized by IR and Raman spectroscopies. The band assignment was corroborated by DFT calculation. The course of reduction vanadium(V) to vanadium(IV) was monitored by UV-vis spectroscopy.

Conventional chemotherapy often lacks specificity, leading to significant side effects and highlighting the need for more targeted cancer therapies. The overexpression of cyclooxygenase (COX) enzymes in various malignancies, including colorectal cancer, makes COX inhibition a promising therapeutic strategy. Non-steroidal antiinflammatory drugs (NSAIDs), such as Ibuprofen, are well-known COX inhibitors. In this study, we synthesized two types of cyclopentadienyl-arene ruthenium (CAR)-Ibuprofen conjugates: compounds 1-5, featuring g6-coordinated Ibuprofen derivatives, and compound 7, with Ibuprofen attached via an ester linkage to the complex periphery. Cytotoxicity assays against colorectal cancer cell lines (SW-620, SW-480) and non-cancerous HEK-293 cells revealed that compounds 1, 5, and 7 exhibit anti-proliferative activity in the low micromolar range, although without selectivity. These complexes also showed effective inhibition of COX enzymatic activity. Western blot analysis indicated that their primary mechanism involves induction of cell cycle arrest, rather than activation of apoptotic or autophagic pathways.

Three novel fluorinated Ln(iii) metal-organic frameworks (Ln-F-MOFs) containing holmium for UPJS-21(Ho), dysprosium for UPJS-21(Dy), and ytterbium for UPJS-22(Yb) were prepared and studied. The formulas of compounds were: {[Ho2(L)3(DMF)0.65(DMA)1.35]& centerdot;0.75DMF & centerdot;0.75DMA}n, {[Dy2(L)3(DMF)0.65(DMA)1.35]& centerdot;0.75DMF & centerdot;0.75DMA}n, and {[Yb2(L)2(CH3COO)2]& centerdot;1DMF & centerdot;1DMA}n. The structures of UPJS-21(Ho) and UPJS-22(Yb) were solved from single-crystal measurements. Both structural forms consist of two-dimensional polymeric layers interacting through weaker intramolecular interactions, like hydrogen bonds involving fluoro, nitrogen and hydrogen atoms. The single crystals of UPJS-21(Dy) with sufficient quality were not obtained, but based on the powder XRD measurements, the third compound, UPJS-21(Dy), is isostructural with UPJS-21(Ho). The surface of UPJS-21(Ho) shows hydrophobic behaviour referred to as a "rose petal effect." All complexes are thermally stable up to 300 degrees C. The photoluminescence properties of the complexes were also investigated. For UPJS-21(Ho) and UPJS-21(Dy), distinct 4f-4f electron transitions unique to the respective lanthanide ion were observed, while for UPJS-22(Yb), only weak pi-pi* transitions of the aromatic ring associated with the (L)2- ligand were recorded. The magnetic behaviour of UPJS-21(Ho) and UPJS-21(Dy) is characterised by a substantial reduction of the magnetic moment at low temperatures due to the low mJ of the ground state Stark level. On the other hand, the deformed pentagonal bipyramidal coordination of Yb(iii) ions in UPJS-22(Yb) induced a strong axial anisotropy, yielding an energy gap between the ground and the first excited doublet of 191.4 cm-1. Moreover, adsorption of N2, CO2, and H2 was also studied for UPJS-21(Ho) and UPJS-21(Dy) complexes.

Trivalent boron Lewis acids activate H2 for catalytic hydrogenations, yet only one trivalent indium analog is known to do so. Nevertheless, heavier main-group elements also form five-, six-, and seven-coordinate compounds. However, complexes of Ga and In generally fail at hydrogenation catalysis, without clear guiding principles for their design. We show that coordination geometry, hydride thermodynamics, and the counteranion govern catalytic imine hydrogenation at In(III) pincer complexes. Cationic five-coordinate In complexes bearing NNN-, PNN-, and PNP-pincer ligands with [InX4]- anions catalyze this reaction under 120 °C and 15 bar of H2. Catalytic activity correlated with the Gibbs free energy of H2 activation. This endergonic step determined turnover. Rather than classical Lewis acidity descriptors, hydride and fluoride affinity, and Gutmann-Beckett acidity, cis-trans isomerism of key intermediates controlled H2 activation thermodynamics. Indium complexes outperformed lighter group-13 Al and Ga congeners not for their higher Lewis acidity, but for their more favorable hydride formation thermodynamics. The ligands modulated Lewis base binding without overcoming hydride thermodynamic limitations. Finally, the [InX4]- anions may activate the imine substrate toward reduction. Our findings explain the hydrogenation activity of indium Lewis acids, establishing coordination geometry, hydride thermodynamics, and counteranion as key parameters for their rational design.

