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A novel inorganic complex formulated as [Co(dipic)(2,2´-bipyridine) (H2O)]3 × 10H2O, where dipic2− = pyridine-2,6-dicarboxylato has been synthesized via a facile sonochemical process. Molecular structure of inorganic complex was characterized by several methods. The results of single crystal X-ray diffraction (SCXRD) revealed that the complex crystallizes in space group Pī of a triclinic system. The sorbent of Co3O4/SiO2 was prepared by thermal treatment of the silica supported complex at 500 °C. For comparative purposes, the sorbent of Co3O4/SiO2 was prepared by solvothermal and impregnation methods. After characterization, the catalytic performance of the sorbents was comparatively studied for the removal of methylene blue (MB) from contaminated water source. The sorbent which prepared through thermal decomposition of inorganic complex showed improved ability in the removal of methylene blue due to the physicochemical properties, such as higher surface area, smaller particle size, and lower agglomeration.

A series of zinc(II) phthalocyanine complexes peripherally octa-substituted by methyl groups and with axially ligated N-donor ligands, (Zn(Me)8Pc-L, where L is pyridine (4), 3-methylpyridine (5), 3,4-lutidine (6) and 3,5-lutidine (7)), was synthesized. All the Zn(Me)8Pc-L complexes 4–7 were obtained in the crystalline form, suitable for X-ray single crystal analysis. The effect of the peripheral substituents as well as the ligation effect of the axial ligands on the structure were analyzed. In all the here studied zinc(II) phthalocyanine derivatives, the interaction of the metal center with the N atom of the axial ligand results in its displacement by ~ 0.4 A from the N4-isoindole plane of phthalocyaninate macrocycle that adopts a saucer-shaped form. The X-ray geometry and stereochemistry of the zinc(II) phthalocyanine derivatives were compared with that obtained by DFT methods. Analysis of the Hirshfeld's surface shows a reduction of the π···π interactions with the simultaneous increase of the C H···N, C H···N, H···H and C H··· π interactions in the investigated complexes 4–7. Partial MO energy diagrams and the calculated absorption spectra of the Zn(Me)8Pc-L derivatives 4–7 exhibit a bathochromic shift of the maximum absorption wavelength (λmax) in comparison with the spectrum of Zn(Me)8Pc by about 20 nm. Complexes 4–7 have a strong absorption band in the therapeutic window (600–900 nm) and the HOMO-LUMO energy gap is sufficient to excite the ground state of oxygen and therefore they can be tested as potential photosensitizers for PDT.

While metal–organic frameworks (MOFs) or, more generally, coordination polymers (CPs) built using linkers possessing two different functional groups are known very well in the literature, the effect of a third functional group on the physicochemical properties of those materials is weakly recognized. To study this issue we designed an aminocarboxyphosphonic ligand, 3-amino-5-(dihydroxyphosphoryl)benzoic acid (H3APB), which is an amino derivative of meta-phosphonobenzoic acid. By self-assembly with a copper(II) source, we obtained the three-dimensional CP {[Cu3(APB)2(H2O)6]·6H2O}n, 1, featuring rare binodal 4,5-connected tcs topology. By comparison with previously known representatives of that topology, we put forward a hypothesis that CPs of rare topologies, such as tcs, are obtained when polytopic, differentially substituted ligands are used. The structure of 1 is layered, but not in the manner typical for “traditional” metal phosphonates and carboxyphosphonates, and it was found to be flexible; structur...

For the first time, the crystalline complex of salinomycin with benzylamine was obtained and its molecular structure was studied using single crystal X-ray diffraction, FT-IR, 1 H NMR, 13 C NMR, 2D NMR and ESI MS methods. These studies provided evidence that the proton from the carboxylic group of salinomycin ( SAL ) is transferred to the amine group of benzylamine ( BnA ) forming the host-guest complex ( SAL-BnA ). It was shown that the SAL-BnA complex both in solid state and in chloroform solution is stabilized by the intramolecular O—H⋯O hydrogen bonds and also by the intermolecular hydrogen bonding interactions of the carboxylate, ketone and/or hydroxyl groups of SAL with water molecules present in the investigated system. The solvated acetonitrile molecules are additionally located in the voids between the SAL-BnA complex molecules in the crystal structure, while water molecules involved in the dihydrated crystalline SAL-BnA complex partially move into the solvent upon dissolution in chloroform.

The reaction of a phosphonate-diester tetraphenylmethane-based tecton, tetrakis[4-(diethoxyphosphoryl)phenyl]methane, (L) with cobalt(II) chloride afforded a centrosymmetric coordination polymer (CP), [L·2Co(H2O)42+·2CoCl42−]n, 2-Cl, possessing simultaneously octahedral (Oh) and tetrahedral (Td) metal centers. This material served as a model compound for the demonstration of factors influencing the spectral dependence of one of the nonlinear optical (NLO) phenomena, the third-harmonic generation (THG). The spectrally-resolved THG (SR-THG) measurements in the range from 1125 to 1750 nm revealed that a maximum of THG response is obtained when the fundamental beam is around 1300 nm. The SR-THG study was combined with an analysis of the self-absorption effects of pumping and of third-harmonic radiation; based on these results, we put forward a hypothesis that the THG action spectrum is influenced more by the ability of the material to self-absorb the third harmonic rather than by the extent of self-absorption of the pumping radiation. Apart from investigations of NLO properties, we have explored coordination and particularly the supramolecular interactions that build up the 2-Cl CP. Despite the tetrahedral, spatial shape of the ligand L, CP 2-Cl has a two-dimensional net. The structure was found to be strongly supported by O–H⋯Cl hydrogen bonds, since each CoCl42− complex anion is an acceptor of eight of such interactions within a distorted square grid layer of cobalt(II) ions. While coordination and hydrogen-bonded nets are both featuring the sql topology when treated separately, the consideration of both of them as topological paths yields a trinodal 4,4,6-connected net, described by the point symbol (42·84)(45·6)2(46·66·83)2. SR-THG and structural studies of 2-Cl have been also supported by far- and mid-infrared spectroscopy, UV-Vis-NIR solid state absorption analysis, thermogravimetry and preliminary magnetic characterization.

A family of supramolecular complexes of melamine with chlorophenylacetic acid isomers using solvent-assisted and evaporation-based techniques has been prepared. Crystallization of melamine with 2-chlorophenylacetic acid yield hydrated ionic supramolecular complex (1), whereas crystallization of melamine with 3- and 4-chlorophenylacetic acids leads to formation of neutral supramolecular complexes (2, 3), all with base to acid ratio of 1:2. Within chlorophenylacetic acid isomers only in 2-chlorophenylacetic acid isomer as the stronger acid the proton transfer to melamine takes place. The crystal structures of supramolecular complexes have been determined. The supramolecular assembly is driven by the noncovalent interactions, most commonly by the hydrogen bonds. The components of the crystals interact via N H⋯O and O H⋯N with a graph of R22(8) forming respective ionic or neutral supramolecular complexes. All three supramolecular complexes studied interact each other via a pair of N H⋯O hydrogen bonds forming pseudo one-dimensional supramolecular chains along [1–10] and [−110] in 1 and along [010] in 2 and 3. Hirshfeld surface and analysis of 2D fingerprint plots have been analysed both quantitatively and qualitatively interactions 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.

