Ewa Rozycka-Sokolowska

First Approach to Nitrogen‐Containing Fused Aromatic Hydrocarbons as Targets for Organoelectronics Utilizing a New Transformation of O‐Protected Diaryl Methanols

A new concise approach for the construction of heteroatom analogues of polycyclic aromatic benzo[g]quinoline, benzo[b]carbazole, and pyrido[b]carbazole systems via diaryl methanols is described. This transformation involves formation of a central benzene ring fused to two aromatic 5- or 6-membered rings of pyrrole and/or pyridine by using a combination of two aromatic aldehydes, of which at least one contains a ring nitrogen. Analysis of the UV and fluorescent properties, Stokes shifts, quantum yields in solution, and pi-stacking interactions in the crystal structures of the new materials was performed. These polycyclic aromatic compounds show potential as small-molecule organoelectronic materials.

Synthesis and optoelectronic properties of hexahydroxylated 10-O-R-substituted anthracenes via a new modification of the Friedel-Crafts reaction using O-protected ortho-acetal diarylmethanols.

A new modification of the Friedel-Crafts type intramolecular cyclization involving O-protected ortho-acetal diarylmethanols as a new type of reactant, was carried out for the first time in a medium containing a large amount of water at room temperature and enabled synthesis of a series of electron-rich, hexahydroxylated 10-O-R-substituted anthracenes, where R is an alkyl (Me, nBu, n-C(16)H(33)) or arylalkyl group (CH(2)Ph, CH(2)-2-Napht, CH(2)C(6)H(4)CH(2)OAr) and also evaluation of their electronic and optoelectronic properties in solution, crystal, and solid thin film. In this transformation, a central 10-O-R-substituted benzene ring was formed, fused to rings originating from two independent aromatic aldehydes. The reaction proceeded via two identified mechanisms involving acetal and/or free aldehyde groups. The acid sensitive acetal and dibenzyl alkoxy functions have never been used together in the intramolecular Friedel-Crafts type cyclization. The new compounds revealed deep blue fluorescence and quantum yields in solution around 0.3. The electrical properties investigated for thin films obtained by vacuum deposition on glass were 10-O-R-substituent dependent and showed much faster transient current decay in the case of the 10-O-CH(2)Ph derivative than for the material with a 10-O-Me substituent (the lifetime of charge carriers was 25 times shorter in this case). The AFM images of thin films, Stokes shifts, and X-ray analysis of π-stacking interactions in crystals of the new materials have been also obtained.

Two isostructural halogen derivatives of 9-ethylcarbazole: crystal structure, Hirshfeld surface analysis, and structural comparison with other simple analogs

This article describes a detailed study of the molecular packing and intermolecular interactions in crystals of two derivatives of 9-ethylcarbazole, i.e., 3-chloro- and 3-bromo-9-ethylcarbazole (1 and 2, respectively). A significance of this study lies both in the comparison drawn between the crystal structures of these compounds and those of several of their simple analogs [i.e., 3,6-dibromo-9-ethylcarbazole (3), 3,6-dibromo-9-methylcarbazole (4), 3,6-dibromocarbazole (5), 3-bromocarbazole (6), 3,6-diiodocarbazole (7), 9-ethylcarbazole (8), 9-methylcarbazole (9) and carbazole (10)], and in the preliminary assessment of their suitability as active materials for organic electronics. This comparison shows a close similarity in the packing of molecules of three of them (i.e., 3, 4, 6) that form the π-stacks along the shortest crystallographic axes, with a substantial spatial overlap between adjacent molecules in the stacks, depending mainly on the length of substituent at position 9 of carbazole skeleton and on the ratio of (%C···H)/(%C···C) interactions. Similar to them, in the crystal structures of 1 and 2 there is slipped face-to-face π···π interaction, but in contrast this interaction connects two molecules of these compounds into the dimers that are further connected by C–H···π interaction. The molecular packing in crystals of these compounds is intermediate between the arrangement of molecules of 3, 4, and 6, where the slipped π-stacking is predominant, and the typical herringbone packing in compounds 5 and 7–10. Thus, it can be supposed that out of ten compounds analyzed here, only 3, 4, and 6 will turn to be the most promising materials for device applications (particularly for field-effect transistors).

