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Large blue rectangular crystals of the 2D layered coordination polymer 1 have been obtained. The interest for this complex is two-fold. First, complex 1 is made of 2D layers packing along the (0–11) direction favored by the presence of lattice and coordinated water molecules. And second, nanostructures that could be derived by delamination are potentially suitable for catalytic purposes. Therefore it represents an excellent example to study the role of interlayer solvent molecules on the ultrasound-assisted delamination of functionally-active 2D metal-organic frameworks in water, a field of growing interest. With this aim, ultrasound-assisted delamination of the crystals was optimized with time, leading to stable nanosheet colloidal water suspensions with very homogeneous dimensions. Alternative bottom-up synthesis of related nanocrystals under ultrasound sonication yielded similar shaped crystals with much higher size dispersions. Finally, experimental results evidence that the nanostructures have higher catalytic activities in comparison to their bulk counterparts, due to larger metallic center exposition. These outcomes confirm that the combination of liquid phase exfoliation and a suitable synthetic design of 2D coordination polymers represents a very fruitful approach for the synthesis of functional nanosheets with an enhancement of catalytic active sites, and in general, with boosted functional properties., This work was supported by grant RTI2018-098027-B-C21 from the Spanish Government funds and by the European Regional Development Fund (ERDF). The ICN2 is funded by the CERCA programme/Generalitat de Catalunya. The ICN2 is supported by the Severo Ochoa Centres of Excellence programme, funded by the Spanish Research Agency (AEI, grant no. SEV-2017-0706). Noemí Contreras Pereda’s project that gave rise to these results received the support of a fellowship from “laCaixa” Foundation (ID 100010434). The fellowship code is LCF/BQ/ES17/11600012. Renhao Dong acknowledgements the financial support from ERC Starting Grant (FC2DMOF, No. 852909) and DFG project (SPP 1928, COORNETs).

The importance of dopamine (DA) detection as a biomarker for several diseases, especially Parkinson''s disease, has persuaded scientists to develop new nanomaterials for efficient sensing of DA in clinical samples. Ultrathin metal-organic nanosheets due to their exceptional thickness, large surface area, and flexibility are endowed with many accessible active sites and optimal surface interaction with the target analyte molecules. In this regard, a novel layered fluorescent metal-organic nanomaterial with a honeycomb topology based on europium, [Eu(pzdc)(Hpzdc)(H2O)]n (ECP) (H2pzdc = 2,3-pyrazine dicarboxylic acid), was synthesized. X-ray crystallography revealed that the 3D supramolecular architecture of ECP is constructed from noncovalent interactions of coordinated water molecules between the 2D layers along the b axis. These layers that are only ∼4 nm thick were conveniently separated through ultrasound-induced liquid phase exfoliation. Optical studies show that the reduction of ECP thickness enhances the fluorescence intensity and serves as an efficient optical marker for DA detection. ECP nanoflakes exhibited fast response and high selectivity for DA detection in clinical samples. Good linearity for DA detection in the range of 0.1-10 μM with a detection limit of 21 nM proves the potential of ECP nanoflakes in DA sensing applications.

This scenario was designed to investigate the protein corona pattern on the pillar-layer surface of a Cu-based metal–organic framework (MOF) in human plasma. The [Cu(L)(L/)].1.3DMA (MOF-1) {L = 4, 4/-bipyridine and L/ = 5-aminoisophthalic acid}, was synthesized through the sonochemical irradiation approach as well as characterized by various techniques like scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray powder diffraction and single-crystal X-ray diffraction. The space group was determined to be an orthorhombic space group (Pbam) by single-crystal X-ray diffraction. Single-crystal X-ray analyses on MOF-1 showed that Cu+2 ion was 6-coordinated. Besides, to study and clarify interactions between MOFs and biological milieu, human whole blood plasma was selected as a model. Fluorescence spectroscopy and SDS-PAGE techniques were employed to explore quantitative and qualitative in situ characterization of protein corona as well. Furthermore, cell viability in a cancerous cell lines was evaluated by MTT assay in the presence and absence of the corona. The results from SDS-PAGE illustrated that the most adsorbed quantity among plasma proteins belongs to fibrinogen (α, β and γ chains), and this protein showed the maximum frequency on the MOF-1s surface, so the possible interactions of MOF-1s with fibrinogen also studied using fluorescence spectroscopy and corresponding data were plotted. According to the obtained data from MTT assay, these structures have concentration-dependent toxicity. In brief, based on the obtained data in the current study, the designed MOF can be introduced as a new desirable carrier for drug/gen delivery after further prerequisite assessments.

A new paramagnetic heteronuclear complex formulated as [K3Fe(μ-ox)3(H2O)3]n (1), where ox2- is oxalate, has been synthesized under hydrothermal condition. The molecular structure of complex 1 was characterized by elemental analysis, Fourier-transform infrared spectroscopy (FT-IR) and single-crystal X-ray diffraction (SCXRD). The results of SC-XRD analysis revealed that complex 1 crystallizes in the centrosymmetric space group P21/c of a monoclinic system with cell dimension a = 7.7175 (4) A, b = 19.8009 (7) A, c = 10.2623 (5) A, and β = 107.634 (5)° at 100 K. The thermal behavior of complex 1 was studied by thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The magnetic behavior of complex 1 was studied at room temperature by a vibration sample magnetometer (VSM). Thermal decomposition of the silica and alumina supports of complex 1 at 650 °C resulted in the main catalysts, Fe2O3-K2O/SiO2 and Fe2O3-K2O/Al2O3. The catalytic activity of the main catalysts was evaluated for CO hydrogenation. For comparative purposes, the reference catalysts of Fe2O3-K2O/SiO2 and Fe2O3-K2O/Al2O3 were prepared by the impregnation method. The structure and composition of the catalysts were investigated by FT-IR spectroscopy, powder X-ray diffraction (PXRD), N2 adsorption-desorption analysis, scanning electron microscopy (SEM), inductively coupled plasma atomic emission spectroscopy (ICP-AES) and energy dispersive X-ray analysis (EDX). We tested all catalysts for hydrogenation of CO at 5 bar of pressure in the temperature range of 593-673 K. It was found that the main catalysts have better CO conversion and selectivity to desired products, such as light olefins, than the reference catalysts.