A three-dimensional coordination polymer, {(Mo2O6)(4,4′-bpy)}n (1) (4,4′-bpy=4,4′-bipyridine), was synthesized under solvothermal conditions and characterized by single crystal X-ray diffraction analysis, powder X-ray diffraction (XRD), Fourier transformation infrared (FT-IR) spectroscopy and thermogravimetric analysis (TGA). The coordination polymer was also prepared in nanoscale via an ultrasound-assisted top-down process. The nanosized coordination polymer was characterized by means of scanning electron microscopy (SEM), XRD and FT-IR spectroscopy. The prepared oxomolybdate-based coordination polymer, in bulk and nanoscale, was applied as heterogeneous catalyst for the epoxidation of some olefins using tert-butyl hydroperoxide (TBHP) as oxidant. The 3-D coordination polymer, particularly in nanoscale, demonstrated good activity and stability in the epoxidation reaction and could be easily recovered and reused in the reaction.

Reactivity of magnesium phthalocyanine (MgPc) in the dry 3,5-lutidine (3,5-lut), in the 3,5-lut/DMSO and in 3,5-lut/acetylacetone (acacH) systems has been investigated. Reaction of MgPc with dry 3,5-lut leads to formation of MgPc(3,5-lut)2 compound (1), in which the Mg atom is characterized by rarely encountering in magnesium phthalocyanines 4+2 type of coordination. Depending on the thermal conditions and the 3,5-lut quantity in the system the solvothermal reaction of MgPc with 3,5-lut/DMSO system leads to formation of three crystalline complexes: MgPc(H2O)·(3,5-lut) (2), MgPc(H2O)·2(3,5-lut) (3) and 2[MgPc(H2O)]·7(3,5-lut) (4). The presence of water in the crystalline complexes is governed by a high affinity of MgPc to water. 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 3,5-lut/acacH system leads to formation of crystalline Mg(acac)2(3,5-lut)2 compound (5). The structure of all complexes has been determined by X-ray single crystal diffraction. All compounds were also characterized by thermogravimetric analysis and the compounds 1–4 were also characterized by UV–Vis spectroscopy in solution, whereas compound 5 was characterized by vibrational spectroscopy (IR and Raman).

Discovery of E/Z or trans–cis photoisomerization in the azobenzenes and their derivatives had tremendous impact on the whole domain of photochromic materials including photochromic polymers and liquid crystals. Here we show similar configurational photoinduced transformation in a simple derivative of pyrazoline. The X-ray crystallographic investigations of (E)-3-(4-nitrostyryl)-1-phenyl-4,5-dihydro-1H-pyrazole (abbreviated as PY-pNO2) in grown crystals show two different structures comprising of either cis or trans molecules. The performed quantum chemical calculations confirm the existence of both configurations of PY-pNO2 at the room temperature. Photophysical properties of this compound derived from quantum chemical calculations predict possibility of trans to cis switching of PY-pNO2 by light. Indeed, molecules of PY-pNO2 embedded in PMMA polymeric matrix when illuminated with 532 nm linearly polarized laser light show the induced optical anisotropy, i.e., birefringence characteristic for photoisomeri...

Three complexes of zinc phthalocyanine (ZnPc) monoaxially ligated by imidazole, N-methylimidazole and N-(2-pyrimidinyl)imidazole were obtained in crystalline forms. Complexes containing imidazole and N-methylimidazole crystallise in the centrosymmetric space group of the triclinic system, while with the N-(2-pyrimidinyl)imidazole complex crystallises in P21/n space group of monoclinic system. Interaction of the electropositive polarised Zn centre of a planar ZnPc with nucleophilic ring nitrogen atom of imidazole derivatives leads to deviation of Zn form the N4-plane of phthalocyaninato(2-) macrocycle by ∼0.45 A. Steric hindrance of the axial ligands of ZnPc-L complexes modify the π∙∙∙π interactions between the Pc(2-) macrocycles when compared to that of the parent ZnPc pigment. The calculated three-dimensional MESP maps are helpful for understanding of the interaction between the ZnPc and imidazole derivatives forming the monoaxially ligated complexes. Theoretical calculations of axial bonds energies and UV–Vis spectroscopic measurements in solutions also were performed.

Different salts of 5-sulfoisophthalic acid with aminosubstituted monocyclic Lewis bases, 2-aminipyridine, 3-aminopyridine, 4-aminopyridine, 2,6-diaminopyridine, have been prepared and studied by means of X-ray crystallography, Fourier transform infrared and Raman spectroscopy, and thermogravimetric–differential thermal analysis and differental scanning calorimetry methods. The crystal networks have been analyzed in view of competitive hydrogen bond interactions issued between multiple functional groups in different topological and stoichiomeric combinations allowing for formation of variable synthons. A statistical analysis of the most prominent homo- and heteromeric motifs, which can be formed between the functional groups, has been performed with the use of the Mercury Solid Form module in order to look for preferred interactions in extended network formation. Eighteen different synthons are used in the presented crystal networks, some of which are really prolific and others are unique. The role of wate...

A new one-dimensional (1D) coordination polymer, [Zn(4,4′-bpy)(H2O)4](ADC)·4H2O (1) (4,4′-bpy=4,4′-bipyridine and H2ADC=acetylenedicarboxylic acid), was synthesized at room temperature. The crystal structure of the coordination polymer was determined by single-crystal X-ray diffraction analysis. Compound 1 was also characterized by FT-IR, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). The catalytic activity of 1 was evaluated in the color removal of Bismarck brown as a representative of dye pollutant in water under mild conditions. Coordination polymer 1 exhibited good catalytic activity and stability in the decolorization of Bismarck brown and could be easily recovered and reused for at least three cycles.

New chemical compounds have been synthesized and their physicochemical properties have been characterized. N’-[2,4-dihydroxyphenyl) methylidene]-4-(4-fluorophenyl) piperazine-1-carbothiohydrazide, a novel semicarbazone has been obtained in the three stages of intermediate process and by the final crystallization from the methanol solution. The final and intermediate products have been studied using 1H, 13C NMR and MS spectroscopic techniques. The semicarbazone was applied as a ligand for the Tb3+ ion complexation and the obtained terbium compound has been characterized by elemental chemical analysis as well as by the IR, Raman, and electron absorption and emission techniques. Its molecular structure has been proposed. The probability of the ligand-to-metal energy transfer has been discussed.

