Marina Fonari - Academia.edu (original) (raw)
Papers by Marina Fonari
Acta crystallographica. Section C, Crystal structure communications, 2006
In the title compound, 2C8H18NO3+.2C7H6NO2-.3H2O, proton transfer occurs from the carboxylic acid... more In the title compound, 2C8H18NO3+.2C7H6NO2-.3H2O, proton transfer occurs from the carboxylic acid group of the 4-aminobenzoic acid (PABA) molecule to the amine group of the macrocycle, resulting in the formation of a salt-like adduct. The anions are combined into helical chains which are further bound by the water molecules into sheets. The macrocyclic cations are situated between these layers and are bound to the anions both directly and via bridging water molecules. The structure exhibits a diverse system of hydrogen bonding.
Crystallography Reports, 2007
The crystal structures of [(cys-syn-cys-dicyclohexano-18-crown-6 H3O)][TaF6] and [(cys-syn-cys-di... more The crystal structures of [(cys-syn-cys-dicyclohexano-18-crown-6 H3O)][TaF6] and [(cys-syn-cys-dicyclohexano-18-crown-6 H3O)][NbF6] complex compounds are determined using X-ray diffraction analysis. The tantalum complex has two polymorphic modifications, namely, the monoclinic (I) and triclinic (II) modifications. The unit cell parameters of these compounds are as follows: a = 8.507(4) , b = 11.947(5) , c = 27.392(12) , β = 93.11(1), Z = 4,
Polyhedron, 2008
The interaction of ZrO2/HfO2 or Nb2O5/Ta2O5 with an aqueous solution of hydrofluoric acid in the ... more The interaction of ZrO2/HfO2 or Nb2O5/Ta2O5 with an aqueous solution of hydrofluoric acid in the presence of aza-crown ether resulted in novel organically templated metal oxyfluorides of the compositions [(HA15C5)2][Ta2F10O] (1), [(HA18C6·H2O)(A18C6·H2O)][(H2O)Nb2F9O]·H2O (2), [(HA18C6·H2O)(M2F10·2H2O)·(H3O)·H2O] (3, 4) and [(H2DA18C6)(M2F10·2H2O)·2H2O] (5, 6) (M=Zr, Hf, A15C5=aza-15-crown-5, A18C6=aza-18-crown-6, DA18C6=diaza-18-crown-6). Complexes 1–6 were identified by single crystal X-ray diffraction. In 1, the negative charge of
Polyhedron, 2007
Two synthetic pathways, the interaction of Nb2O5 or Ta2O5 with an aqueous solution of hydrofluori... more Two synthetic pathways, the interaction of Nb2O5 or Ta2O5 with an aqueous solution of hydrofluoric acid, HF, in the presence of 18-crown-6 (18C6), 15-crown-5 (15C5), benzo-15-crown-5 (B15C5) or benzo-12-crown-4 (B12C4), and the direct interaction of the corresponding pentafluorides, MF5 (M=Ta, Nb), in the presence of HF with the same crown ethers result in crystalline complexes of the same composition, [18C6·H3O][NbF6]
Tetrahedron, 2006
4-Hydroxy-L-proline, an amino acid, an important component of collagen, was transformed into its ... more 4-Hydroxy-L-proline, an amino acid, an important component of collagen, was transformed into its N-nitroso-derivative, (4R)-4-hydroxy-1-nitroso-L-proline, 1 by butylnitrite in the acidic medium. The structure is a cyclic hydroxy-N-nitrosoacid with the carboxyl and hydroxyl groups trans to each other. The carboxyl group is in the syn-conformation. In the structure, the neutral molecules are connected via classical intermolecular O-H/O hydrogen bonds involving the hydroxyl and carboxyl groups [O/O¼2.6251(14) Å ], and form chains along the a-axis direction. The chains are linked into sheets via O-H/O hydrogen bond, [O/O¼2.6813 Å ] with participation of oxygen atom of nitroso group. Ab initio calculations based on density functional theory at the B3LYP/6-311++G(d, p) level of theory were performed to analyze the influence of 4-hydroxy-L-proline (Hyp) nitrosation on the conformation of the synthesized N-nitroso-compound. The geometry optimization of 1 and initial 4-hydroxy-L-proline was carried out in the gas phase and in solution using the polarizable continuum model. The single-point calculation was performed for the crystal structure of 1. The most stable conformer of 1 is observed in an aqueous solution. In this state, the pyrrolidine ring adopts an envelope conformation, which is also maintained in the gas phase. The twisted conformation of the pyrrolidine ring is present in all states of Hyp and in the crystal structure of 1. In 1 the interchange of five-membered ring conformation in solution and in the gas phase in comparison with the crystal is accompanied by an increase of the dipole moment of the molecule, which is maximal in solution.
Inorganic chemistry, Jan 14, 2007
The hexaazamacrocycle 1,4,7,10,13,16-hexaazacyclooctadecane, [18]ane-N6, forms mono- and dinuclea... more The hexaazamacrocycle 1,4,7,10,13,16-hexaazacyclooctadecane, [18]ane-N6, forms mono- and dinuclear derivatives with copper chloride depending on the reaction stoichiometries and times. The mononuclear derivative, [Cu([18]ane-N6)]Cl2.H2O, presents the macrocycle wrapped around the metal atom in a distorted octahedral coordinative environment, while the dinuclear derivative, [Cu2([18]ane-N6)Cl2]Cl2.4H2O, is formed by a central Cu2Cl2 core surrounded by an almost planar macrocycle. The crystal structure of both derivatives is stabilized by a network of hydrogen bonds involving the amine macrocyclic groups, the chloride anions, and the crystallization water molecules. The copper atoms in the dinuclear derivative show a strong antiferromagnetic coupling, as expected for the crystal structure parameters. A mononuclear nickel derivative has also been obtained from nickel nitrate by following the same synthetic procedure. These compounds react with TCNQ salts with formation of two types of ...