The reaction of potassium tetrachloroplatinate(II) with dimethylsulfide and a mixture of HBr/KBr affords trans-[PtBr2(SMe2)2]; [PtBr2(Me2bpy)] (Me2bpy =4,4'-dimethyl-2,2'-bipyridine) was prepared from the reaction of trans-[PtBr2(SMe2)2] with Me2bpy. The crystal structure of the yellow form of [PtBr2(bu2bpy)] (bu2bpy =4,4'-di-tert-butyl-2,2'-bipyridine) was determined by X-ray crystallography. The X-ray single-crystal structure determination of complex [PtBr2(bu2bpy)] reveals that the platinum adopts a square planar geometry with a twofold axis through the platinum atoms. Thermal properties of the related series of diimine platinum(II) complexes [PtX2(bu2bpy)] (X = Cl, Br, I) reveal that the thermal stabilities increase [PtI2(bu2bpy)] 2(bu2bpy)] 2(bu2bpy)]. [PtBr2(bpy)] (bpy =2,2'-bipyridine), [PtBr2(Me2bpy)] and [PtX2(bu2bpy)] (X = Cl, Br, I) were studied by MTT assay against two human breast cancer cell lines of MCF-7 and MDA-MB-468 with [PtCl2(bu2bpy)] having a higher cytotoxic effect towards both cancer cell lines, which shows the significant role of the halide and diimine ligand. Semi-spherical Pt(0) nanoparticles (NPCs) were prepared by the simple calcination of [PtX2(bu2bpy)] (X = Cl, Br, I) at 800 °C in air.`

The reaction of electron rich [PtMe2(NN)] with SnMe2Cl2 in a 1:3/Pt:Sn mole ratio resulted in formation of Pt(IV) complexes [PtMe2(SnMe2Cl)Cl(NN)] {NN = 4,4′-Me2bpy (4,4′-dimethyl-2,2′-bipyridine) (7); 5,5′-Me2bpy (5,5′-dimethyl-2,2′-bipyridine) (8); bphen (4,7-diphenyl-1,10-phenanthroline) (9)}. NMR data show that the resulting complexes exist as the sole product corresponding to that of trans oxidative addition of SnMe2Cl2. The yellow polymorph of complex [PtCl2(5,5′-Me2bpy)] (10) was characterized by X-ray crystallography from the reaction of [PtMe2(5,5′-Me2bpy)] and excess of SnMe2Cl2 due to the reductive elimination of 8. On the other hand, the reaction of [PtMe2(NN)] with SnEt2Cl2 in a 1:3/Pt:Sn mole ratio resulted in formation of new complexes [PtMe2(SnEt2Cl)Cl(4,4′-Me2bpy)] (11), [PtMe2(SnEt2Cl)Cl(5,5′-Me2bpy)].SnEt2Cl2 (12) and [PtMe2(SnEt2Cl)Cl(bu2bpy)].SnEt2Cl2 (bu2bpy = 4,4′-di-tert-butyl-2,2′-dipyridine) (13). NMR data indicate that the Pt SnEt2Cl bond is weaker than the Pt SnMe2Cl bond. The X-ray crystal structure of 13 reveals that organoplatinum(IV) complex acts as a donor to the SnEt2Cl2 to form an adduct in a distorted trigonal bipyramid with the axial Cl⋯Sn Cl and equatorial SnEt2Cl units. Moreover, the X-ray crystal structure of the new yellow form of [PtClMe(4,4′-Me2bpy)] (14), which has been formed by the crystallization of a mixture of [PtMe2(4,4′-Me2bpy)] and excess of SnEt2Cl2, is described. The reaction of dimethylplatinum(II) complexes with dimethyltin diisothiocanate are reported for the first time which occur via Sn-NCS bond cleavage to afford the organoplatinum(IV) complexes [PtMe2(SnMe2NCS)(SCN)(NN)] {NN = bpy (17); phen (18); 5,5′-Me2bpy (19); bu2bpy (20); bphen (21)}. The crystal structures of the novel thiocyanatoplatinum(IV) complexes [PtMe2(SCN)2(bpy)] (22) and [PtMe2(SCN)2(5,5′-Me2bpy)]. H2O (23) are discussed which have been obtained due to the α-elimination of SnMe2. The crystal structures of 22–23 show that platinum adopts a slightly distorted octahedral geometry with trans- Pt(SCN)2 configuration in which SCN is bonded through sulfur atom while the nitrogen atom is coordinated to tin. NMR data indicate that the products dissociate via α-elimination of SnMe2 or reductive elimination of organotin(IV) compound and the stability of the organoplatinum(IV) compounds varies according to the trends [PtMe2(SnMe2Cl)Cl(NN)]>[PtMe2(SnMe2NCS)(SCN)(NN)]>[PtMe2(SnEt2Cl)Cl(NN)].

Single crystals of (H 2 NNH 3 ) 3 CdBr 5 were grown and their properties were investigated. DSC, DTG, structural studies, optical polarized microscopy observations and dielectric studies are presented. TGA showed the stability of the substance up to about 455 K and decomposition above this temperature. DSC studies revealed the first order structural phase transitions at 294/292 on heating/cooling runs. X-ray structural studies showed a change of symmetry from orthorhombic to monoclinic and the transition seems to belong to the mmmF2/m Aizu's species. In optical studies performed with a polarizing microscope, the ferroelastic type of domain structure and the phase front appearance were observed. Dielectric measurements clearly evidenced the first-order phase transition as a jump-like decrease of permittivity on cooling and increase on heating. Structural and dielectric studies indicate the order-disorder character of the phase transition.

In this paper, we show a strategy to modify salphen-type Schiff base ligands with naphtol (SYML1) and pyrocathecol (2,3-dihydroxyphenyl) groups (SYML2), or a combination of both (ASYML). Each of these ligands can be used to obtain polynuclear metal complexes following two different strategies. One relies on using metals that are either too large for the N2O2 cavity or not fond of coordination number 4 and the other one relies on forcing the polynuclear species by adding functional groups to the hydroxybenzaldehayde in order to have extra coordination sites in the ligand. We report and characterize the mononuclear complexes SYML1-Cu and SYML1-Ce, along with the dinuclear complex SYML1-Fe and the tetranuclear species SYML2-Mn. The asymmetric ligand ASYML routinely hydrolyzes into the symmetric ligands in the reaction mixtures. SYML1-Fe displays a nearly linear Fe-O-Fe bridge with very strong antiferromagnetic coupling between the Fe(III) ions.

Colchicine is a well-known compound with strong antiproliferative activity that has had limited use in chemotherapy because of its toxicity. In order to create more potent anticancer agents, a series of novel colchicine derivatives have been obtained by simultaneous modification at C7 (amides and sulfonamides) and at C10 (methylamino group) positions and characterized by spectroscopic methods. All the synthesized compounds have been tested in vitro to evaluate their cytotoxicity toward A549, MCF-7, LoVo, LoVo/DX and BALB/3T3 cell lines. Additionally, the activity of the studied compounds was investigated using computational methods involving molecular docking of the colchicine derivatives to &beta, tubulin. The majority of the obtained derivatives exhibited higher cytotoxicity than colchicine, doxorubicin or cisplatin against tested cancer cell lines. Furthermore, molecular modeling studies of the obtained compounds revealed their possible binding modes into the colchicine binding site of tubulin.