Novel arylpiperazine-1,2-benzothiazine derivatives have been designed and synthesized as potential anti-inflammatory agents. Their structure and properties have been studied using spectroscopic techniques (1H NMR, 13C NMR, FT-IR), MS, elemental analyses, and single-crystal X-ray diffraction (SCXRD, for compound 7b). This study aimed to evaluate the inhibitory activity of new derivatives against both cyclooxygenase isoforms COX-1 and COX-2 due to the similarity of new compounds to oxicams drugs from the NSAIDs group. All new compounds were divided into two series – A and B – with a different linker between thiazine and piperazines nitrogens. Series A included the three-carbon aliphatic linker and series B – two-carbon with a carbonyl group. According to in vitro and molecular docking studies all new compounds exhibited cyclooxygenase inhibitory activity. The series of A compounds included COX-1 inhibitors only. In contrast, the B series showed inhibition of both COX-1 and COX-2, which suggested the importance of the acetoxy linker for COX-2 inhibition. Moreover, the most selective compound 7b, towards COX-2, was non-toxic for the normal human cell line (in concentration of 10 µM) comparable to reference drug meloxicam. Additionally, investigation of influence on model membranes confirmed the ability of the compound 7b to penetrate lipid bilayers which seemed to be important to the influence with membrane protein-cyclooxygenase.

New 1D coordination polymer (CP); namely, [Cd(L)(N3)2]n (1) [L = 2-Picolylamine], was synthesized using branch tube method. Using sonochemical method led to the achievement of nano and micro structures of 1. These structures have been characterized by FT-IR spectroscopy, elemental analysis, powder X-Ray diffraction (P-XRD) and scanning electron microscopy (SEM). Crystal structure of (1) was characterized via the single-crystal X-ray diffraction technique. In the crystal structure of 1, the cadmium atoms are coordinated by six nitrogen atoms in a distorted octahedral geometry. The effects of different reaction times and solvent on morphology of structures was studied, and the results showed that formation of micro structures is dependent on reaction time and type of solvent.

A dimeric tungstophosphate, Na14[Co4(PW9O35)2].28H2O (1), was synthesized via a simple one-pot method and characterized by single-crystal X-ray crystallography. Nanocluster 1 was exhibited to be able to selective oxidation of aliphatic and aromatic sulfides to sulfoxides in the presence of hydrogen peroxide at room temperature with high performance. Further investigations showed that this catalyst could reuse four times without a significant reduction in its activity for the oxidation of methyl phenyl sulfide.

Two new Cu(II) and Ni(II) complexes of a tetradentate N2O2 Schiff base ligand (H2L = N,N'-bis-(4-hydroxysalicylidene)-ethylenediamine) were synthesized. The structures of the H2L ligand and its complexes (1 and 2) were unambiguously determined by elemental analysis, FT-IR, 1H NMR, and UV–Vis spectroscopy. The crystal structures of the complexes were also determined by X-ray crystallography technique. In addition, the complexes were tested as a modifier for a glassy carbon electrode (GCE) to prepare an electrochemical sensor for detection of hydrazine in real samples. The prepared sensor with Ni(II) complex showed admirable sensitivity and selectivity for determination of hydrazine at 0.55 V without any interference of other common substrates. A dynamic linear range of 0.5–150 µM with a detection limit (LOD) of 166.66 nM and sensitivity of 0.1174 μA µM−1 cm−2 was achieved. The obtained LOD was much lower than that specified in the U.S. Environmental Protection Agency (EPA) regulations. The prepared sensor was also successfully applied to detect hydrazine in Tehran’s Jajrood river water as a real sample.

Crystallization of melamine with phenylacetic acid from water solution yields melamin-1-ium phenylacetate phenylacetic acid monohydrate supramolecular complex (1). The compound crystallises in the centrosymmetric space group of the triclinic system. In the crystals, beside the ionic interaction, the protonated melamin-1-ium cation (MH+) interacts with phenylacetate anion via two N–H⋯O hydrogen bonds with a graph of R22(8) forming supramolecular {MH…phenylacetate} complex that further interacts with neutral acid molecule by a combination of O–H⋯N and N–H⋯O hydrogen bonds with a graph of R32(10) and then with water molecule via N–H⋯O hydrogen bond forming supramolecular complex of 1. The supramolecular assembly of melamin-1-ium phenylacetate phenylacetic acid monohydrate units is driven by the noncovalent interactions with neighbours via N–H⋯N, N–H⋯O and O–H⋯O with a graph of R22(8), R32(8) and R43(10) into hydrogen-bonded tapes. The tapes are further organised into stacks. Hirshfeld surface and the analysis of the 2D-fingerprint plots are illustrating both qualitatively and quantitatively interactions governing the formation of the supramolecular architecture. The compound was also characterized by the FT-IR and Raman spectroscopy. Assignment of the bands have been supported by the isotropic frequency shift.

Mononuclear Zinc (II) compound –based nano-structure with [Zn(L)2(CH3COO)2] {as compound 1} formulation was synthesized by reacting ligand 2-Amino-3-Methyl pyridine with Zinc (II) acetate dihydrate and potassium iodide via sonochemical method and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), infrared spectroscopy (IR) and elemental analyses. Single crystal X-ray diffraction was used to determine the structure of compound 1. The Zn(II) cation has a distorted tetrahedral environment composed of two nitrogen atoms from two 2-amino-3-methyl pyridine ligands and two oxygen atoms from two acetate groups. The topological analysis demonstrated that the topology of compound 1 was 1,2,3,4,4M12–1. The Hirshfeld Surface Analysis (HSA) of the crystal packing of compound 1 was discussed in detail to evaluate the interactions among the crystal packing. Thermal stability of the crystal and nano-structures of compound 1 was investigated using thermal gravimetric analyses (TGA) and differential scanning calorimetry (DSC). Calcination of nano-structures of compound 1 at 550 °C produced zinc(II) oxide, which was subsequently characterized using scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and IR spectroscopy. Two strains of gram-negative bacteria (Escherichia coli) and gram-positive bacteria (Staphylococcus aureus) were cultured in the presence of nano-structures of compound 1 to assess their biological activities. This compound displayed sufficient antibacterial activity in an abiotic environment. Cytotoxicity assays of the crystal and nano-structure of compound 1 were performed on L929 human cells. These compounds showed no toxic effect.