3-substituted derivatives of picolinic acid, 3-methylpicolinic acid (3-MePicH) and 3-hydroxypicolinic acid (3-OHPicH), were used to investigate their complex-forming, structural, spectral, and thermal properties toward biologically active silver(I) and zinc(II) ions. In the case of the 3-MePicH ligand, potentiometric and 1H NMR titrations confirmed the formation of complex species [Ag(3-MePic)], [Zn(3-MePic)]+, and [Zn(3-MePic)₂]. In contrast, the 3-OHPicH ligand was incorporated into the coordination sphere of the Ag(I) and Zn(II) central atoms only in the form of protonated complex species. Under ecofriendly conditions, the complexes were isolated in solid state; their IR, NMR, thermal analyses, molar conductivity and for the zinc(II) complex with the 3-methylpicolinate ligand also single-crystal analysis confirmed their composition: [Ag(3-MePic)]·0.5H₂O (Ag3-MePic), [Zn(3-MePic)₂(H₂O)] (Zn3-MePic), [Ag(3-OHPic)] (Ag3-OHPic), [Zn(3-OHPic)₂(H₂O)₂] (Zn3-OHPic). The stability of the investigated complexes in biologically relevant solvents made it possible to evaluate their antimicrobial and anticancer activity. Compared with AgPic (the analogous silver(I) complex with picolinic acid), a more significant antibacterial and antifungal activity for Ag3-OHPic was confirmed, as well as higher cytotoxicity for both pyridine-substituted silver(I) complexes against A549 (36.3 μM) and Jurkat (37.8 μM) cells. The interactions of the silver(I) complexes with human serum albumin and calf thymus DNA were also investigated, followed by an evaluation of their potential inhibitory effects on human topoisomerases I and II. Among the tested compounds, Ag3-MePic exhibited the most pronounced inhibitory activity against Topoisomerase II at a concentration of 0.5 μM.

A series of helical quinolizinium salts were prepared utilizing Rh-catalyzed [2+2+2]cyclotrimerization and C-H activation processes as the crucial synthetic steps. The cyclotrimerization of appropriately substituted diynes with trimethylsilylethyne under Rh-catalyzed conditions provided the 1-arylisoquinolines in up to 61% isolated yields. Their Rh-catalyzed C-H activation/annulation with various aryl and alkyl disubstituted alkynes gave rise to [7]-helical quinolizinium salts in high isolated yields (up to 93%). Enantioselective C-H activation was also tried with asymmetric induction up to 62% ee. The respective boron and platinum complexes of 1-arylisoquinolines were prepared as well. All prepared compounds exhibit fluorescence in the orange-red light region (606-682 nm) with ΦFs 28-99%.

Three 2-thiophenecarboxylate (Tio2c) complexes with different central atoms Ag(I), Zn(II) and Ga(III), [Ag(Tio2c)]2 (AgTio2c), {[Zn2(Tio2c)4]2}n (ZnTio2c) and [Ga(Tio2c)3]·H2O (GaTio2c), were synthesized and elemental, spectral and thermal analyses were used for their characterization. The AgTio2c and ZnTio2c single crystal structures confirmed the most common bidentate bridging coordination mode with typical strong argentophilic interactions in the case of AgTio2c complex. Complexes' stability in biological test stock solution were confirmed by 1H NMR spectroscopy. Potentiometric data analysis by BSTAC program resulted in the determination of the stability constants of four complex species, [Zn(Tio2c)]+ (log β110 = 2.06 ± 0.04), [Zn(Tio2c)(OH)] (log β11-1 = -5.0 ± 0.1), [Zn(Tio2c)(OH)2]- (log β11-2 = -12.9 ± 0.4) and [Zn(Tio2c)2(OH)2]2- (log β12-2 = -8.54 ± 0.04) with low abundance in aqueous solution. Theoretical estimation of the complex species in aqueous solution indicates a rather monodentate Tio2c coordination mode in the [Zn(Tio2c)]+ species, while the hydroxido complex species prefer a rather bidentate O,O'-bond of the carboxylate. Antimicrobial and anticancer bioassays clearly confirmed the highest biological activity (toxicity) of the AgTio2c complex. The activity of ZnTio2c was slightly higher (or the same) compared to GaTio2c. The HSA (human serum albumin) binding behaviour of the AgTio2c, ZnTio2c and GaTio2c complexes was investigated using fluorescence spectroscopy and results revealed that the calculated Kb values were in the order of 104 M-1.