Reaction of 2-imino-4-thiobiuret with boric acid (in molar ration of 1:1) in aqueous solution at the mild conditions leads to formation of a heterocyclic compound of 2,2-dihdroxy-4-amino-6-thio-1,3,5-trihydrotriaza-2-boracyclohex-3-en (1). This compound crystallizes directly from the reaction solution after a few days, giving light yellowish transparent monoclinic crystals (P21/n). X-ray single crystal analysis shows that the heteroring and the thio- and amine groups are co-planar, whereas the plane of hydroxyl groups linked to boron are almost perpendicular to plane of the ring. The 2,2-dihdroxy-4-amino-6-thio-1,3,5-trihydrotriaza-2-boracyclohex-3-en molecules are arrangement via O–H...S hydrogen bonds in the stacks along b-axis, and the stacks are interacting each other via N–H...O hydrogen bonds forming a three-dimensional supramolecular architecture. The qualitative and quantitative intermolecular interactions in the crystal were analyzed using the Hirshfeld surface and 2D-fingerprint plots. The compound was also characterised by the FT-IR and Raman spectroscopy. The IR and FT-Raman spectra were made for protiated (1) and its deuterated analogue (1d). The IR and FT-Raman spectra for molecule in the gas-phase were calculated using DFT. DFT calculations and the isotropic frequency shift are helpful in assignments of the vibration bands. The calculated HOMO and LUMO energy gap explain the charge transfer interactions taking place within the molecule.

One lead(II) coordination polymer compound (CPC) [Pb(L)(NCS)]n (1) (2D layer), in which L stands for C5H4NCOO {pyridine-3-carboxylate(−) anion}, has been synthesized following two different experimental approaches; branched tube and sonochemical irradiation methods. Independently of the methodology used, the same crystalline phase is obtained for complex. Single crystal X-ray analyses of compound 1 showed that Pb2+ ions are 5-coordinated, and Hirschfeld surface analyses were studied for 1, showing the role of sonochemistry to modulate both morphology and dimensions of the resulting crystalline material. In order to study the effects of the solvent and time of reaction on the formation of [Pb(L)(NCS)]n (1) CPC, some experiments were designed, and four samples of 1 were synthesized by sonochemical process. Less time of reaction resulted in the formation of compound 1 mainly like micro-nano rods. With more time of reaction, various morphologies, mainly microhexagonal of 1, were obtained. These four samples have been used as new precursors for the preparation of lead(II)oxide micro-nano structures via solid-state thermal decomposition process. Mix morphology, mainly like sphere micro-nano structures of lead(II)oxide could be prepared from 1. These micro-nano structures were characterized by IR spectroscopy, X-ray powder diffraction (XRD) and scanning electron microscopy (SEM).

A copper (I) complex containing 2,9-dimethyl-1,10-phenanthroline (dmph), [Cu(dmph)2]Cl·6H2O, was prepared by reaction of CuCl2·2H2O and 2,9-dimethyl-1,10-phenanthroline in an aqueous solution at pH = 11 and characterized using elemental analysis, IR, EDX and X-ray crystallography. The complex consists of a mononuclear copper (I) surrounded by four coordinating nitrogen atoms of two dmph ligands, one Cl− anion and six H2O molecules. This novel cupper (I) complex was used as a catalyst for alkyne-azide cycloaddition (CuAAC) reaction to produce several 1,2,3-triazoles in high yields. The presented catalytic system fulfils the requirements of “click chemistry” with its soft and appropriate conditions, notably in water as solvent with low catalyst amount without any co-catalyst or activator.

In the current study, we hydrothermally synthesized polyoxomolybdate-based hybrid materials, [Zn(4,4´-bpy)2(H2O)4]3(Mo8O26)2(NH4)2(4,4´-bpy)6 (1) and [(4,4´-H2bpy)2(H2P2Mo5O23)].2H2O (2) based on β-octamolybdate and Strandberg-type structures using 4,4´-bipyridine (4,4´-bpy) ligand. Structure of the obtained materials was investigated by single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), FT-IR and inductive coupled plasma optical emission spectroscopy (ICP-OES). The crystals were insoluble in water and employed as catalysts for the catalytic wet air oxidation (CWAO) as well as catalytic wet oxidation (CWO) of Direct Blue 71 (DB) as a representative of a tri-azo dye pollutant under mild conditions. The POM catalysts exhibited good catalytic activity under ambient conditions and could be reused without loss of crystallinity and activity.

The single crystals of hexakis(1-(diaminomethylene)thiouron-1-ium) benzene-1,2,3,4,5,6-hexacarboxylate (mellitate(6-)) tetrahydrate suitable for the X-ray analysis were grown using a solution growth technique at room temperature. The compound crystallises in centrosymmetric space group of the triclinic system. The conformation of six crystallographically independent 1-(diaminomethylene)thiouron-1-ium cations is not strictly planar, but twisted. Both planar arms of the cations are oppositely rotated by 6.1(1) ÷ 20.9(1)o around the C N bonds involving the central N atom. All of the carboxylate groups of mellitate(6-) anion are inclined to the plane of aromatic six-membered carbon ring by 43.0(1) ÷ 72.0(1)o. Oppositely charged components i.e. 1-(diaminomethylene)thiouron-1-ium cations and mellitate(6-) anion interact each other via N H⋯O hydrogen bonds forming hexakis(1-(diaminomethylene)thiouron-1-ium) mellitate units that further interact with the water molecules forming hexakis(1-(diaminomethylene)thiouron-1-ium) mellitate tetrahydrate supramolecular architecture. Hirshfeld surface and the analysis of 2D fingerprint plots are used for illustrate both qualitatively and quantitatively interactions between the units governing the supramolecular assemblies. The compound was also characterised by vibrational spectroscopy. The vibrational assignment have been supported by the isotopic frequency shift.

A solid state Eu3+ complex with dehydroacetic acid (DHA) has been synthesized and characterized by elemental analysis, UV–visible, FT-IR, FT-Raman, powder and single-crystal X-ray diffraction and optical spectroscopy studies. The complex has formula [Eu(DHA)2(H2O)5]NO3 with DHA = C8H7O4−, where the europium ions is in monocapped distorted square antiprism environment with coordination number nine. Its photophysical properties have been analyzed in terms of its molecular structure and DFT calculations performed for the representative crystal fragment including Eu3+ and two DHA ligands. The luminescence and dynamics of the excited states depopulation have been studied using femtosecond laser excitation. The energy transfer mechanism between the ligand and Eu3+ electronic energy levels has been proposed. The obtained results have been compared to those of Gd3+ dehydroacetic derivative.