![Research paper thumbnail of Structure of Dibenzocrown Ethers and their H-Bonded Adducts. 2. Structure Peculiarities of Supramolecular Assemblages Formed by [1.5]Dibenzo-18Crown6 and Some NH-Donors](https://attachments.academia-assets.com/44409859/thumbnails/1.jpg)
](Journal of Inclusion Phenomena and Macrocyclic Chemistry, 2005
![Research paper thumbnail of Two polymorphs of phenanthro[4,5-abc]phenazine-18-crown-6: Preparation, X-ray diffraction and DFT studies](https://attachments.academia-assets.com/44409836/thumbnails/1.jpg)
](Journal of Molecular Structure, 2011
Phenanthro[4,5- abc]phenazine-18-crown-6 chromophore ( 1) was synthesized, and its two polymorphi... more Phenanthro[4,5- abc]phenazine-18-crown-6 chromophore ( 1) was synthesized, and its two polymorphic modifications were obtained by recrystallization from dichloromethane/methanol and dichloromethane/hexane solvent mixtures. Both polymorphs 1a and 1b crystallize in the same monoclinic P2 1/ c space group, and represent conformational polymorphs, which differ by the conformation of the macrocyclic cavity. The crystal structures obtained have been compared with molecular structures computed by density functional theory (DFT). As revealed by quantum chemical calculations, both polymorphs reach different minima on potential energy surface that supports our results that different solvents template distinctive conformational isomers found in crystals.
Crystengcomm, 2009
The sulfamide derivative of triphenylmethanol, 3-[hydroxy(diphenyl)methyl]benzenesulfonamide (H 2... more The sulfamide derivative of triphenylmethanol, 3-[hydroxy(diphenyl)methyl]benzenesulfonamide (H 2 NSO 2 Ph)Ph 2 COH was synthesized and, alongside with the parent triphenylmethanol and triphenylmethylamine, was investigated for selective interactions with crown ethers of different dimensionality (12-18-membered cycles). The molecule of 12-crown-4 (12C4) appeared to be the best candidate for Ph 3 COH, Ph 3 CNH 2 and Ph 3 CNH 3 NCS,while(H2NSO2Ph)Ph2COHformsthecomplexexclusivelywith18−crown−6(18C6).Thetriphenylammoniatrifluoroacetate,Ph3CNH3NCS, while (H 2 NSO 2 Ph)Ph 2 COH forms the complex exclusively with 18-crown-6 (18C6). The triphenylammonia trifluoroacetate, Ph 3 CNH 3 NCS,while(H2NSO2Ph)Ph2COHformsthecomplexexclusivelywith18−crown−6(18C6).Thetriphenylammoniatrifluoroacetate,Ph3CNH3CF 3 COO, selectively forms the complex only with 2-methoxyethanol. The crystalline products of the compositions (Ph 3 COH) 2 12C4,(Ph3CNH2)212C4, (Ph 3 CNH 2 ) 2 12C4,(Ph3CNH2)212C4, (Ph 3 CNH 3 NCS)2NCS) 2 NCS)212C4, [(H 2 NSO 2 Ph)Ph 2 COH] 2 18C6andPh3CNH318C6 and Ph 3 CNH 3 18C6andPh3CNH3CF 3 COO CH 3 OCH 2 CH 2 OH were obtained and studied by X-ray single crystal diffraction.
2014 International Conference Laser Optics, 2014
ABSTRACT Performed study on the co-crystallization of heterocyclic molecules of aminopyridine ser... more ABSTRACT Performed study on the co-crystallization of heterocyclic molecules of aminopyridine series with a nonlinear optical chromophore (4-Nitrophenol) and receiving molecular crystals with non-centrosymmetric crystal lattice based on them. Experiments on the growth of single crystals of these substances by slow evaporation technique in a closed volume. The dependence of the crystal symmetry on the growing conditions. A comparative study of nonlinear optical properties of crystals based on aminopyridines and measured their nonlinear optical coefficients.