Regioselective synthesis is a crucial concept in organic chemistry, enabling the selective formation of different regioisomers from the same type of starting materials. This approach is particularly valuable in pharmaceutical and materials sciences, where the arrangement of functional groups influences the biological activities and properties of the molecule. Pyridines are ubiquitous in organic chemistry due to their prevalence in natural products and pharmaceuticals. In addition, the introduction of boron substituents into pyridine rings enables subsequent functionalization further enhancing their utility. Herein, we present a synthetic strategy for the selective formation of either 2‐ and 3‐polysubstituted borylated pyridines via Ru‐ and Co‐catalyzed [2 + 2 + 2] cyclotrimerization reactions. Efficient synthesis and utilization of functionalized diynes allow the exploration of their reactivity in cyclotrimerization reactions with a wide variety of nitriles. The broad applicability of the methods to form pyridines with high efficiency and regioselectivity based on the used type of boronic acid derivative is shown. The application includes successful photocatalyzed cyclizations as well as the implementation of one‐pot cyclotrimerization‐coupling protocols. The findings not only provide a practical route to valuable borylated pyridines but also offer insights into the mechanistic aspects governing selectivity in these reactions.

The fascinating feature of metal-organic frameworks is that they can respond to external stimuli, unlike other inorganic materials. This feature corresponds to the framework's flexibility, which originates with the long-range crystalline order of the framework accompanied by cooperative structural transformability. We have synthesized a novel metal-organic framework comprised of Cu(I) nodes with pyrazine linkers and benzene-1,3,5-tricarboxylate acting as template anions, named CUCAM-1 [Cu(Py)2(BTC)]n. In the presence of polar solvent systems, CUCAM-1 undergoes an irreversible structural transformation to yield a mixed phase that consists of HKUST-1 [Cu3(BTC)2(H2O)3]n and another CUCAM-2 [Cu(Py)(BTC)]n MOFs, whose novel structure is successfully revealed by continuous rotation electron diffraction from the mixture. In this structural transformation, a new ligand exchange occurs where template anions become ligands, confirmed by single crystal X-ray analysis. Further, structural transformation and the mechanism are explained by ab initio molecular dynamics (AIMD) simulations. Interestingly, different halides (F-, Cl-, and Br-) can be accompanied to affect/control the composition of the second phase by favoring the formation of the HKUST-1 phase over CUCAM-2, which was evident by the powder X-ray diffraction studies. Furthermore, the structural transformation induced by I- resulted in a colorimetric response due to the formation of a new MOF CUCAM-3, paving the way for use as an iodide detector.