Reactivity of magnesium phthalocyanine (MgPc) in the dry 3,4-lutidine (3,4-lut), in the 3,4-lut/DMSO, in DMSO and in 3,4-lut/acetylacetone (acacH) systems has been investigated. Reaction of MgPc with dry 3,4-lut leads to formation of MgPc(3,4-lut) compound (1), in which the Mg atom is characterised by rarely encountering in magnesium phtalocyanines 4 + 1 N-type of coordination. In presence of the water tracer, depending on the reaction conditions and the 3,4-lut quantity in the MgPc/3,4-lut/DMSO system the solvothermal reaction leads to formation of three complexes in the crystalline form: MgPc(H2O)·2(3,4-lut) – (2), [MgPc(3,4-lut)][MgPc(H2O)·2(3,4-lut)]·½(3,4-lut) – (3) and [MgPc(H2O)·(3,4-lut)][MgPc(DMSO)]·½(DMSO) – (4). Reaction of MgPc with DMSO yields crystalline MgPc(DMSO) complex (5). In these complexes in the solid-state the central Mg atom of MgPc exhibits 4 + 1 coordination. The reaction of MgPc in the case of 3,4-lut/acacH system leads to demetallation of MgPc and formation of crystalline Mg(acac)2(H2O)2 compound (6) that after several days at ambient air in the mother liquor transforms into organic crystalline compound of C10H12O2 (7). The structure of 1–7 has been determined by X-ray single crystal diffraction. All MgPc-derivatives (1–5) were characterised by thermogravimetric analysis. Partial MO energy diagrams and the calculated absorption spectra of the MgPc-derivatives were compared with the experimental electronic absorption spectra in 3,4-lutidine and DMSO solutions. These results point that the axial ligation of MgPc by O- and N-donor ligands do not change significantly the energy gap of the HOMO-LUMO levels which is compared with that of the parent MgPc pigment.

Designable coordination polymers with suitable chemical diversities and biocompatible structures have been proposed as a promising class of vehicles for drug delivery systems. Here, we hydrothermally synthesized a novel one-dimensional (1D) coordination polymer, [Zn(H2O)6K2(H2BTC)2(H2O)4](H2BTC)2·2H2O, where H3BTC = benzene-1,3,5-tricarboxylic acid (trimesic acid), cp.1. As the hydrogen bonds stabilized 1D chains in three dimensions, the cp.1 could be a good candidate for delivering small-molecule chemotherapeutics such as 5-fluorouracil (5-Fu). The synthesized cp.1 showed a remarkable 5-Fu loading of 66% with encapsulation efficiency of 98% and almost complete release process. The 5-Fu-loaded cp.1 displayed a time-dependent cytotoxicity effect against breast cancer cell lines MCF-7 and 4T1. The cellular uptake of cp.1 particles was investigated via confocal laser scanning microscopy using fluorescein isothiocyanate and LysoTracker Red staining. Furthermore, the in vivo antitumor impact of 5-Fu-loaded cp.1 was studied on 4T1 breast cancer BALB/c mice model. The intratumor treatment of 5-Fu-loaded cp.1 demonstrated beneficial antitumor efficacy by postponing tumor growth. These results suggest that the 5-Fu-loaded cp.1 microparticles with a great locoregional delivery can be efficient anticancer drug carriers for further clinical treatments.

Four novel compounds, [NH3CH2CH2OH][MIIIMII(HCOO)6] with MIII = Fe and MII = Mn (HEAFeMn), MIII = Fe and MII = Ni (HEAFeNi), MIII = Cr and MII = Mn (HEACrMn) and MIII = Cr and MII = Co (HEACrCo), have been synthesized. They crystallize in the trigonal niccolite-type structure (space group P 3 ¯ 1c). Magnetic studies revealed that HEAFeNi, HEAFeMn and HEACrCo are weak ferromagnets with the ordering temperature of 43, 27 and 11 K, respectively, whereas HEACrMn does not order magnetically at least down to 2 K. A source of the ferromagnetic component is most likely a canting of the antiferromagnetically ordered moments by a small angle resulting from antisymmetric exchange or single-ion anisotropy. Raman and IR data confirm that all obtained samples are isostructural. Optical studies of HEACrMn show that local crystal field around Cr3+ ion is of intermediate strength with the Dq/B value of 2.57. Luminescence studies indicate that HEACrMn exhibits efficient Cr3+-based emission. Below 200 K, the 2E-4A2 phosphorescence observed as two bands at 686 and 696 nm becomes predominate.

The single crystals of tetrakis(1-(diaminomethylene)thiouron-1-ium) pyromellate suitable for the X-ray analysis were grown using a solution growth technique at room temperature. The compound crystallises in the centrosymmetric space group P21/c of the monoclinic system. Asymmetric unit consists of half of the tetrakis(1-(diaminomethylene)thiouron-1-ium) pyromellate molecule. Both independent parts of the 1-(diaminomethylene)-thiouron-1-ium cations are not strictly planar, but twisted. Both planar arms of the cation are oppositely rotated around the C N bonds involving the central N atom of the cation. The arrangement of the oppositely charged components, i.e. 1-(diaminomethylene)-thiouron-1-ium cations and pyromellate(4-) anion is determined by the N H⋯O hydrogen bonds with R22(8) and R21(6) graphs forming supramolecular tetrakis(1-(diaminomethylene)-thiouron-1-ium) pyromellate units that further interact each other forming three dimensional hydrogen bonded network. Hirshfeld surface and the analysis of the 2D-fingerprint plots are illustrating both qualitatively and quantitatively interactions governing the formation of the supramolecular tetrakis(1-(diaminomethylene)-thiouron-1-ium) pyromellate complex as well as the mutual arrangement of the supramolecules in the crystal. The compound was also characterized by the FT-IR and Raman spectroscopy. Assignment of the bands have been supported by the isotropic frequency shift.

Herein a simple method for N-methylation of ethanolamines with paraformaldehyde as a dual methylation and reducing agent has been investigated. Two new cobalt complexes, Co[Methyl 6-(morpoline methyl) picolinate]2Cl2 and Co(2,6 bis morpholine methyl pyridine)Cl2 were prepared and applied as homogeneous catalyst in reductive methylation reaction. All experiments have progressed with excellent conversion and selectivity toward N,N dimethyl ethanolamine. On the other hand, Pyrolysis of prepared cobalt complexes on activated carbon at 550 °C leads to the formation of cobalt oxide nano-particles. These heterogeneous catalysts were shown similar activities in this reaction. Single-crystal X-ray crystallography, Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) were used for characterization of prepared catalysts.