Two nickel(II) complexes with substituted bipyridine ligand of the type [Ni(NN)3](ClO4)2, where NN is 4,4′-dimethyl-2,2′-bipyridine (dimethylbpy) (1) and 4,4′-dimethoxy-2,2′-bipyridine (dimethoxybpy) (2), have been synthesized, characterized, and their interaction with DNA and bovine serum albumin (BSA) studied by different physical methods. X-ray crystal structure of 1 shows a six-coordinate complex in a distorted octahedral geometry. DNA-binding studies of 1 and 2 reveal that both complexes sit in DNA groove and then interact with neighboring nucleotides differently; 2 undergoes a partial intercalation. This is supported by molecular-docking studies, where hydrophobic interactions are apparent between 1 and DNA as compared to hydrogen bonding, hydrophobic, and π–π interactions between 2 and DNA minor groove. Moreover, the two complexes exhibit oxidative cleavage of supercoiled plasmid DNA in the presence of hydrogen peroxide as an activator in the order of 1 > 2. In terms of interaction with BSA, the results of spectroscopic methods and molecular docking show that 1 binds with BSA only via hydrophobic contacts while 2 interacts through hydrophobic and hydrogen bonding. It has been extensively demonstrated that the nature of the methyl- and methoxy-groups in ligands is a strong determinant of the bioactivity of nickel(II) complexes. This may justify the above differences in biomolecular interactions. In addition, the in vitro cytotoxicity of the complexes on human carcinoma cells lines (MCF-7, HT-29, and U-87) has been examined by MTT assay. According to our observations, 1 and 2 display cytotoxicity activity against selected cell lines. Communicated by Ramaswamy H. Sarma

At one extreme of the proton-transfer spectrum in cocrystals, proton transfer is absent, whilst at the opposite extreme, in salts, the proton-transfer process is complete. However, for acid–base pairs with a small ΔpK a (pK a of base − pK a of acid), prediction of the extent of proton transfer is not possible as there is a continuum between the salt and cocrystal ends. In this context, we attempt to illustrate that in these systems, in addition to ΔpK a, the crystalline environment could change the extent of proton transfer. To this end, two compounds of salicylic acid (SaH) and adenine (Ad) have been prepared. Despite the same small ΔpK a value (≈1.2), different ionization states are found. Both crystals, namely adeninium salicylate monohydrate, C5H6N5 +·C7H5O3 −·H2O, I, and adeninium salicylate–adenine–salicylic acid–water (1/2/1/2), C5H6N5 +·C7H5O3 −·2C5H5N5·C7H6O3·2H2O, II, have been characterized by single-crystal X-ray diffraction, IR spectroscopy and elemental analysis (C, H and N) techniques. In addition, the intermolecular hydrogen-bonding interactions of compounds I and II have been investigated and quantified in detail on the basis of Hirshfeld surface analysis and fingerprint plots. Throughout the study, we use crystal engineering, which is based on modifications of the intermolecular interactions, thus offering a more comprehensive screening of the salt–cocrystal continuum in comparison with pure pK a analysis.

Polyoxovanadate, (NH4)2[Zn(H2O)6]2[V10O28]∙4H2O was synthesized and characterized by the single crystal X-ray analysis. (NH4)2[Zn(H2O)6]2[V10O28]∙4H2O was found to be an efficient catalyst for one-pot synthesis of propargylamines by three component (A3) coupling of aldehydes, amines and alkynes without any co-catalyst or activator under solvent-free condition. In the presence of this catalytic system both aromatic and aliphatic aldehydes and alkynes could react and so produce the corresponding propargylamines in good to excellent yields.

The coordination properties of diethylenetriamine (DETA) as a ligand containing three donor nitrogen atoms, two terminal primary amino groups and one secondary central amino group, with respect to divalent zinc ion in ZnPc were examined. The ZnPcDETA complex in the powder form was obtained by the solvothermal reaction of ZnPc with DETA. Recrystallization of the crude product from 3,4-lutidine yields non-centrosymmetric monoclinic solvated crystals (ZnPcDETA)3.3,4-lut (1) with the space group of Cc. As show the X-ray single crystal analysis in ZnPcDETA complex, the DETA coordinates via terminal amine group to the divalent zinc ion of a planar ZnPc molecule in axial position. Interaction of the N atom of DETA containing a lone electron pair with divalent zinc ion of ZnPc and the formation of the Zn-N coordination bond leads to deviation of the Zn from the N4-isoindole plane of Pc by ∼0.5 A toward the N-atom of the axial DETA ligand as well as to saucer-shaped distortion of the Pc macrocycle. Arrangement of ZnPcDETA molecules in the 3,4-lutidine solvate crystal with the composition of (ZnPcDETA)3.(3,4-lutidine) - (1) is determined by the van der Waals forces and by the weak N-H…N hydrogen bonds. The lack of the π… π interaction between the phthalocyaninate(2-) macrocycles in the crystals (1) is clearly evidenced by the Hirshfeld surface analysis, and increases significantly their solubility in most common solvents, even in water, when comparing to the parent ZnPc pigment with limited solubility in solvents and insoluble in water. This feature together with the strong absorption in the therapeutic window within the 600-900 nm makes it a potentially good photosensitizer. DFT calculations performed for the ZnPc-derivatives with DETA, coordinated via terminal or central amine group of DETA as well as for the bridged complex (through the terminal amino groups of the DETA ligand of two ZnPc molecules) show the possibility to obtain all three of these complexes. UV-Vis absorption spectra ZnPcDETA complex (1) in solutions as well as the diffuse reflectance spectroscopy (DSR) supported by the TD-DFT calculations were used for the characterization of the spectroscopic properties. SHG efficiency of 1 is ∼10 % in relation to that of KDP.

Two single crystals of 1-(diaminomethylene) thiouron-1-ium benzoate ( 1 ) and bis(1-(diaminomethylene)thiouron-1-ium) phthalate trihydrate ( 2 ) were grown using a solution growth technique. The compound 1 crystallises in the centrosymmetric P 2 1 /c space group of the monoclinic system, whereas the compound 2 in the centrosymmetric Pbcn space group of orthorhombic system. The solid-state organisation of 1 and 2 has been analysed with respect to cation-anion and hydrogen bonding interactions. The oppositely charged units interact via almost linear hydrogen bonds with the graphs of R 2 2 (8) and R 2 1 (6) forming molecular complexes. In the crystal 1 the R 2 2 (8) motif is formed by donation to the carboxylate group from amine group joined to C1 and from imine group and R 2 1 (6) motif is formed by donation to the O2 from amine group joined to C2 and from imine group, whereas in crystal 2 the graphs are formed oppositely. Interactions between the hydrogen-bonded molecular complexes in 1 lead to formation of layered 2D structure, whereas in 2 , due to presence of hydrated water molecules lead to formation of 3D hydrogen-bonded supramolecular network. The obtained deuterated analogues of 1 and 2 crystallise similar as H-compound in the monoclinic and orthorhombic system with quite similar lattice parameters. The compounds were also characterised by the FT-IR and Raman spectroscopies. The characteristic bands of the functional and skeletal groups are discussed.