Journal of Materials Chemistry C, 2013
Benzo[1,2-b:6,5-b 0 ]dithiophene(dithiazole)-4,5-dione derivatives: synthesis, electronic propert... more Benzo[1,2-b:6,5-b 0 ]dithiophene(dithiazole)-4,5-dione derivatives: synthesis, electronic properties, crystal packing and charge transport † A series of dihalo-and bis-aroyl-substituted benzo[1,2-b:6,5-b 0 ]dithiophene-4,5-diones were synthesized, and their electronic, electrochemical, and electrical properties investigated. Synthetic strategies to increase (i) the conjugation length of the base molecular structurethrough introduction of thiophene units bearing electronically neutral substituents (hydrogen or alkyl groups) or strong electron-withdrawing pentafluorobenzoyl group(s)and (ii) the electron affinityby moving to a benzo[1,2-d:4,3-d 0 ]bis(thiazole)-4,5-dione structurewere developed. Molecular packing in the single crystal was studied by single-crystal Xray structural analysis, and this information was subsequently used in the determination of the electronic band structures, densities of states (DOS), effective transfer integrals, and effective charge-carrier masses via density functional theory (DFT) methods. The charge-carrier transport properties of the benzo[1,2-b:6,5-b 0 ] dithiophene-4,5-dione and benzo[1,2-d:4,3-d 0 ]bis(thiazole)-4,5-dione derivatives were investigated through the fabrication and characterization of organic field-effect transistors (OFETs) via both solution-processed and vacuum-deposited films. 2,7-Bis-pentafluorobenzoyl-benzo[1,2-b:6,5-b 0 ]dithiophene-4,5-dione (10a) exhibited field-effect behavior with an average electron mobility m e ¼ 4.4 (AE1.7) Â 10 À4 cm 2 V À1 s À1 when the active layer was vacuum-deposited, and a larger m e ¼ 6.9 Â 10 À3 cm 2 V À1 s À1 when the active layer was solution-processed. These results are in stark contrast with the DFT-determined electronic band structure and effective mass, which indicate that the material possesses good intrinsic charge-carrier transport characteristics. The combined results reveal the importance of thin-film processing and that further processing refinements could lead to improved device performance. Only one material with benzo[1,2d:4,3-d 0 ]bis(thiazole)-4,5-dione core, 2,7-bis-(4-n-hexyl-thiophene-2-yl)-benzo[1,2-d:4,3-d 0 ]bis(thiazole)-4,5dione (19d), showed average m e ¼ 8.2 Â 10 À5 cm 2 V À1 s À1 in OFET with solution-processed active layer.
Chemistry-a European Journal, 2005
The first three representatives of the new family of oxacyclophanes incorporating two 2,7-dioxyfl... more The first three representatives of the new family of oxacyclophanes incorporating two 2,7-dioxyfluorenone fragments, connected by [-CH(2)CH(2)O-](m) spacers (m=2-4), have been synthesized. The yield of the smallest oxacyclophane (m=2) is considerably higher with respect to the larger ones (m=3 and m=4), which are formed in comparable yields. Molecular modeling and NMR spectra analysis of the model compounds suggest that an essential difference in oxacyclophanes yields is caused by formation of quasi-cyclic intermediates, which are preorganized for macrocyclization owing to intramolecular pi-pi stacking interactions between the fluorenone units. The solid-state structures of these oxacyclophanes exhibit intra- and intermolecular pi-pi stacking interactions that dictate their rectangular shape in the fluorenone backbone and crystal packing of the molecules with the parallel or T-shape arrangement. The crystal packing in all cases is also sustained by weak C--HO hydrogen bonds. FAB mass spectral analysis of mixtures of the larger oxacyclophanes (m=3 and m=4) and a paraquat moiety revealed peaks corresponding to the loss of one and two PF(6) (-) counterions from the 1:1 complexes formed. However, no signals were observed for complexes of the paraquat moiety with the smaller oxacyclophane (m=2). Computer molecular modeling of complexes revealed a pseudorotaxane-like incorporation of the paraquat unit, sandwiched within a macrocyclic cavity between the almost parallel-aligned fluorenone rings of the larger oxacyclophanes (m=3 and m=4). In contrast to this, only external complexes of the smallest oxacyclophane (m=2) with a paraquat unit have been found in the energy window of 10 kcal mol(-1).
Journal of Fluorine Chemistry, 2004
Preparation and characterization of the ammonium hexafluorosilicate salts, 2[R] + [SiF 6 ] 2À (R ... more Preparation and characterization of the ammonium hexafluorosilicate salts, 2[R] + [SiF 6 ] 2À (R = 4-(aminosulfonyl)benzenammonium) (1), and 2[R] + [SiF 6 ] 2À .4H 2 O (R = 4-carboxybenzenammonium), (2), are described. These salts, prepared from the reaction of the 4aminobenzenesulfonamide or the 4-aminobenzoic acid with fluorosilicic acid, were characterized by IR, mass spectrometry and X-ray diffraction. 1 and 2 crystallize in monoclinic crystal system (space group P2 1 /c and P2 1 /n, respectively), with Z = 2 in both cases. Compounds exhibit an extensive system of hydrogen bonding. #
Journal of Fluorine Chemistry, 2004