The crystal structure of 6-chloro-2,4-dihydro-1H-3,1-benzoxazine-2,4-dione (5-chloroisatoic anhydride), C8H4ClNO3, has been determined and analysed in terms of connectivity and packing patterns. The compound crystallizes in the noncentrosymmetric space groupPna21with one molecule in the asymmetric unit. The role of different weak interactions is discussed with respect to three-dimensional network organization. Molecules are extended into one-dimensional helical arrangements, making use of N—H...O hydrogen bonds and π–π interactions. The helices are further organized into monolayersviaweak C—H...O and lone pair–π interactions, and the monolayers are packed into a noncentrosymmetric three-dimensional architecture by C—Cl...π interactions and C—H...Cl and Cl...Cl contacts. A Hirshfeld surface (HS) analysis was carried out and two-dimensional (2D) fingerprint plots were generated to visualize the intermolecular interactions and to provide quantitative data for their relative contributions. In addition, tests of the antimicrobial activity andin vitrocytotoxity effects against fitoblast L929 were performed and are discussed.

We report synthesis of four novel heterometallic MOFs, [(NH4)(H2O)][CrIIIMII(HCOO)6] with MII = Zn (NH4CrZn), Co (NH4CrCo), Mn (NH4CrMn) and Ni (NH4CrNi). X-ray diffraction shows that NH4CrZn crystallizes in the trigonal structure (space group P 3 ¯ 1c) with ordered Cr3+ and Zn2+ centers while NH4CrCo, NH4CrMn and NH4CrNi crystallize in the hexagonal system with chiral space group of P6322 and statistical occupation of the same sites by Cr3+ and M2+ ions. Raman and IR data confirm presence of water molecules and different confinement of the ammonium cations in the cavities of chiral and niccolite type metal formate frameworks. Optical studies show that Cr3+ ions in NH4CrZn and NH4CrMn are located at sites of strong crystal field with the Dq/B values of 2.54 and 2.47, respectively. Luminescence studies show that these compounds exhibit efficient Cr3+-based emission with the decay time of 8.1 μs (0.44 ms) at 295 K (10 K) for NH4CrMn and 8.3 μs (0.78 ms) for NH4CrZn.

A family of supramolecular complexes of melamine with fluorophenylacetic acid isomers using solvent-assisted and evaporation-based techniques has been prepared. Crystallization of melamine with 2-fluorophenylacetic acid yield hydrated ionic supramolecular complex ( 1 ), whereas crystallization of melamine with 3- and 4-fluorophenylacetic acids leads to formation of neutral supramolecular complexes ( 2 , 3 ), all with base to acid ratio of 1:2. The supramolecular assembly is driven by the noncovalent interactions, most commonly by the hydrogen bonds. The components of the crystal 1 interact via N H⋯O and O H⋯N hydrogen bonds with R 2 2 (8) and R 3 2 (10) graphs forming ionic supramolecular complex, whereas the components in the crystals 2 and 3 interact with a graph of R 2 2 (8) forming neutral supramolecular complexes. The singly protonated melamin-1-ium residues in 1 interact each other via a pair of N H⋯N hydrogen bonds forming one dimensional chains along [−110] that interact via N H⋯O with deprotonated and neutral 2-fluorophenylacetic acid units and water molecules forming ribbon. In 2 and 3 co-crystals the melamine interacts with 3- and 4-fluorophenylacetic acids via a pair of N H⋯O hydrogen bonds forming pseudo one-dimensional supramolecular chains along [010] direction. Hirshfeld surface and analysis of 2D fingerprint plots have been analysed both quantitatively and qualitatively interactions that governing the supramolecular organisation. The IR and Raman vibrational characterization of the supramolecular complexes 1 – 3 was supported by the spectra of their deuterated analogues.

The single crystals of 1-(diaminomethylene)thiouron-1-ium 2-pyridinecarboxylate, (C2H7N4S)-(C5NH4COO), (1) suitable for the X-ray analysis were grown using a solution growth technique room temperature. Recrystallization of 1 in heavy water (three-times) yield respective deuterated analogue, (C2D7N4S) (C5NH4COO), (1d). The X-ray analyses show that both, protonated and deuterated, compounds crystallize in the same crystal system with quite similar lattice parameters. X-ray analysis on a single crystal of 1 measured at 100 K and RT showed that no structural phase changes were observed between RT and 100 K. At both temperatures, crystal 1 belongs to the centrosymmetric space group of the triclinic system with two molecules in an asymmetric unit. In both molecules of the asymmetric unit the opposite charged units interact each other via the same R22(8) hydrogen bonding graph that is formed by donation of the amine groups linked to the same carbon atom to both oxygen atoms of the COO– of the 2-pyridinecarboxylate anions. The 1-(diaminomethylene)thiouron-1-ium 2-pyridinecarboxylate units are interact each other via additional N–H…O and N–H…N hydrogen bonds formed between these independent hydrogen bonded R22(8) units forming layers parallel to (001) crystallographic plane. The interactions between layers is significantly weaker than within the layers since the layers interact via much weaker N H…S hydrogen bonds. Thus the (001) crystallographic plane is a cleave plane of the crystals 1. Hirshfeld surface and the analysis of 2D fingerprint plots are illustrating both quantitatively and qualitatively interactions governing the supramolecular assemblies. The compound was also characterised by the FT-IR and Raman spectroscopy. Assignment of the vibrational bands have been supported by the DFT calculations and the isotropic frequency shift.

Three new d 8 transitions metal complexes containing substituted-2,2′:6′,2″-terpyridine ligands of [Ni II (pytpy) 2 ]Cl 2 . H 2 O (pytpy = 4′- (4-pyridyl)-2,2′:6′,2″-terpyridine) ( 1 ), [Pt(tpyOH)Cl] + Cl − . 2H 2 O ( 2 ) (tpyOH = 4′-hydroxy-2,2′:6′,2″-terpyridine) and [Pt(tpySH)Cl] + Cl − .2H 2 O ( 3 ) (tpySH = 4′-mercapto-2,2′:6′,2″-terpyridine) have been prepared. The crystal structure of 1 reveals that the nickel(II) is six-coordinated by six nitrogen atoms of pytpy in a distorted octahedral geometry NiN 6 , while the platinum complex ( 2 ) is four-coordinated by one Cl − and three nitrogen atoms of tpyOH in a distorted square planar geometry PtClN 3 . The lattice crystal water molecule plays a significant structure directing role in the complexes 1 and 2 . Many strong noncovalent interactions are present in the crystal structure of 1 and 2 . For example, the supramolecular network of C H⋯Cl, O H⋯Cl and Cl⋯Cl interactions connected molecules and ions in the crystalline 1 , while there are several Pt⋯Pt, C H⋯Cl, H 2 O⋯H 2 O, C OH⋯H 2 O, Cl⋯H 2 O and π-π interactions in 2 . The solution luminescence properties of 2 and 3 have been investigated. The emissions of the platinum complexes 2 and 3 exhibit the high-energy intense π→π* intraligand and low-energy MLCT transitions in solution. The solid-state emissions of complexes 1–3 due to the MLCT and π-π interactions are also observed in the solid state. The thermal stability of all complexes reveals that the loss of terpyridine ligand is observed at higher temperatures due to the strong metal-nitrogen bonds of terpyridine ligands.