A one-dimensional coordination polymer, {(NH4)4Mo8O26}n (1), was synthesized based on polyoxomolybdate nanoclusters under hydrothermal conditions. The crystal structure of the hybrid was determined by single crystal X-ray diffraction analysis. The 1-D coordination polymer 1 was also characterized by FT-IR, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and inductive coupled plasma optical emission spectroscopy (ICP-OES). The catalytic properties of the prepared compound were evaluated in the epoxidation of some olefins using tert-butyl hydroperoxide (TBHP) or H2O2 as the oxidant. The 1-D polyoxomolybdate polymer exhibited good activity and stability in the catalytic epoxidation of olefins.

The luminescence properties of two series of heteronuclear lanthanide-based coordination polymers were studied. The heteronuclear compounds were synthesized via mechanosynthesis routes. These series have the general chemical formula [Ln1−xLn′x(pzdc)(Hpzdc)(H2O)3]n (Ln = La3+ or Ce3+, Ln′ = Sm3+, Eu3+, Tb3+, or Dy3+, x = 0.050, 0.075 or 0.100) where H2pzdc stands for 2,3-pyrazinedicarboxylic acid (Hpzdc− = mono-deprotonated and pzdc2− = bis-deprotonated). The heteronuclear compounds that belong to each series are isostructural to a new two-dimensional La(III) coordination polymer and to an already reported homonuclear two-dimensional Ce(III) coordination polymer, [La(pzdc)(Hpzdc)(H2O)3]n and [Ce(pzdc)(Hpzdc)(H2O)3]n, respectively. These two crystal structures are isostructural as well. The La(III) and Ce(III) compounds have been synthesized via conventional heating and mechanosynthesis. The La(III) coordination polymer was structurally characterized by single crystal X-ray diffraction and was shown to consist of 2D sheets that construct a three-dimensional supramolecular architecture via non-covalent interactions i.e. hydrogen bonding. To find the optimal lanthanide-ion concentrations, the systems were doped with 5%, 7.5% or 10% of a spectroscopically active ion (Sm3+, Eu3+, Tb3+, or Dy3+) to investigate the luminescence properties.

Three zinc(II) ions in combination with two units of enantiopure [3+3] triphenolic Schiff-base macrocycles 1, 2, 3, or 4 form cage-like chiral complexes. The formation of these complexes is accompanied by the enantioselective self-recognition of chiral macrocyclic units. The X-ray crystal structures of these trinuclear complexes show hollow metal-organic molecules. In some crystal forms, these barrel-shaped complexes are arranged in a window-to-window fashion, which results in the formation of 1D channels and a combination of both intrinsic and extrinsic porosity. The microporous nature of the [Zn3 12 ] complex is reflected in its N2 , Ar, H2 , and CO2 adsorption properties. The N2 and Ar adsorption isotherms show pressure-gating behavior, which is without precedent for any noncovalent porous material. A comparison of the structures of the [Zn3 12 ] and [Zn3 32 ] complexes with that of the free macrocycle H3 1 reveals a striking structural similarity. In H3 1, two macrocyclic units are stitched together by hydrogen bonds to form a cage very similar to that formed by two macrocyclic units stitched together by Zn(II) ions. This structural similarity is manifested also by the gas adsorption properties of the free H3 1 macrocycle. Recrystallization of [Zn3 12 ] in the presence of racemic 2-butanol resulted in the enantioselective binding of (S)-2-butanol inside the cage through the coordination to one of the Zn(II) ions.

Nanoparticles of a new two-dimensional cerium(III) coordination polymer compound, [Ce(pzdc)(pzdcH)(H2O)3]n (1), (H2pzdc = 2,3-pyrazinedicarboxylic acid), have been synthesized by a sonochemical process and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), FT-IR spectroscopy and elemental analyses. Compound 1 was structurally characterized by single crystal X-ray diffraction and was shown that it consists of 2D sheets that construct a three-dimensional supramolecular architecture via non-covalent interactions i.e. hydrogen bonding. The thermal stability of compound 1 both for its crystals and nanostructures has been studied by the thermal gravimetric (TG) method and compared with each other. The role of ultrasound irradiation power and the concentration of initial reactants on the size and morphology of the nano-structured compound 1, has been investigated. Calcination of compound 1 at 800 °C under air atmosphere yields ceria nanoparticles. Furthermore, the fluorescent properties of compound 1 at room temperature were studied.

The single crystals of 1-(diaminomethylene)thiouron-1-ium 4-hydroxybenzenesulfonate were grown using a solution growth technique. The compound crystallises in the centrosymmetric P 2 1 / c space group of the monoclinic system. The conformation of the 1-(diaminomethylene)thiouron-1-ium cation is not strictly planar, but twisted. Both arms of the cation are oppositely rotated by 8.5(1)° around the C N bonds involving the central N atom. The arrangement of oppositely charged components, i.e. 1-(diaminomethylene)thiouron-1-ium cations and 4-hydroxybenzenesulfonate anions in the crystal is mainly determined by ionic and hydrogen-bonding interactions forming supramolecular network. The possible hydrogen-bonding interactions between cation and anion units were analysed on the basis of molecular orbital calculations. The obtained deuterated analogue crystallises similar as H-compound in the monoclinic system ( P 2 1 /c ) with quite similar lattice parameters. The compound was also characterised by the FT-IR and Raman spectroscopies. The characteristic bands of the functional and skeletal groups of the protiated and deuterated analogue of 1-(diaminomethylene)thiouron-1-ium 4-hydroxybenzenesulfonate are discussed.

Three copper(II) complexes, [Cu2(O2CC4H3O)4(H2O)2]·H2O (1), {[Cu2(O2CC4H3O)4(bipy)2(H2O)2]·2H2O}n(2), and {[Cu(bpp)2(H2O)](O2CC4H3O)2·7H2O} (3) [O2CC4H3O = 2-furanocarboxylate anion, bipy = 4, 4′-bipyridine, and bpp = 1, 3-bis(4-pyridyl)propane] were synthesized and their crystal and molecular structures were determined by single-crystal X-ray diffraction analysis. Compound 1 consists on bimetallic tetracarboxylate units exhibiting a common paddle wheel structure. The paddle wheel units are connected by hydrogen bonding along the crystallographic b axis and π–π stacking interactions between the furano rings along the crystallographic c axis, giving rise to a 2D supramolecular array. Compounds 2 and 3 were made up in the presence of 4, 4′-bipyridine and 1, 3-bis(4-pyridyl)propane ligands, respectively, to produce 1D polymeric chains by metal-ligand interactions. The presence of other weak non-covalent interactions in these compounds extends the systems dimensionality to form 3D supramolecular networks.