Preparation and characterization of the ammonium hexafluorosilicate salts, 2[R]+[SiF6]2− (R = 4-(... more Preparation and characterization of the ammonium hexafluorosilicate salts, 2[R]+[SiF6]2− (R = 4-(aminosulfonyl)benzenammonium) (1), and 2[R]+[SiF6]2−.4H2O (R = 4-carboxybenzenammonium), (2), are described. These salts, prepared from the reaction of the 4-aminobenzenesulfonamide or the 4-aminobenzoic acid with fluorosilicic acid, were characterized by IR, mass spectrometry and X-ray diffraction. 1 and 2 crystallize in monoclinic crystal system (space group P21/c and P21/n, respectively),
Journal of Fluorine Chemistry, 2008
The preparation and characterization of three isomeric carboxypyridinium and carboxyquinolinium h... more The preparation and characterization of three isomeric carboxypyridinium and carboxyquinolinium hexafluorosilicate salts is described. The salts of the general formulas (LH)2[SiF6] (I–III, L=2-carboxypyridine, 3-carboxypyridine, 4-carboxypyridine) and (LH)2[SiF6]·2H2O (IV, L=2-carboxyquinoline) were prepared from the protonation reaction of the corresponding pyridine carbonic acid by the fluorosilicic acid. The compounds were characterized by IR, mass-spectrometry, thermogravimetric analysis, solubility data, and in the case
Crystal Growth & Design, 2014
Ten Zn(II) and Cd(II) metal−organic materials were synthesized and studied by the X-ray method. A... more Ten Zn(II) and Cd(II) metal−organic materials were synthesized and studied by the X-ray method. Among these 10 structures, two represent binuclear clusters, and two are one-dimensional (1D) coordination polymers, while five are laminar two-dimensional (2D) solids and one is the three-dimensional (3D) framework. The investigation has been aimed at rational design of coordination polymers decorated by oxime ligands to increase the accessible adsorption area in these newly synthesized solids. The ligands used include three aliphatic dicarboxylic acids, HOOC-(CH 2 ) n -COOH [n = 1, 2, 4 corresponding to malonic (H 2 mal), succinic (H 2 suc), and adipic (H 2 adi) acids], and three neutral oxime ligands [pyridine-2-aldoxime (2-pyao), pyridine-4-aldoxime (4-pyao), and 1,2cyclohexanedionedioxime Niox)]. These novel hybrid solids with the compositions [Zn 2 (suc) 2 (2-pyao) 4 ]·2H 2 O 1, [Cd 2 (suc)(2-pyao) 4 (H 2 O) 2 ][BF 4 ] 2 2, [Cd(suc)-(2-pyao) 2 ] n 3, [Zn(mal)(4-pyao)(H 2 O)] n 4, [Cd(mal)(4-pyao)(H 2 O)] n 5, [Zn-(suc)(4-pyao)] n 6, [Zn(adi)(4-pyao) 2 ] n 7, {[Cd(adi)(4-pyao) 2 ]·dmf} n 8, [Zn-(adi)(Niox)] n 9, and [Cd(adi)(Niox)] n 10 [dmf − N,N′-dimethylformamide] demonstrate a variable class of coordination supramolecular architectures dictated by the distinctions in the metals' and oxime ligands' coordination capacities and preferences, and length and flexibility of the dicarboxylic linkers. The discrete aggregates 1 and 2 differ by the components' ratio and conformation of the bridging succinate anion; compounds 3 and 7 are 1D arrays, and compounds 4, 5, 6, 8, and 9 represent 2D layers of different topologies. Compound 10 is a 3D grid afforded by the concerted contribution of the longest in this series adipate anion, and the bigger atomic radius Cd(II) vs. Zn(II). The adsorptive properties of 7 and 9 are reported. For the laminar solid 9, the quantum chemical simulations of the adsorption capacity are in line with the experimental results. All new materials reveal dual green-blue wavelength emission in the solid state.
Journal of Molecular Structure - J MOL STRUCT, 2007
The reaction of thionicotinamide (3-thioamidopyridine) with 18-membered crown ethers, 18-crown-6 ... more The reaction of thionicotinamide (3-thioamidopyridine) with 18-membered crown ethers, 18-crown-6 (18C6), benzo-18-crown-6 (B18C6) and cis–anti–cis-dicyclohexyl-18-crown-6 (D18C6) results in the molecular complexes of 1:1 ratio for 18C6 (complex 1) and B18C6 (complex 2) and monohydrate of 2:1:1 ratio for D18C6 (complex 3), respectively. The complexes are sustained by combination of N–H⋯O, O–H⋯N and C–H⋯O hydrogen bonds, and the components are associated into molecular adduct (1) or infinite chain (2 and 3).
Tetrahedron Letters, 2003
Two representatives of a novel class of cyclophanes containing two fragments of 2,7-dioxy-9H-fluo... more Two representatives of a novel class of cyclophanes containing two fragments of 2,7-dioxy-9H-fluoren-9-one bridged by triethylene glycol and p-xylyl linking units have been prepared. X-Ray analysis shows that the former has an anti-conformation and the cavity is self-filling with fluorenone moieties.
Tetrahedron Letters, 2004
Two representatives of a novel class of crownophanes containing fragments of fluorenone and stilb... more Two representatives of a novel class of crownophanes containing fragments of fluorenone and stilbene bridged by units of diethylene glycol and triethylene glycol, respectively, have been synthesized. The crystal structure and complexation behavior of these crownophanes were studied. They form much stronger complexes with dibenzylammonium hexafluorophosphate (log K a value in CH 3 CN is equal to 3.92 ± 0.06 and 4.40 ± 0.05, respectively) than benzocrown ethers. This makes them an attractive alternative for benzocrown ethers as components in supramolecular synthesis. Ó 2004 Elsevier Ltd. All rights reserved.