For the first time, a tridecavanadate isopolyvanadate species, [VIVVV12O38]12- (V13), has been identified and synthesized via a pH-controlled slow-evaporation method yielding water-insoluble, black rod-shaped crystals of {[La(H2O)3]2[La(H2O)5]4[mu-V10O28][mu 6-VIVVV12O38]}24H2O, exhibiting a polymeric structure and characterized through single-crystal X-ray diffraction (XRD) analysis, infrared spectroscopy, atomic absorption spectroscopy (AAS), inductively coupled plasma optical emission spectroscopy (ICP-OES), CHN analysis, photoelectron X-ray spectroscopy and thermal analysis (TGA/DTA). A distinctive feature of V13 is its six-fold tetradentate coordination mu 6-eta 4:eta 4:eta 4:eta 4:eta 4:eta 4 with La(iii), showcasing notable bonding characteristics. It was feasible to synthesize two coordination isomers of V13, denoted as 1a and 1b, sequentially. These coordination isomers primarily differ in their La : V molar ratios of the corresponding starting materials, being 3 : 4 for 1a and 2 : 4 for 1b, which in turn influences the crystallization time, purity, structural type, and crystal parameters of the resultant products, but the final products of both 1a and 1b have the same La : V molar ratio as 6 : 23. 1a adopts a linear one-dimensional coordination polymer structure, whereas 1b forms a zig-zag one-dimensional coordination polymer. Additionally, 1b coexists in the solid state with crystals of an unprecedented decavanadate with the proposed formula {[La(H2O)7]2[mu-V10O28]}8H2O (2) exhibiting a rare coordination mode mu-eta 2:eta 2 of the decavanadato ligand. Therefore, the novel V13 expands the horizons of the polyoxovanadates' structural library by adding a new isopolyvanadate species, opening up avenues for the future to explore and investigate other metal cations with comparable ionic radii to that of La(iii) in addition to probing their intrinsic material aptitude and application potential.

Syntheses of enantioenriched helical dispiroindeno[2,1-c]fluorenes (DSIF) possessing one or two pCp moieties are presented. These are based on the conversion of (Sp)- and (Rp) pCp-carbaldehydes 1 to triynediols 2 and 6 that were converted to enantioenriched DSIFs 4 and 8 via a catalytic [2+2+2] cyclotrimerization, oxidation, and spirocyclization sequence. Photophysical properties were measured, and compounds 4 and 8 are highly fluorescent in the violet-blue light region with |glum| values in the order of 10-4 and 10-3, and BCPL values 1.1 and 7.6, respectively.

This study aimed primarily at completing and extending the characterization of the crystallographic, spectroscopic and optical properties of polar, biaxial, optically negative 2-aminopyrimidinium(1+) hydrogen phosphite. Besides the redetermination of the low-temperature crystal structure (space group P21), high-quality single crystals of this salt were grown from an aqueous solution, and their optical properties were studied. The determination of the refractive indices in the wavelength range of 435-1083 nm showed anomalous dispersion of the refractive indices, resulting in a point of uniaxiality. The crystal allows phase matching for collinear second harmonic generation (SHG) processes of both type I and type II in a broad wavelength range. SHG properties were studied for powdered size-fractioned samples and oriented single-crystal cuts. The optical damage threshold experiments confirmed excellent optical resistance - at least 220 TWm-2 and 70 TWm-2 for 800 and 1000 nm irradiation, respectively. The low-temperature crystallographic study was also extended for three monoclinic salts of 2-aminopyrimidine and sulfuric acid - i.e. bis(2-aminopyrimidinium(1+) sulfate monohydrate (space group P21/n) and two polymorphs of 2-aminopyrimidinium(1+) hydrogen sulfate (both with space group P21/c). The vibrational spectra of all title compounds were assigned using single-molecule quantum chemical computations (including Potential Energy Distribution analysis) in combination with the nuclear site group analysis. Spectroscopic results concerning sulfates of 2-aminopyrimidine provided valuable reference materials for the vibrational spectroscopic study and also addressed the question of their polymorphism. An optimal computational approach employing solid-state DFT calculations has also been sought to model the vibrational spectra of 2-aminopyrimidinium (1+) hydrogen phosphite crystals.

A new iron(III) sulfato complex [Fe2(bpy)2(H2O)2(µ-O)(µ-SO4)2]·3H2O has been prepared from iron(II) chloride by using potassium peroxydisulfate being the oxidation agent and the source of sulfato ligands as well. The compound has been characterized by infrared, Raman and Mössbauer spectroscopies. X-ray structure analysis confirmed the presence of the Fe(III)–O–Fe(III) core in the complex. Both sulfato groups are bonded in the form of bridged bis(monodentate) ligands. The coordination polyhedra about the central atoms are completed by 2,2′-bipyridine and water molecules, forming thus distorted octahedra. A thorough comparison of bonding parameters of all dinuclear oxido-bridged sulfato complexes of iron(III) that have been solved by X-ray structure analysis revealed several strong correlations between these parameters and bonding mode of sulfato ligands. The characteristic vibrational bands of the FeOFe group has been observed at 770 cm−1 (IR) for νas(FeOFe) and at 513 cm−1 (IR) and 520 cm−1 (Raman) for νs(FeOFe). The assignment of characteristic bands was corroborated by DFT calculation. The isomer shift values obtained in Mössbauer spectra indicate high-spin Fe3+, while the large quadrupole splitting is characteristic of oxygen bridged Fe3+ ions.