Two complexes of zinc phthalocyanine monoaxially ligated by 3,4-dimethylpyridine (1) and 4-ethylpyridine (2) were obtained in crystalline forms. Compound 1 depending on the crystallisation condition crystallises in two crystalline modifications, i.e. monoclinic (P21/c, 1m) and orthorhombic (Pccn, 1o), whereas compound 2 crystallises only in one orthorhombic form (Pccn space system). Structures 1o and 2 are isotypic; an explanation of that behaviour was proposed. Each structure contains the zinc phthalocyanine and the ligand molecules in molar ratio 1:1, which was confirmed by X-ray single diffraction and thermogravimetric analysis. Ligation of the ZnPc by N-ring aromatic ligands with formation of complexes 1 and 2 does not change the colouring properties, but increases their solubility in the organic solvents comparing to the parent ZnPc pigment.

A three-dimensional (3D) bimetallic oxide compound, [CuMo3O10]·H2O (1), was synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction, powder X-ray diffraction (PXRD), FT-IR and atomic absorption spectroscopy. Nanoparticles of compound 1 were also prepared by a sonochemical process and characterized by means of scanning electron microscopy (SEM), PXRD and FT-IR analyses. The catalytic activity of 1 and its nanoparticles has been investigated in the catalytic wet air oxidation (CWAO) of Bismarck brown as a typical diazo dye. It was found that the prepared compounds are active and stable heterogeneous catalysts under the reaction conditions and can be easily recovered and reused for at least five cycles.

The compound {[Zn( l -Tyr)2(μ-4,4′-bpy)]·4H2O}n (1) crystallizes in the centrosymmetric space group P21 of the monoclinic system with cell parameters a = 9.6022(2) A, b = 13.5031(3) A, c = 11.6648(3) A and β = 99.493(2)°, with Z = 2. The elongated octahedral coordination sphere around the Zn(II) ion is created by two trans-chelated l -tyrosinate anions via N and O atoms in the basal plane and two nitrogen atoms of 4,4′-bipyridine (4,4′-bpy) centered at the apexes. The 4,4′-bpy molecules bridge adjacent Zn(II) centers, separated by 11.665 A, with the resulting formation of 1D-coordination polymer chains assembled into a three-dimensional network by multiple hydrogen bonding interactions. The vibrational assignments of the experimental FT-IR spectrum of complex 1 were performed on the basis of DFT calculations performed for the optimized structure of the complex [Zn( l -Tyr)2(μ-4,4′-bpy)] and the isolated ligands. The calculated DFT interaction energies (ΔE) reveal that N2-coordinated 4,4′-bipy is about 13% more strongly bounded to Zn(II) than N1-coordinated 4,4′-bipy (ΔE −13.25 and −15.02 kcal mol−1, respectively). These values are one order of magnitude lower than the ΔE value calculated for a bidentately bonded l -tyrosinate anion (c.a. −155 kcal mol−1) and may explain the result of NMR and Vis–UV solution studies, which suggest that in a DMSO solution of complex 1 the 4,4′-bypy molecules are removed from the Zn(II) coordination sphere of the [Zn( l -Tyr)2] unit.

Two novel inorganic-organic hybrid materials, namely, (NH4)2CuMo8O26(C10H8N2)2 (1) and Mo8O26(C10H10N2)2(C10H8N2)·2(H2O) (2) have been synthesized based on β-octamolybdate cluster and 4,4'-bipyridine (4,4'-bpy) ligand under solvothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses and characterized by FT-IR, atomic absorption spectroscopy, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). In addition, microcrystals of 1 were used to synthesize its nanocrystals via an ultrasound-assisted top-down method. The nanocrystals were characterized by scanning electron microscopy (SEM), PXRD and FT-IR analyses. The prepared hybrid materials have been proved to be active heterogeneous catalysts for catalytic wet air oxidation (CWAO) of some dyes under mild conditions. Leaching experiments showed that the catalysts had good stability under the reaction conditions and could be easily recycled and reused after a simple treatment.

New 1D-coordination polymer {[Ni(L-Tyr)2(μ-4,4′-bpy)]·4H2O}n (1) (L-Tyr = L-tyrosine, 4,4′-bpy = 4,4′-bipyridine) is composed of L-tyrosinate anions chelated nickel(II) centres via N amino and O carboxylate atoms, whereas the apices of the elongated octahedral coordination sphere are occupied by the N atoms of 4,4′-bipyridine. Its molecular structure was determined by single-crystal X-ray diffraction and characterized using vibrational (FT-IR), Raman spectroscopy (FT-Raman), electronic (NIR-Vis-UV) and high field electron paramagnetic resonance (HF-EPR) spectroscopy and thermal (TG-DTA, DSC) and magnetic methods. The tetragonality distortion parameter (T) equals 0.945. The gx, gy and gz parameters (HF-EPR spectra) are slightly temperature dependent and the set gx = 2.178(5), gy = 2.156(4), gz = 2.19(1), D = −5.76(2) cm−1, E = −0.41(1) cm−1 was found at 5 K. The analysis of the temperature and field dependent magnetization shows the weakness of magnetic interactions in 1.

We report the synthesis, crystal structure, thermal, dielectric, phonon and magnetic properties of the [CH3C(NH2)2][Mn(HCOO)3] (AceMn) compound. Our results show that this compound crystallizes in the perovskite-like orthorhombic structure, space group Imma. It undergoes a structural phase transition at 304 K into a monoclinic structure, space group P21/n. X-ray diffraction, dielectric, IR and Raman studies show that the ordering of the acetamidinium cations triggers the phase transition. Low-temperature magnetic studies show that this compound exhibits weak ferromagnetic properties below 9.0 K.

The purpose of the present study was to investigate a simple approach for synthesis of new 1D copper (II) coordination polymer as a precursor for preparation of nano-structures based on crystallography and Hirshfeld surface analysis method. In doing so, A novel 1D copper(II) coordination polymer compound of [Cu(tp)(phen)]n (1) (tp = 1,4-benzendicarboxylic acid and phen: 1,10-Phenanthroline) was synthesized using two different methods, such as branched-tube and sonochemical methods. The X-Ray Diffraction (XRD) results revealed that with applying both methods, the produced compounds have a same crystalline phase. A Single crystal X-ray analysis of produced compound 1 using the branched-tube method showed that Cu2+ ions are 6-coordinated. The contribution of intermolecular interactions in compound 1 were studied by Hirshfeld Surface Analysis method. The role of sonication power, reaction time, concentrations of reactants, temperature on the growth and final morphology of the obtained nanostructures were studied by the sonochemical method. While, the concentrations of reactants and reaction time directly affected the final size of nano-structures of compound 1, the sonication power and temperature showed an inverse impact. Compound 1 was used as a new precursors for preparation of Cu(II) oxide structures via solid-state thermal decomposition process. The nano-structures of compound 1 were further analyzed by IR spectroscopy, powder X-ray diffraction (PXRD) and Scanning Electron Microscopy (SEM).