Tetrahedron, 2005
The hydrochlorothiazide, 6-chloro-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide-1,1-dioxide... more The hydrochlorothiazide, 6-chloro-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide-1,1-dioxide, (HCTZ), widely used as a diuretic and anti-hypertensive drug, was transformed into its N-nitroso-derivative, 6-chloro-4-nitroso-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide-1,1-dioxide (O]N-HCTZ) by sodium nitrite in an acidic medium. The crystalline complexes of O]N-HCTZ with 18-crown-6 (18C6) and cis-anti-cis-dicyclohexyl-18C6 (DCH6B) demonstrated different H-bonding modes from those present in the co-crystals of HCTZ with the same crown ethers. The influence of the nitroso-group on the binding mode and crystal packing is discussed. q
Acta crystallographica. Section C, Crystal structure communications, 2006
In the title compound, 2C8H18NO3+.2C7H6NO2-.3H2O, proton transfer occurs from the carboxylic acid... more In the title compound, 2C8H18NO3+.2C7H6NO2-.3H2O, proton transfer occurs from the carboxylic acid group of the 4-aminobenzoic acid (PABA) molecule to the amine group of the macrocycle, resulting in the formation of a salt-like adduct. The anions are combined into helical chains which are further bound by the water molecules into sheets. The macrocyclic cations are situated between these layers and are bound to the anions both directly and via bridging water molecules. The structure exhibits a diverse system of hydrogen bonding.
Crystallography Reports, 2007
The crystal structures of [(cys-syn-cys-dicyclohexano-18-crown-6 H3O)][TaF6] and [(cys-syn-cys-di... more The crystal structures of [(cys-syn-cys-dicyclohexano-18-crown-6 H3O)][TaF6] and [(cys-syn-cys-dicyclohexano-18-crown-6 H3O)][NbF6] complex compounds are determined using X-ray diffraction analysis. The tantalum complex has two polymorphic modifications, namely, the monoclinic (I) and triclinic (II) modifications. The unit cell parameters of these compounds are as follows: a = 8.507(4) , b = 11.947(5) , c = 27.392(12) , β = 93.11(1), Z = 4,
Polyhedron, 2008
The interaction of ZrO2/HfO2 or Nb2O5/Ta2O5 with an aqueous solution of hydrofluoric acid in the ... more The interaction of ZrO2/HfO2 or Nb2O5/Ta2O5 with an aqueous solution of hydrofluoric acid in the presence of aza-crown ether resulted in novel organically templated metal oxyfluorides of the compositions [(HA15C5)2][Ta2F10O] (1), [(HA18C6·H2O)(A18C6·H2O)][(H2O)Nb2F9O]·H2O (2), [(HA18C6·H2O)(M2F10·2H2O)·(H3O)·H2O] (3, 4) and [(H2DA18C6)(M2F10·2H2O)·2H2O] (5, 6) (M=Zr, Hf, A15C5=aza-15-crown-5, A18C6=aza-18-crown-6, DA18C6=diaza-18-crown-6). Complexes 1–6 were identified by single crystal X-ray diffraction. In 1, the negative charge of
Polyhedron, 2007
Two synthetic pathways, the interaction of Nb2O5 or Ta2O5 with an aqueous solution of hydrofluori... more Two synthetic pathways, the interaction of Nb2O5 or Ta2O5 with an aqueous solution of hydrofluoric acid, HF, in the presence of 18-crown-6 (18C6), 15-crown-5 (15C5), benzo-15-crown-5 (B15C5) or benzo-12-crown-4 (B12C4), and the direct interaction of the corresponding pentafluorides, MF5 (M=Ta, Nb), in the presence of HF with the same crown ethers result in crystalline complexes of the same composition, [18C6·H3O][NbF6]
Tetrahedron, 2006
4-Hydroxy-L-proline, an amino acid, an important component of collagen, was transformed into its ... more 4-Hydroxy-L-proline, an amino acid, an important component of collagen, was transformed into its N-nitroso-derivative, (4R)-4-hydroxy-1-nitroso-L-proline, 1 by butylnitrite in the acidic medium. The structure is a cyclic hydroxy-N-nitrosoacid with the carboxyl and hydroxyl groups trans to each other. The carboxyl group is in the syn-conformation. In the structure, the neutral molecules are connected via classical intermolecular O-H/O hydrogen bonds involving the hydroxyl and carboxyl groups [O/O¼2.6251(14) Å ], and form chains along the a-axis direction. The chains are linked into sheets via O-H/O hydrogen bond, [O/O¼2.6813 Å ] with participation of oxygen atom of nitroso group. Ab initio calculations based on density functional theory at the B3LYP/6-311++G(d, p) level of theory were performed to analyze the influence of 4-hydroxy-L-proline (Hyp) nitrosation on the conformation of the synthesized N-nitroso-compound. The geometry optimization of 1 and initial 4-hydroxy-L-proline was carried out in the gas phase and in solution using the polarizable continuum model. The single-point calculation was performed for the crystal structure of 1. The most stable conformer of 1 is observed in an aqueous solution. In this state, the pyrrolidine ring adopts an envelope conformation, which is also maintained in the gas phase. The twisted conformation of the pyrrolidine ring is present in all states of Hyp and in the crystal structure of 1. In 1 the interchange of five-membered ring conformation in solution and in the gas phase in comparison with the crystal is accompanied by an increase of the dipole moment of the molecule, which is maximal in solution.