Multidrug-resistant bacterial infections continue to be a rising global health concern. Herein, we describe the development of a novel class of 3-substituted benzoazepinedione derivatives with promising antibacterial activity. The pivotal compound, benzoazepinedione carboxylate 9, represents a highly electrophilic Michael acceptor, enabling divergent access to a wide range of thia-, aza-, oxa-, and phospha-Michael adducts. Notably, most prepared compounds exhibited potent antibacterial activity against both drug-susceptible and drug-resistant strains of Staphylococcus aureus (MIC90 of up to 2 μg mL-1). The cytotoxicity assessment in the VERO6 cell line revealed that thia-adduct 10d (IC50 of 36.5 μg mL-1) exhibits lower toxicity compared to its parent electrophile 9 (IC50 of 14.3 μg mL-1), which is in agreement with the hypothesis of covalently modified prodrugs. Additionally, stability studies of the prepared compounds in CD3OD and a DMSO-PBS mixture confirmed that thia-Michael adducts 10 are stable under neutral conditions while dynamic under mildly basic conditions. Moreover, 3D reconstructed tissue models (human lung epithelial EpiAirway™ and a human small intestine model) did not exhibit a viability decrease below 80% of the untreated control at all concentrations tested, indicating tolerance to higher concentrations of potential drugs and prodrugs.

In this paper, two new compounds, (1) and (2), have been synthesized by a one pot process at the reflux condition. Both compounds were characterized by infrared and UV-visible spectroscopy techniques, as well as by X-ray diffraction. The compound (1) crystallizes in the monoclinic system with the space group P21/n and the compound (2) crystallizes in the monoclinic system but with the space group P21/c. The structure consists of a non-protonated heptamolybdates polyanions, stabilized by organoammonium groups and water molecules. The cohesion of the three-dimensional structure is ensured by hydrogen bonds between the polyanions, the organoammonium groups, and the water molecules, thereby providing significant stability to the compound.

Two In(III) - pyridinecarboxylates ([In(Pic)2(NO3)(H2O)] (InPic; HPic = picolinic acid), [In(HDpic)(Dpic)(H2O)2]·5H2O (InDpic; H2Dpic = dipicolinic acid), have been synthesized by one-step procedure. The complexes composition was confirmed by physicochemical analyses and X-ray diffraction confirmed molecular structure of both complexes. Moreover, complex species speciation was described in both systems by potentiometry and 1H NMR spectroscopy and mononuclear complex species were determined; [In(Pic)]2+ (logβ011 = 6.94(4)), [In(Pic)2]+ (logβ021 = 11.98(9)), [In(Dpic)]+ (logβ011 = 10.42(6)), [In(Dpic)2]- (logβ021 = 17.58(7)) and [In(Dpic)2(OH)]2- (logβ-121 = 10.18(6)). To confirm the complexes stability in 1 % DMSO, 1H NMR spectra were measured (immediately after dissolution up to 96 h). Antimicrobial and anticancer assays indicate a more significant sensitivity of S. aureus bacteria and MDA-MB-231 cancer cells to the InPic complex (IC50 = 25 and 340.7 μM) than to the InDpic (IC50 = 50 and 975.4 μM). The interaction and binding mechanism of picolinic/dipicolinic acid and their indium(III) complexes with HSA (human serum albumin) were studied using fluorescence and CD spectroscopy. The results confirmed that the studied compounds had bound successfully to HSA, and the binding parameters and constants (KSV, Kq, Kb) were calculated together with the number of binding sites. The binding forces were identified based on calculated thermodynamic parameters (ΔG, ΔH, ΔS). Synchronous spectra were used to study the microenvironment of Tyr and Trp residues and displacement assays revealed that site I was the preferred binding site. After binding, conformational changes were found to have occurred in the HSA molecule and the % α-helical content had decreased.