Three novel isomorphous coordination polymers with a general formula [M(HO3P–C5H4N–PO3H)2(H2O)2]n [MII = Co (1), Zn (2) and Cd (3)] have been synthesized and characterized by powder and single-crystal X-ray diffraction, vibrational spectroscopy (IR and Raman) and simultaneous thermal analysis (TG-DTA-MS). Crystal structure analyses of compounds 1–3 have revealed that both phosphonate groups of (pyridin-1-ium-3,5-diyl)diphosphonate ligands serve to extend the metal cations into a strongly undulated grid structure parallel to the (101) plane. The adjacent monolayers are held together via multiple hydrogen bonds and offset face-to-face π–π interactions. The interlayer interaction energy values, estimated using the CRYSTAL code, have revealed that the stabilization energies of compounds 1–3 are quite similar, where 1 is least and 3 most advantageous. Computational studies have been further related to the results of thermal analyses. In the case of compound 1, which has unpaired electrons at the metal centre, the investigation has been supplemented by magnetic measurements. The magnetic properties of 1 (1.7–300 K) have been analyzed assuming that any possible exchange interactions are very weak. The obtained best-fit parameters are: Δ (axial splitting of 4T1g term) = −478 cm−1, λ (spin–orbit coupling) = −103 cm−1, α (orbital reduction factor) = 1.38, and zJ′ (mean-field exchange parameter) = −0.11 cm−1. The negative value of Δ implies that the ground state is the orbital doublet, which cannot be treated within the spin-Hamiltonian approach.

A missing member of the tetraphenylmethane-based family of supramolecular tectons, tetrakis(4-phosphonophenyl)methane, TPPM (1), has been obtained, characterized, and reacted with organic amines that possess modulated conformational flexibility. The obtained adducts serve as a diverse platform for the investigation of the amine templating effect on phenyl embraces, the resulting supramolecular network, and its topology. Hirshfeld surface (HS) analysis has been employed for the investigation of phenyl embraces, which led to the indication of characteristic HS features of 4PE and 6PE phenyl embraces. One can also observe a new subtype of phenyl embrace, namely, HBA-PE (hydrogen bond-assisted phenyl embrace), which constitutes the cooperation of two interactions: strong hydrogen bonding and a phenyl embrace. A topological insight into TPPM hydrogen-bonded networks is also provided. As a result, we found a connection of the amine template type with the periodicity of the underlying supramolecular network. Add...

Reactivity of holmium diphthalocyanine with iodide HoPc 2 I in the acetylacetone/water system has been investigated. Depending on the water quantity in the system the solvothermal reaction of HoPc 2 I with acacH/water leads to formation of four different compounds. All these four compounds were obtained in the crystalline form. In equilibrium proportion of HoPc 2 I to water (molar proportion of 1:1) in excess of acacH the unique complex of [Ho(oPc)(acac)(OAc)]I·0.5(CH 3 COCH 3 ) – ( 1 ) has been obtained. The neutral open phthalocyanine chelate ligand (oPc) is formed from phthalocyaninate ligand in sequence of numerous processes. The oPc chelate ligand shows alternate single and double bonds due to presence of imine bridge (NH). The imine bridge breaks the π-delocalisation within the whole oPc chelate ligand. The sequence of single and double bonds in the oPc ligand has been confirmed by DFT calculations. Increasing of water quantity in the reacting system leads to formation of three different holmium acetates: anhydrous holmium acetate Ho(CH 3 COO) 3 – 2 , bis(holmiumacetate) monohydrate [Ho(CH 3 COO) 3 ] 2 ·H 2 O – 3 and bis[holmium(diacetate)(triaqua)iodide] monohydrate [Ho(CH 3 COO) 2 (H 2 O) 3 I] 2 ·H 2 O – 4 . These three holmium acetates differ in the amount of water and have different structures.

Two new cobalt(II) phosphonate salts, {3[Co(H2O)6]2(C12H18O9P3)}·11H2O (1) and {[Co(H2O)6](C12H19O9P3)}·6H2O (2), were obtained in crystalline form. Compound 1 crystallises in the centrosymmetric space group of the triclinic system, whereas compound 2 crystallises in the P21/n space group of the monoclinic system. The asymmetric unit of 1 consists of one and a half hexaaqua cobalt(II) ions, one phosphonic acid residue and five and a half lattice water molecules. One Co2+ ion lies in a special position and the other one in a general position. In 1, both independent Co2+ cations are surrounded by water molecules forming distorted octahedral coordination geometry. The asymmetric unit of 2 consists of one hexaaqua cobalt(II) ion, phosphonic acid residue and six lattice water molecules. In crystal 2, similarly as in crystal 1, the environment of the Co2+ consists of water molecules that form distorted octahedral coordination geometry. The hexaaqua cobalt(II) cations interact with phosphonate counter ions and together with the solvated water molecules they form a three-dimensional hydrogen bonding supramolecular network. Magnetic susceptibility measurements exhibit paramagnetic behaviour with very weak antiferromagnetic interactions for both compounds.

4-Nitrobenzylphosphonic acid ( 1a ) has been synthesized and structurally characterized by vibrational spectroscopy (IR and Raman) and single-crystal X-ray diffraction. Additionally, Hirshfeld surface analysis and computational methods have been used to compare the intermolecular interactions in the crystal structures of 1a and its carboxylic analogue, 4-nitrobenzylcarboxylic acid ( 4-NBCA ). The crystal structure analysis of 1a has revealed that the acid molecules are extended into helical chains along the b axis using one of the hydrogen bonds established between phosphonic groups. The second (P)O H⋯O(P) hydrogen bond cross-links the inversion-related chains to form a thick monolayer with phosphonic groups arranged inwards and aromatic rings outwards. The nitro groups serve to link the neighbouring monolayers by weak C H⋯O(N) hydrogen bonds. Computations have confirmed the great contribution of electrostatic interactions for the crystal lattice stability. The cohesive energy, computed for the crystal structure of 1a exceeds 200 kJ mol −1 in magnitude and is nearly twice as large as that of 4-NBCA . The calculated cohesive energy values have been further related to the results of thermal analyses.

A natural antibiotic – Lasalocid is able to form stable complexes with ammonia and organic amines. New complexes of lasalocid with benzylamine and ammonia were obtained in the crystal forms and studied using X-ray, FT-IR, 1H NMR, 13C NMR and DFT methods. These studies have shown that in both complexes the proton is transferred from the carboxylic group to the amine group with the formation of a pseudo-cyclic structure of lasalocid anion complexing the protonated amine or NH 4 + cation. The spectroscopic and DFT studies demonstrated that the structure of the complex formed between Lasalocid and benzylamine in the solid is also conserved in the solution and gas phase. In contrast, the structure of the complex formed between lasalocid and ammonium cation found in the solid state undergoes dissociation in chloroform solution accompanied with a change in the coordination form of the NH 4 + cation.