Inorganic chemistry, Jan 14, 2007
The hexaazamacrocycle 1,4,7,10,13,16-hexaazacyclooctadecane, [18]ane-N6, forms mono- and dinuclea... more The hexaazamacrocycle 1,4,7,10,13,16-hexaazacyclooctadecane, [18]ane-N6, forms mono- and dinuclear derivatives with copper chloride depending on the reaction stoichiometries and times. The mononuclear derivative, [Cu([18]ane-N6)]Cl2.H2O, presents the macrocycle wrapped around the metal atom in a distorted octahedral coordinative environment, while the dinuclear derivative, [Cu2([18]ane-N6)Cl2]Cl2.4H2O, is formed by a central Cu2Cl2 core surrounded by an almost planar macrocycle. The crystal structure of both derivatives is stabilized by a network of hydrogen bonds involving the amine macrocyclic groups, the chloride anions, and the crystallization water molecules. The copper atoms in the dinuclear derivative show a strong antiferromagnetic coupling, as expected for the crystal structure parameters. A mononuclear nickel derivative has also been obtained from nickel nitrate by following the same synthetic procedure. These compounds react with TCNQ salts with formation of two types of ...
Journal of Inclusion Phenomena and Macrocyclic Chemistry, 2005
Journal of Molecular Structure, 2011
Phenanthro[4,5- abc]phenazine-18-crown-6 chromophore ( 1) was synthesized, and its two polymorphi... more Phenanthro[4,5- abc]phenazine-18-crown-6 chromophore ( 1) was synthesized, and its two polymorphic modifications were obtained by recrystallization from dichloromethane/methanol and dichloromethane/hexane solvent mixtures. Both polymorphs 1a and 1b crystallize in the same monoclinic P2 1/ c space group, and represent conformational polymorphs, which differ by the conformation of the macrocyclic cavity. The crystal structures obtained have been compared with molecular structures computed by density functional theory (DFT). As revealed by quantum chemical calculations, both polymorphs reach different minima on potential energy surface that supports our results that different solvents template distinctive conformational isomers found in crystals.
Crystengcomm, 2009
The sulfamide derivative of triphenylmethanol, 3-[hydroxy(diphenyl)methyl]benzenesulfonamide (H 2... more The sulfamide derivative of triphenylmethanol, 3-[hydroxy(diphenyl)methyl]benzenesulfonamide (H 2 NSO 2 Ph)Ph 2 COH was synthesized and, alongside with the parent triphenylmethanol and triphenylmethylamine, was investigated for selective interactions with crown ethers of different dimensionality (12-18-membered cycles). The molecule of 12-crown-4 (12C4) appeared to be the best candidate for Ph 3 COH, Ph 3 CNH 2 and Ph 3 CNH 3 NCS,while(H2NSO2Ph)Ph2COHformsthecomplexexclusivelywith18−crown−6(18C6).Thetriphenylammoniatrifluoroacetate,Ph3CNH3NCS, while (H 2 NSO 2 Ph)Ph 2 COH forms the complex exclusively with 18-crown-6 (18C6). The triphenylammonia trifluoroacetate, Ph 3 CNH 3 NCS,while(H2NSO2Ph)Ph2COHformsthecomplexexclusivelywith18−crown−6(18C6).Thetriphenylammoniatrifluoroacetate,Ph3CNH3CF 3 COO, selectively forms the complex only with 2-methoxyethanol. The crystalline products of the compositions (Ph 3 COH) 2 12C4,(Ph3CNH2)212C4, (Ph 3 CNH 2 ) 2 12C4,(Ph3CNH2)212C4, (Ph 3 CNH 3 NCS)2NCS) 2 NCS)212C4, [(H 2 NSO 2 Ph)Ph 2 COH] 2 18C6andPh3CNH318C6 and Ph 3 CNH 3 18C6andPh3CNH3CF 3 COO CH 3 OCH 2 CH 2 OH were obtained and studied by X-ray single crystal diffraction.
2014 International Conference Laser Optics, 2014
ABSTRACT Performed study on the co-crystallization of heterocyclic molecules of aminopyridine ser... more ABSTRACT Performed study on the co-crystallization of heterocyclic molecules of aminopyridine series with a nonlinear optical chromophore (4-Nitrophenol) and receiving molecular crystals with non-centrosymmetric crystal lattice based on them. Experiments on the growth of single crystals of these substances by slow evaporation technique in a closed volume. The dependence of the crystal symmetry on the growing conditions. A comparative study of nonlinear optical properties of crystals based on aminopyridines and measured their nonlinear optical coefficients.