A new para-iodo-N-benzyl amide of salinomycin was synthesized and characterized by NMR, FT-IR, DFT, single crystal X-ray diffraction and theoretical methods. The results obtained for the crystal, in solution and in gas phase provided evidence of pseudo-cyclic structure of this compound stabilized by intramolecular hydrogen bonds. It was shown that the compound studied forms stable 1:1 complexes with monovalent (Li+, Na+, K+, Rb+ and Cs+) and divalent (Mg2+, Ca2+, Sr2+ and Ba2+) cations demonstrating that the chemical modification of salinomycin carboxyl group considerably changes the ionophoretic properties of this antibiotic. For the first time, the ESI MS fragmentations of the complex of para-iodo-N-benzyl amide of salinomycin with Na+ are also discussed in details.

Two new diphenic acid based proton transfer compounds (creatH)(diphH).H2O (1) and (pydaH)(diphH).3H2O (2) (where creat = creatinine, pyda = 2,6-diaminopyridine and diphH2 = diphenic acid) were synthesized. Their solid-state structures were determined and non-covalent interactions responsible for extending their supramolecular networks were characterized. The Density Functional Theory (DFT) and Natural Bond Orbital (NBO) calculations as well as Atoms in Molecules (AIM) analysis were used to analyze the non-covalent interactions in both compounds.

The reaction between [MoO2(acac)2] and an ONO type Schiff-base ligand (L = 4-bromo-2-((2-hydroxy-5-methylphenylimino)methyl)phenol) resulted a new oligomer molybdenum complex ([MoO2(L)]n). The oligomer complex was characterized by elemental analysis, FT-IR, 1H and 13C NMR spectroscopies. A suitable single crystal of the complex was grown in DMSO and characterized by X-ray single crystal diffraction as monomer stabilized by one DMSO molecule, [MoO2L(DMSO)]. The [MoO2(L)]n complex was used as a catalyst in epoxidation of olefins. Besides the high activity and selectivity, very high turnover numbers were a remarkable advantage of the catalytic system.

A treatment of piperazine (H2pipz) and pyridine-2,6-dicarboxylic acid (H2pydc) with CeIII ion led to the formation of a new binuclear cerium(III) complex (H2pipz)[Ce2(pydc)4(H2O)4]·(H2O) (1). Compound 1 was characterized by elemental analyses, IR spectroscopy, thermal gravimetric and single crystal X-ray diffraction. The binuclear unit of 1 contains CeIII cations bridged by two anionic pydc2− ligands. The Cerium(III) ion is nine-coordinated by seven oxygen atoms from two water molecules and five carboxylate groups, and two nitrogen atoms from two pydc2− ligands. Non-covalent interactions i.e. hydrogen bonds are present in the crystal structure of 1 and assemble the binuclear units and the co-crystallized water and piperazine molecules into a 3D architecture. Compound 1 was used for the preparation of the CeO2 nanoparticles. Synthesized CeO2 nanoparticles were characterized by IR spectroscopy, powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM). Furthermore, the solid-state luminescent properties of compound 1 at room temperature were studied.

The single crystals of 1-(diaminomethylene)thiouron-1-ium propionate suitable for the X-ray analysis were grown using a solution growth technique room temperature. The compound crystallises in the centrosymmetric C2/c space group of the monoclinic system. The conformation of the 1-(diaminomethylene)thiouron-1-ium cation is not strictly planar, but slightly twisted. Both planar arms of the cation are oppositely rotated by 2.1(1)° around the C N bonds involving the central N atom. The propionate(−) anion is also non-planar, the carboxylate group is turned by 4.3(1)° in relation to the planar carbon chain. The arrangement of oppositely charged components, i.e. 1-(diaminomethylene)thiouron-1-ium cations and propionate(−) anions in the crystal is mainly determined by ionic and N H⋯O hydrogen bonding interactions forming two-dimensional network aligned to (100) plane. The neighbouring 2D layers interact via much weaker N H⋯S hydrogen bonds forming three-dimensional hydrogen bonded network. Hirshfeld surface and the analysis of 2D fingerprint plots are illustrating both quantitatively and qualitatively interactions governing the supramolecular assemblies. The compound was also characterised by the FT-IR and Raman spectroscopy. The vibrational assignments have been supported by the isotopic frequency shift.

The crystal and molecular structures of aquo 4,6-dimethyl- 5H -[1,2,3]triazolo[4,5- c ]pyridine in a zwitterionic form have been determined by X-ray diffraction and DFT quantum chemical calculations. The compound adopts a triclinic crystal structure, space group P-1 = C i 1 (No. 2) with Z = 2 and the unit cell parameters: a = 6.7452 A, b = 9.5292 A, c = 9.5554 A and α = 69.279°, β = 73.951°, γ = 74.242°. The temperature dependence of its IR and Raman spectra have been measured and discussed in terms of proton transfer dynamics. The molecular structure and simulated vibrational spectra of the studied compound have been determined using the DFT B3LYP/6-311G(2d,2p) approach. Vibrational characteristics of a triazolo-pyridinium system in the studied compound has been proposed. A role of water molecules in stabilization of the compound space structure has been considered.