A series of 12 novel ester derivatives of naturally occurring polyether antibiotic - salinomycin were synthesized, characterised by spectroscopic method and evaluated for their in vitro antibacterial activity and cytotoxicity. The new esters were demonstrated to form complexes with monovalent and divalent metal cation of 1:1 stoichiometry in contrast to the salinomycin which forms only complexes with monovalent cations. All the obtained compounds show potent antiproliferative activity against human cancer cell lines and a good selectivity index for cancer versus mammalian cells. Additionally, 3 compounds showed higher antiproliferative activity against the drug-resistant cancer cells and lower toxicity towards normal cells than those of unmodified salinomycin and standard anticancer drugs such as cisplatin and doxorubicin. Some of the synthesized compounds showed good inhibitory activity against Staphylococcus strains and clinical isolates of methicillin-resistant Staphylococcus aureus (MRSA) and Staphylococcus epidermidis (MRSE). These studies show that salinomycin esters are interesting scaffolds for the development of novel anticancer and Gram-positive antibacterial agents.

A series of 11 novel amides of salinomycin were synthesized for the first time. All the obtained compounds were found to show potent antiproliferative activity against human cancer cell lines including the drug-resistant cancer cells. Four new salinomycin derivatives revealed good antibacterial activity against clinical isolates of methicillin-resistant Staphylococcus epidermidis (MRSE).

Two pentacoordinated complexes of magnesium phthalocyanine (MgPc) with n-butanol and n-pentanol, (MgPc(C4H9OH) and MgPc(C5H11OH)), were obtained. Both complexes crystallise in the centrosymmetric space group of the triclinic system with two molecules per unit cell. Owing the interactions between the positively polarised Mg center and the electronegatively polarised oxygen atom of the n-alcohol the Mg atom is significantly displaced from the plane defined by the four isoindole N atoms of Pc2− macrocycle. The interaction causes a distortion of a planar Pc2− macrocycle to the saucer-shape form. Due to the steric hindrance of the axial ligand, the crystals of MgPc(C4H9OH) and MgPc(C5H11OH) are about three times more soluble than the parent MgPc, since both structures are less stabilised by the π–π interactions between the aromatic Pc2− macrocycles. Ligation of the MgPc by n-alcohols does not change the colouring properties compared to the parent MgPc pigment. DFT calculations show that the reaction of MgPc with n-butanol and n-pentanol with formation of the respective complexes is favoured by −60.32 and −66.02 kJ/mol, respectively. These energies correlate well with their thermal stability. The calculated 3D molecular electrostatic potential maps for reagents (MgPc, n-butanol and n-pentanol) and the products MgPc(C4H9OH) and MgPc(C5H11OH) are helpful for understanding the interactions between the MgPc and n-butanol or n-pentanol as well as for the organisation and arrangement of MgPc(C4H9OH) and MgPc(C5H11OH) molecules in the crystals.

Fourier transform IR and Raman spectra, XRD studies and DFT quantum chemical calculations have been used to characterize the structural and vibrational properties of 2-hydroxy-5-methylpyridine-3-carboxylic acid. In the unit-cell of this compound two molecules related by the inversion center interact via O H⋯N hydrogen bonds. The double hydrogen bridge system is spaced parallel to the (1 0 2) crystallographic plane forming eight-membered arrangement characteristic for pyridine derivatives. The six-membered ring is the second characteristic unit formed via the intramolecular O H⋯O hydrogen bond. The geometry optimization of the monomer and dimer have been performed applying the Gaussian03 program package. All calculations were performed in the B3LYP/6-31G(d,p) basis set using the XRD data as input parameters. The relation between the molecular and crystal structures has been discussed in terms of the hydrogen bonds formed in the unit cell. The vibrations of the dimer have been discussed in terms of the resonance inside the system built of five rings coupled via hydrogen bonds.

Treatment of HfPcI2·Pht (Pc = C32H16N82–; Pht = phthalonitrile) or bromide analogue HfPcBr2·Pht with acetylacetone (acacH) led to the formation of a HfPc(acac)2 complex that, depending on the crystallization conditions, crystallized with solvent acacH molecules to form mono- and disolvate crystals: HfPc(acac)2·acacH (1) and HfPc(acac)2·2acacH (2). Treatment of the partially oxidized iodine sandwich-type hafnium(IV) diphthalocyanine HfPc2(I3)2/3, in which two of three HfPc2 units are a one-electron-oxidized [HfPc2]+ unit with a π-radical character, with benzonitrile (BN) or 4-methylpyridine (4-Mepy) under ambient conditions led to the formation of μ2(O,OH)(C6H5COO)(HfPc)2 (3), which is bridged by O2– and OH– and stapled together by deprotonated benzoic acid complex, and μ2(O,OH)(C5H4NCOO)(HfPc)2 (4), which is bridged by O2– and OH– and stapled by deprotonated isonicotinic acid. Complexes 1–4 were structurally characterized by X-ray single-crystal analysis. In these complexes, the eight or seven coordination number of the closed-shell (d0) Hf4+ cation is saturated by four isoindole nitrogen atoms of the phthalocyaninate macrocycle and by four oxygen atoms in 1 and in 2 or three oxygen atoms in 3 and 4. Interaction of the Hf4+ cation with the isoindole nitrogen atoms of Pc macrocycle led to the distortion of the aromatic Pc macrocycle to the flattened crown, with the Hf4+ cation about 1.2 A out of the N4-isoindole plane of the Pc macrocycle. The complexes were also characterized by UV/Vis spectroscopy.

The solid-state organization of alkylammonium sulfoisophthalates has been analysed with respect to competing carboxylic–carboxylic and carboxylic–sulfonate interactions and preferred geometry of the amine–sulfonate interactions. All three compounds studied display layered structures with sulfoisophthalic monoanions arranged into sip-layers and alkylammonium cations crosslinking them. The size and geometry of the cation influences in a considerable way the hydrogen bond organization in the monolayers. The 2D anionic network is flat in compound 1, and becomes strongly corrugated in the presence of diethylammonium ion in compound 2. However, the bulky diisopropylammonium ion interrupts the network dimensionality and the monolayer in 3 is formed from sip chains, which are hydrogen-bonded into ribbons. Multiple weak interribbon interactions, established between the electron clouds of the aromatic rings and the lone pairs of O atoms, as well as, between the π electrons of the carbonyl double bonds hold together the neighbouring ribbons in the monolayer of 3. The common bridging–bridging ammonium–sulfonate synthon is observed in crystals 1 and 3. However, the ammonium–sulfonate synthon in crystal 2 appears to be a unique coupling of bridging–bridging and bifurcated interactions.