Journal of Materials Chemistry C, 2013
Benzo[1,2-b:6,5-b 0 ]dithiophene(dithiazole)-4,5-dione derivatives: synthesis, electronic propert... more Benzo[1,2-b:6,5-b 0 ]dithiophene(dithiazole)-4,5-dione derivatives: synthesis, electronic properties, crystal packing and charge transport † A series of dihalo-and bis-aroyl-substituted benzo[1,2-b:6,5-b 0 ]dithiophene-4,5-diones were synthesized, and their electronic, electrochemical, and electrical properties investigated. Synthetic strategies to increase (i) the conjugation length of the base molecular structurethrough introduction of thiophene units bearing electronically neutral substituents (hydrogen or alkyl groups) or strong electron-withdrawing pentafluorobenzoyl group(s)and (ii) the electron affinityby moving to a benzo[1,2-d:4,3-d 0 ]bis(thiazole)-4,5-dione structurewere developed. Molecular packing in the single crystal was studied by single-crystal Xray structural analysis, and this information was subsequently used in the determination of the electronic band structures, densities of states (DOS), effective transfer integrals, and effective charge-carrier masses via density functional theory (DFT) methods. The charge-carrier transport properties of the benzo[1,2-b:6,5-b 0 ] dithiophene-4,5-dione and benzo[1,2-d:4,3-d 0 ]bis(thiazole)-4,5-dione derivatives were investigated through the fabrication and characterization of organic field-effect transistors (OFETs) via both solution-processed and vacuum-deposited films. 2,7-Bis-pentafluorobenzoyl-benzo[1,2-b:6,5-b 0 ]dithiophene-4,5-dione (10a) exhibited field-effect behavior with an average electron mobility m e ¼ 4.4 (AE1.7) Â 10 À4 cm 2 V À1 s À1 when the active layer was vacuum-deposited, and a larger m e ¼ 6.9 Â 10 À3 cm 2 V À1 s À1 when the active layer was solution-processed. These results are in stark contrast with the DFT-determined electronic band structure and effective mass, which indicate that the material possesses good intrinsic charge-carrier transport characteristics. The combined results reveal the importance of thin-film processing and that further processing refinements could lead to improved device performance. Only one material with benzo[1,2d:4,3-d 0 ]bis(thiazole)-4,5-dione core, 2,7-bis-(4-n-hexyl-thiophene-2-yl)-benzo[1,2-d:4,3-d 0 ]bis(thiazole)-4,5dione (19d), showed average m e ¼ 8.2 Â 10 À5 cm 2 V À1 s À1 in OFET with solution-processed active layer.
Chemistry-a European Journal, 2005
The first three representatives of the new family of oxacyclophanes incorporating two 2,7-dioxyfl... more The first three representatives of the new family of oxacyclophanes incorporating two 2,7-dioxyfluorenone fragments, connected by [-CH(2)CH(2)O-](m) spacers (m=2-4), have been synthesized. The yield of the smallest oxacyclophane (m=2) is considerably higher with respect to the larger ones (m=3 and m=4), which are formed in comparable yields. Molecular modeling and NMR spectra analysis of the model compounds suggest that an essential difference in oxacyclophanes yields is caused by formation of quasi-cyclic intermediates, which are preorganized for macrocyclization owing to intramolecular pi-pi stacking interactions between the fluorenone units. The solid-state structures of these oxacyclophanes exhibit intra- and intermolecular pi-pi stacking interactions that dictate their rectangular shape in the fluorenone backbone and crystal packing of the molecules with the parallel or T-shape arrangement. The crystal packing in all cases is also sustained by weak C--HO hydrogen bonds. FAB mass spectral analysis of mixtures of the larger oxacyclophanes (m=3 and m=4) and a paraquat moiety revealed peaks corresponding to the loss of one and two PF(6) (-) counterions from the 1:1 complexes formed. However, no signals were observed for complexes of the paraquat moiety with the smaller oxacyclophane (m=2). Computer molecular modeling of complexes revealed a pseudorotaxane-like incorporation of the paraquat unit, sandwiched within a macrocyclic cavity between the almost parallel-aligned fluorenone rings of the larger oxacyclophanes (m=3 and m=4). In contrast to this, only external complexes of the smallest oxacyclophane (m=2) with a paraquat unit have been found in the energy window of 10 kcal mol(-1).
Journal of Fluorine Chemistry, 2004
Preparation and characterization of the ammonium hexafluorosilicate salts, 2[R] + [SiF 6 ] 2À (R ... more Preparation and characterization of the ammonium hexafluorosilicate salts, 2[R] + [SiF 6 ] 2À (R = 4-(aminosulfonyl)benzenammonium) (1), and 2[R] + [SiF 6 ] 2À .4H 2 O (R = 4-carboxybenzenammonium), (2), are described. These salts, prepared from the reaction of the 4aminobenzenesulfonamide or the 4-aminobenzoic acid with fluorosilicic acid, were characterized by IR, mass spectrometry and X-ray diffraction. 1 and 2 crystallize in monoclinic crystal system (space group P2 1 /c and P2 1 /n, respectively), with Z = 2 in both cases. Compounds exhibit an extensive system of hydrogen bonding. #
Journal of Fluorine Chemistry, 2004
Preparation and characterization of the ammonium hexafluorosilicate salts, 2[R]+[SiF6]2− (R = 4-(... more Preparation and characterization of the ammonium hexafluorosilicate salts, 2[R]+[SiF6]2− (R = 4-(aminosulfonyl)benzenammonium) (1), and 2[R]+[SiF6]2−.4H2O (R = 4-carboxybenzenammonium), (2), are described. These salts, prepared from the reaction of the 4-aminobenzenesulfonamide or the 4-aminobenzoic acid with fluorosilicic acid, were characterized by IR, mass spectrometry and X-ray diffraction. 1 and 2 crystallize in monoclinic crystal system (space group P21/c and P21/n, respectively),