A series of five novel lanthanide-based fluorinated metal-organic frameworks (Ln-F-MOFs) have been synthesized under solvothermal conditions by the reaction of 3,3 '-bis(trifluoromethyl)-[1,1 '-biphenyl]-4,4 '-dicarboxylic acid (H2L) and lanthanide Ln(III) ions (Ln(III)-La, Ce, Pr, Nd and Eu). Powder X-ray diffraction (PXRD) analysis revealed that all prepared complexes are isostructural. A single-crystal X-ray crystallographic study of one representative of the isostructural group, namely {[La-2(L)(3)(DMF)(2)(H2O)(2)]}(n) showed, that compound crystallizes in a triclinic system with space group P-1. The lattice parameter values are a = 8.563(2) angstrom, b = 13.199(3) angstrom, c = 16.008(4) angstrom, alpha = 104.588(7) degrees, beta = 92.904(7) degrees and gamma = 92.717(7) degrees, with two formula units in the unit cell. The overall structure is formed by 2D polymeric layers, which are arranged into a semi-3D supramolecular structure through hydrogen bonds and other intramolecular interactions. The study of the hydrophobic properties of the complexes showed that the complexes exhibit surface hydrophobicity with a "rose petal effect" and a contact angle of approximately 107 degrees. However, the structures are not hydrolytically stable in the long term and the structure starts to delaminate after two days in water. This is a manifestation of the fact that the complexes do not form a 3D polymer network, it is made up of 2D layers connected only by weak non-bonding interactions. The photoluminescence properties of the Ln(III) complexes are determined by the characteristic 5d-4f or 4f-4f electron transitions for the individual lanthanide ions. The magnetic properties of Nd(III), Pr(III) and Eu(III) variants were studied. The magnetic properties of {[Pr-2(L)(3)(DMF)(2)(H2O)(2)]}(n) are characterized by the presence of a low-lying quasi-doublet with 15.6 cm(-1) energy splitting, whereas Eu(III) variant is nonmagnetic at low temperatures, but the magnetic F-7(1) state is accessible by thermal excitation. For Nd(III) complex, the X-band EPR measurements were performed. Since 1D channels with dimensions of 4.90 x 7.23 angstrom(2) are present within the structure, the adsorption of N-2, CO2 and H-2 gases was also studied.

Novel fluorinated lanthanide-based metal-organic frameworks (Ln-F-MOFs) constructed from the 3,3 '-difluorobiphenyl-4,4 '-dicarboxylic acid as a ligand (H2L) and M(III) metal ions (M(III) = Dy for UPJS-18(Dy), Tb for UPJS-18(Tb), Ho for UPJS-18(Ho), Er for UPJS-18(Er), Eu for UPJS-19(Eu), UPJS = materials prepared at the University of Pavol Jozef Saf & aacute;rik in Ko & scaron;ice) have been successfully synthesized under solvothermal conditions leading to a series of MOFs with the same basic formula and the composition {[M-2(L)(3)(DMF)(2)]center dot xDMFyH(2)O}(n). Structural analyses revealed that complexes UPJS-18(Dy), UPJS-18(Tb), UPJS-18(Ho), UPJS-18(Er) are isostructural while complex UPJS-19(Eu) has different but a very similar structural motif. These complexes show high surface hydrophobicity with "rose petal effect", thermal stability up to 300 degrees C and photoluminescence properties determined the characteristic f-f transitions for the individual metal ions. The porosity of some activated coordination polymers was studied by N-2, CO2 and H-2 adsorption, with the highest N-2 and CO2 adsorption capacities observed for the UPJS-18(Dy) complex. Moreover, the H-2 sorption capacity was determined for UPJS-19(Eu). The high water-repelling properties and thermal stability predetermines these materials for industrial as well as everyday-life use, while channels lined with fluorine atoms with their high affinity to fluorinated compounds predetermine the possibility of further investigations in the field of sorption fluorinated waste or fluorinated drugs.