The potassium N -R-sulfonyldithiocarbimates, K 2 (RSO 2 N CS 2 ) [R = CH 3 ( 1a ), CH 3 CH 2 ( 1b ), C 6 H 5 ( 1c ), 2-CH 3 C 6 H 4 ( 1d ) and 4-CH 3 C 6 H 4 ( 1e )], reacted with nickel sulfate or zinc acetate to yield complex anions which were isolated as their tetraphenylphosphonium salts with the formulae (PPh 4 ) 2 [M(RSO 2 N CS 2 ) 2 ], were M = Ni ( 2a – 2e ) and M = Zn ( 3a – 3e ). The compounds 3a – 3e readily react with sulfur in dimethylformamide producing bis(trithiocarbimato)-zinc complexes ( 4a – 4e ) with the formula (PPh 4 ) 2 [Zn(RSO 2 N CS 3 ) 2 ]. Mixed nickel complexes ( 5a – 5e ), (PPh 4 ) 2 [Ni(RSO 2 N CS 2 )(RSO 2 N CS 3 )], were obtained from the zinc compounds 4a – 4e by reaction with nickel sulfate in dimethylsulfoxide. The complexes 5a – 5e are the first examples of N -R-sulfonyldithiocarbimate and N -R-sulfonyltrithiocarbimate heteroleptic nickel complexes. The structures of 5a and 5e were determined by X-ray crystallography. Both compounds crystallize in the centrosymmetric space group of the triclinic system. The Ni 2+ cation is S,S -chelated by one dithio- and one trithiocarbimate ligands, forming distorted square-planar configurations. The square planar geometry around the nickel atom was confirmed for compounds 5a – 5e by electronic, vibrational and nuclear magnetic resonance spectroscopies. High-resolution mass spectrometry and elemental analyses confirmed the molecular formulae.

Thermal reaction of phthalonitrile with hafnium powder under iodine monobromide (IBr) yields a new type molecule: bis(hafnium(IV) stapled phthalocyanine) derivative complex. X-ray single crystal analysis shows that the complex molecule consists of two hafnium phthalocyanine units bridged by the unique internal ligand that stapled by two carbon–carbon [Formula: see text] bonds to both HfPc-units. The internal dianionic ligand consists of two fragments, each of them present the three fourth part of phthalocyaninate ring. Both fragments are linked together through the bridging 1,2-di[amine(imine)methyl]benzene. The X-ray conformation of the bis(hafnium(IV) stapled phthalocyanine) derivative complex cation is confirmed by DFT calculations. An absence of the Q-band in the UV-vis spectrum, the typical band for the fully delocalized [Formula: see text]-electron aromatic phthalocyaninato(2-) ring system, indicates on drastic modification of the chromophore in this Hf-phthalocyanine complex that was confirmed by TD DFT calculations.

Nanoparticles of two zinc(II) coordination polymers (CPs), [Zn(μ-4,4'-bipy)Cl2]n (1) and [Zn(μ-4,4'-bipy)Br2]n (2) L=bpy=4,4'-bipyridine ligand, have been synthesized by use of a sonochemical process and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), Fourier transform infrared spectroscopy (FTIR) spectroscopy and elemental analyses. The single crystal X-ray data of compounds 1 and 2 imply that the Zn+2 ions are four coordinated. Topological analysis shows that 1D coordination networks of 1 and 2 can be classified as underlying nets of topological types 2C1. Nanoparticles of zinc(II) oxide have been prepared by calcination of two different zinc (II) CPs at 450°C that were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and IR spectroscopy.

The importance of rare earth elements in high-tech materials has promoted the necessity to develop new materials for sensing and separating them. Luminescent metal-organic frameworks (MOFs) due to their promising applications as functional materials for chemical sensing and separation, which upon introducing analytes create multi-responsive systems, have been receiving great attention by scientists. In this regard, we have designed and synthesized a novel three-dimensional copper framework, [Cu2(3,4-pydc)2(H2O)5]n.2nH2O (1; 3,4-H2pydc = 3,4-pyridine dicarboxylic acid), in ambient condition with an interesting topology and potential application as a cation exchange material. Upon Tb3+ ions uptake, compound 1 exhibited the antenna effect to sensitize Tb3+ ions and its fluorescent emission was enhanced. It also showed selective sensing ability based on turn-on fluorescence response towards Tb3+ ions, in a mixture of main and transition metal ions and Tb3+ ions. Furthermore, the results showed that the Tb3+ ion exchange process is reversible. Therefore, compound 1 is a promising multifunctional luminescent MOF for simultaneous sensing and chemical separation of Tb3+ ions which is an advantage over the previously used MOFs in this regard. Furthermore, the reusability experiment demonstrated that 1 can be utilized for long-term detection and separation of Tb3+ ions.

As a group of biologically active compounds, polyether antibiotics (ionophores) show a broad spectrum of interesting pharmacological properties, ranging from anti-bacterial to anti-cancer activities. There is increasing evidence that ionophores, including salinomycin (SAL), and their semi-synthetic analogues are promising candidates for the development of drugs against parasitic diseases. Our previous studies have shown that esterification and amidation of the C1 carboxylate moiety of SAL provides compounds with potent activity against Trypanosoma brucei, protozoan parasites responsible for African trypanosomiasis. In this paper, we present the synthetic pathways, crystal structures and anti-trypanosomal activity of C1 esters, amides and hydroxamic acid conjugates of SAL, its C20-oxo and propargylamine analogues as well novel C1/C20 doubly modified derivatives. Evaluation of the trypanocidal and cytotoxic activity using bloodstream forms of Trypanosoma brucei and human myeloid HL-60 cells revealed that the single-modified C20-oxo and propargylamine precursor molecules 10 and 16 were the most anti-trypanosomal and selective compounds with 50% growth inhibition (GI50) values of 0.037 and 0.0035 µM, and selectivity indices of 252 and 300, respectively. Also the salicylhydroxamic acid conjugate of SAL (compound 9) as well as benzhydroxamic acid and salicylhydroxamic acid conjugates of 10 (compounds 11 and 12) showed promising trypanocidal activities with GI50 values between 0.032 to 0.035 µM but less favorable selectivities. The findings confirm that modification of SAL can result in derivatives with improved trypanocidal activity that might be interesting lead compounds for further anti-trypanosomal drug development.

Kynurenic acid (KYN; systematic name: 4-hydroxyquinoline-2-carboxylic acid, C10H7NO3) displays a therapeutic effect in the treatment of some neurological diseases and is used as a broad-spectrum neuroprotective agent. However, it is understudied with respect to its solid-state chemistry and only one crystal form (α-KYN·H2O) has been reported up to now. Therefore, an attempt to synthesize alternative solid-state forms of KYN was undertaken and six new species were obtained: five solvates and one salt. One of them is a new polymorph, β-KYN·H2O, of the already known KYN monohydrate. All crystal species were further studied by single-crystal and powder X-ray diffraction, thermal and spectroscopic methods. In addition to the above methods, differential scanning calorimetry (DSC), in-situ variable-temperature powder X-ray diffraction and Raman microscopy were applied to characterize the phase behaviour of the new forms. All the compounds display a zwitterionic form of KYN and two different enol–keto tautomers are observed depending on the crystallization solvent used.