Journal of Fluorine Chemistry, 2008
The preparation and characterization of three isomeric carboxypyridinium and carboxyquinolinium h... more The preparation and characterization of three isomeric carboxypyridinium and carboxyquinolinium hexafluorosilicate salts is described. The salts of the general formulas (LH)2[SiF6] (I–III, L=2-carboxypyridine, 3-carboxypyridine, 4-carboxypyridine) and (LH)2[SiF6]·2H2O (IV, L=2-carboxyquinoline) were prepared from the protonation reaction of the corresponding pyridine carbonic acid by the fluorosilicic acid. The compounds were characterized by IR, mass-spectrometry, thermogravimetric analysis, solubility data, and in the case
Crystal Growth & Design, 2014
Ten Zn(II) and Cd(II) metal−organic materials were synthesized and studied by the X-ray method. A... more Ten Zn(II) and Cd(II) metal−organic materials were synthesized and studied by the X-ray method. Among these 10 structures, two represent binuclear clusters, and two are one-dimensional (1D) coordination polymers, while five are laminar two-dimensional (2D) solids and one is the three-dimensional (3D) framework. The investigation has been aimed at rational design of coordination polymers decorated by oxime ligands to increase the accessible adsorption area in these newly synthesized solids. The ligands used include three aliphatic dicarboxylic acids, HOOC-(CH 2 ) n -COOH [n = 1, 2, 4 corresponding to malonic (H 2 mal), succinic (H 2 suc), and adipic (H 2 adi) acids], and three neutral oxime ligands [pyridine-2-aldoxime (2-pyao), pyridine-4-aldoxime (4-pyao), and 1,2cyclohexanedionedioxime Niox)]. These novel hybrid solids with the compositions [Zn 2 (suc) 2 (2-pyao) 4 ]·2H 2 O 1, [Cd 2 (suc)(2-pyao) 4 (H 2 O) 2 ][BF 4 ] 2 2, [Cd(suc)-(2-pyao) 2 ] n 3, [Zn(mal)(4-pyao)(H 2 O)] n 4, [Cd(mal)(4-pyao)(H 2 O)] n 5, [Zn-(suc)(4-pyao)] n 6, [Zn(adi)(4-pyao) 2 ] n 7, {[Cd(adi)(4-pyao) 2 ]·dmf} n 8, [Zn-(adi)(Niox)] n 9, and [Cd(adi)(Niox)] n 10 [dmf − N,N′-dimethylformamide] demonstrate a variable class of coordination supramolecular architectures dictated by the distinctions in the metals' and oxime ligands' coordination capacities and preferences, and length and flexibility of the dicarboxylic linkers. The discrete aggregates 1 and 2 differ by the components' ratio and conformation of the bridging succinate anion; compounds 3 and 7 are 1D arrays, and compounds 4, 5, 6, 8, and 9 represent 2D layers of different topologies. Compound 10 is a 3D grid afforded by the concerted contribution of the longest in this series adipate anion, and the bigger atomic radius Cd(II) vs. Zn(II). The adsorptive properties of 7 and 9 are reported. For the laminar solid 9, the quantum chemical simulations of the adsorption capacity are in line with the experimental results. All new materials reveal dual green-blue wavelength emission in the solid state.
Journal of Molecular Structure - J MOL STRUCT, 2007
The reaction of thionicotinamide (3-thioamidopyridine) with 18-membered crown ethers, 18-crown-6 ... more The reaction of thionicotinamide (3-thioamidopyridine) with 18-membered crown ethers, 18-crown-6 (18C6), benzo-18-crown-6 (B18C6) and cis–anti–cis-dicyclohexyl-18-crown-6 (D18C6) results in the molecular complexes of 1:1 ratio for 18C6 (complex 1) and B18C6 (complex 2) and monohydrate of 2:1:1 ratio for D18C6 (complex 3), respectively. The complexes are sustained by combination of N–H⋯O, O–H⋯N and C–H⋯O hydrogen bonds, and the components are associated into molecular adduct (1) or infinite chain (2 and 3).
Tetrahedron Letters, 2003
Two representatives of a novel class of cyclophanes containing two fragments of 2,7-dioxy-9H-fluo... more Two representatives of a novel class of cyclophanes containing two fragments of 2,7-dioxy-9H-fluoren-9-one bridged by triethylene glycol and p-xylyl linking units have been prepared. X-Ray analysis shows that the former has an anti-conformation and the cavity is self-filling with fluorenone moieties.
Tetrahedron Letters, 2004
Two representatives of a novel class of crownophanes containing fragments of fluorenone and stilb... more Two representatives of a novel class of crownophanes containing fragments of fluorenone and stilbene bridged by units of diethylene glycol and triethylene glycol, respectively, have been synthesized. The crystal structure and complexation behavior of these crownophanes were studied. They form much stronger complexes with dibenzylammonium hexafluorophosphate (log K a value in CH 3 CN is equal to 3.92 ± 0.06 and 4.40 ± 0.05, respectively) than benzocrown ethers. This makes them an attractive alternative for benzocrown ethers as components in supramolecular synthesis. Ó 2004 Elsevier Ltd. All rights reserved.
Tetrahedron, 2005
The hydrochlorothiazide, 6-chloro-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide-1,1-dioxide... more The hydrochlorothiazide, 6-chloro-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide-1,1-dioxide, (HCTZ), widely used as a diuretic and anti-hypertensive drug, was transformed into its N-nitroso-derivative, 6-chloro-4-nitroso-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide-1,1-dioxide (O]N-HCTZ) by sodium nitrite in an acidic medium. The crystalline complexes of O]N-HCTZ with 18-crown-6 (18C6) and cis-anti-cis-dicyclohexyl-18C6 (DCH6B) demonstrated different H-bonding modes from those present in the co-crystals of HCTZ with the same crown ethers. The influence of the nitroso-group on the binding mode and crystal packing is discussed. q