Lanthanide-based metal-organic frameworks (MOFs) and coordination polymers (CPs) attract much attention as candidates for optical ratiometric thermometry applications. Thus far, excitation of these materials was mainly performed in the ultraviolet that drastically limits their applicability as sensors, e.g., in tissue biological thermometry. As a remedy for this constraint, for the first time, we leverage a nonlinear optical process, the three-photon absorption property of Eu,Tb-CPs to shift the excitation wavelength from ultraviolet into near-infrared region. Experiments demonstrate that three-photon induced thermometric responses of Eu,Tb-CPs follow excellent optical characteristics similar to those determined for one-photon excitation, yet are not identical. The relative sensitivity reaches a very high value of 2.91%K-1 in the physiological temperature region. We put forward a notion that utilizing multiphoton absorption is a general strategy for realizing NIR-to-VIS remote temperature sensing in practically any CP that is designed for UV-to-VIS thermometry.

The single crystals of 1-(diaminomethylene)thiouron-1-ium 4-aminobenzoate, (C2H7N4S)-(NH2C6H4COO), (1) suitable for the X-ray analysis were grown using a solution growth technique room temperature. Recrystallization of 1 in heavy water (three-times) yield respective deuterated analogue, (C2D7N4S)(ND2C6H4COO), (1d). The X-ray single crystals analyses show that both, protiated and deuterated, compounds crystallize in the same crystal system with quite similar lattice parameters. The conformation of the 1-(diaminomethylene)thiouron-1-ium cation is not strictly planar, but slightly twisted. The 4-aminobenzoate(-) anion is also non-planar. The planar COO− group is inclined to the plane of aromatic ring by 5.2(2)o. In the crystal the oppositely charged units, i.e. 1-(diaminomethylene)thiouron-1-ium cation and 4-aminobenzoate anion interact via two of almost linear N H…O hydrogen bonds with a graph of R22(8), that are further interact each other forming three dimensional hydrogen-bonded network. Hirshfeld surface and the analysis of 2D fingerprint plots are illustrating both quantitatively and qualitatively interactions governing the supramolecular assemblies. The compound was also characterised by the FT-IR and Raman spectroscopy. The vibrational assignments have been supported by the isotopic frequency shift as well as by the DFT calculations.

New europium and terbium [LnCl3L3(H2O)2] polycrystalline complexes were synthesized with the ligand L = 3-bromo-4-methylthio-2,6-lutidine N-oxide. IR, Raman, electron absorption UV-VIS and emission spectra measurements were carried out for these compounds. Re-crystallization of these materials led to formation of single crystals with another composition [LnL(H2O)7]Cl3∙L3, they were characterized by X-ray diffraction technique and spectroscopic measurements. Both types of the materials consist of eight coordinated LnCl3O3O’2 or LnOO’7 polyhedrons containing O - oxygen atoms of the N-oxide group, chlorine atoms or O’ - oxygen atoms of the water units. The crystal structure was solved for two complexes of the formula [Ln(L)(H2O)7]Cl3∙(L)3 where Ln = Eu and Tb. X-ray diffraction analysis reveals that these complexes are isostructural with P21/m space group. The optimization of the molecular system and frequency calculations were carried out using density functional theory (DFT). The DFT quantum chemical calculations of the vibrational wavenumbers were performed for the ligands used for the Eu3+ and Tb3+ ions complexation. The emission measurements were carried out with the femtosecond excitation. The effective ligand-to-metal energy transfer was discovered in the [LnCl3L3(H2O)2] complexes formed in the polycrystalline state.

Nano-structures of two mononuclear Zn(II) complexes, [ZnL2Br2] (1) and [ZnL6].2(I) (2) L = 1-methyl imidazole ligand, were synthesized using a sonochemical method and characterized by infrared spectroscopy (IR), UV-Visible, X-Ray powder diffraction (XRPD), scanning electron microscopy (SEM) and elemental analyses. The single-crystal X-ray (SCXA) data of compounds 1 and 2 exhibited different coordination environment of the Zn2+ ions: distorted tetrahedral in 1 and distorted octahedral in 2. The topological analysis showed that compounds 1 and 2 present novel topology for net: 1.4M5–1 and 1.6M7–1, respectively. The thermal stability of compounds 1 and 2 was investigated through differential scanning calorimetry analyses (DSC) and thermal gravimetric analyses (TGA). Nanostructures of zinc(II) oxide was obtained by simultaneous calcination various zinc(II) complexes at 500 °C and, then, were characterized by IR, SEM and XRD. Moreover, the in vitro antibacterial activities of zinc(II) complexes was investigated against gram-positive (S. aureus) and gram-negative (E. coli) bacteria. The results exhibited appropriate antibacterial activities. MTT assay was used for cytotoxicity of the crystals and nanostructures of compounds 1 and 2.

Colchicine shows very high antimitotic activity, therefore, it is used as a lead compound for generation of new anticancer agents. In the hope of developing novel, useful drugs with more favourable pharmacological profiles, a series of doubly modified colchicine derivatives has been designed, synthesized and characterized. These novel carbamate or thiocarbamate derivatives of 10-demethoxy-10-methylaminocolchicine have been tested for their antiproliferative activity against four human cancer cell lines. Additionally, their mode of action has been evaluated as colchicine binding site inhibitors, using molecular docking studies. Most of the tested compounds showed greater cytotoxicity (IC50 in a low nanomolar range) and were characterized by a higher selectivity index than standard chemotherapeutics such as cisplatin and doxorubicin as well as unmodified colchicine. Their pharmacological use in cancer therapy could possibly be accomplished with lower dosages and result in less acute toxicity problems than in the case of colchicine. In addition, we present a QSAR model for predicting the antiproliferative activity of doubly modified derivatives for two tumour cell lines.

A step-by-step synthesis based on the application of monoprotected 2.6-diformylpyridine intermediate resulted in the formation of enantiopure Eu(III), Yb(III) and Y(III) complexes of unsymmetrical macrocycles L3 and L4 containing two pyridine units and two different diamine and diimine links. The final step in the formation of these mixed amine-imine hexaazamacrocycles was based on a templated condensation of ethylenediamine or enantiopure trans-1,2-diaminocyclohexane with a linear [2 + 1] amine intermediate bearing two pyridinecarboxaldehyde fragments. The identity of these unsymmetrical complexes have been determined on the basis of 2D NMR and ESI MS spectroscopy and confirmed by the X-ray crystal structures of Eu(III) and Yb(III) complexes of macrocycle L3. In these complexes the macrocyclic ligand adopts twist-fold conformation and the twist of the achiral ethylene link is dictated by the conformation of the cyclohexane link. The ten-coordinate Ln(III) ions are bound in equatorial positions by the six nitrogen atoms of the macrocycle and their coordination spheres are completed by two axial bidentate nitrate anions. The luminescent properties of the Eu(III) complexes of L3 and L4 have been characterized.