The structural, magnetic, hydrogenation and electrode properties of REMg2Cu9−xNix alloys (RE=La, Pr,Tb)

AbstractThe LaMg2Cu9, PrMg2Cu9, LaMg2Cu4Ni5, PrMg2Cu4Ni5 and TbMg2Cu6Ni3 alloys were prepared for the investigations of crystal structure, magnetic and hydrogen storage properties. The magnetic properties of several REMg2Cu9−xNix compounds have been studied up to 9 T and from 2 to 300 K. Tb compounds show a ferrimagnetic (with Ni) or antiferromagnetic (without Ni) behaviour, which can be attributed to the Tb magnetic structure. At high temperature a paramagnetic Curie Weiss behaviour is observed and the effective moment corresponds to that of Tb. A magnetic contribution of Pr moment is observed in both Pr compounds, with larger magnetization for PrMg2Cu4Ni5 and a transition at 3 K. The hydrogen absorption occurs at 95 bar for LaMg2Cu9 (3 H f.u.−1) and above 2 bars for LaMg2Cu4Ni5 (1.6 H f.u.−1). The effect of Cu-Ni substitution on the electrochemical properties of LaMg2M9 ternary alloys was investigated leading to maximum discharge capacity of 250–310 mAh g−1.

4-Chloro-1-naphthol

Molecules of the title compound, C(10)H(7)ClO, (I), are connected by a single strong O-H...O hydrogen bond into a simple C(2) chain, which runs parallel to the c axis and is additionally stabilized by intermolecular pi-pi stacking interactions. The significance of this study lies in the comparison drawn between the crystal structure of (I) and those of several of its simple analogues. This comparison shows a close similarity in the packing of the molecules that form pi-stacks along the shortest crystallographic axes. A substantial spatial overlap is observed between adjacent molecules in such a pi-stack, depending mainly on the kind of substituent.

Synthesis of Chiral Aminosulfite and Sulfite from Optically Active 2-Naphthol Derivatives

Abstract Preparation of chiral cyclic aminosulfite and sulfite derived from diastereomerically pure 1-[α-N-1-phenylethyl]benzyl-2-naphthol and 1,1′-bi-2′-naphthol, respectively, are reported. The nucleophilic substitution on the sulfite substrate by using some selected nucleophiles is also discussed.

Triphenylmethanethiol as a Precursor for the Simultaneous Formation of Bis (Triphenylmethyl) Sulfide, Bis(Triphenylmethyl) Trisulfide, and Bis(Triphenylmethyl) Peroxide: Crystal Structures and Hirshfeld Surface Analyses

Abstract Structurally identified, three unexpected products, obtained from the reaction of tritphenylmethanethiol with (+)-R-pulegone, i.e., bis(triphenylmethyl) sulfide, bis(tripheny- lmethyl) trisulfide, and bis(triphenylmethyl) peroxide, have been examined using Hirshfeld surface analysis. This analysis has been also performed for several of their simple analogues. Comparison of the results obtained shows that relative contributions of close contacts to the Hirshfeld surfaces of the molecules depend on the number of sulfur atoms between the central C atoms of compounds Ph3CSnCPh3 (n = 1, 2, 3 and 6), and in the case of Ph3XO2XPh3 (X = C, Si, Ge) compounds on the type of central X atom. GRAPHICAL ABSTRACT

6,6′-Dimethylsulfinyl-2,2′-bipyridine: crystal structure and Hirshfeld surface analysis

The structure of 6,6′-dimethylsulfinyl-2,2′-bipyridine (1) has been determined by a single-crystal X-ray crystallography. This compound crystallizes in the monoclinic P21 space group with a=5.7922(12) Å, b=8.7292(5) Å, c=13.0887(16) Å, β=102.094(14)° and Z=2. The molecule of 1 consists of a 2,2′-bipyridine moiety substituted in the 6 and 6′ positions by dimethylsulfinyl groups. Atoms belonging to one of these two groups are disordered over two positions with an occupation of 0.600(9) for the major component. The molecular structure of 1 has been compared and discussed with several similar compounds. In the solid state, molecules of 1 are linked by two independent weak C‒H···O hydrogen bonds forming the infinite simple C(4) and C(5) chains, and their combined effect is a formation of the ring additionally stabilized by intermolecular π···π stacking and S\dbond O···π interactions. Moreover, Hirshfeld surface analysis has been used for comparison of the interactions in the crystal structure of 1 and in those of several of its simple analogues [i.e. 1-[6-(6-acetylpyridin-2-yl)pyridin-2-yl]ethanone, dimethyl 2,2′-bipyridine-6,6′-dicarboxylate, 6,6′-dimethyl-2,2′-bipyridyl and 2,2′-bipyridyl]. GRAPHICAL ABSTRACT

The new ternary phases of La3(Zn0.874Mg0.126)11 and Ce3(Zn0.863Mg0.137)11

The new ternary intermetallic title compounds, namely trilanthanum undeca(zinc/magnesium), La(3)(Zn(0.874)Mg(0.126))(11), (I), and tricerium undeca(zinc/magnesium), Ce(3)(Zn(0.863)Mg(0.137))(11), (II), are isostructural and crystallize in the orthorhombic La(3)Al(11) structure type. These three phases belong to the same structural family, the representative members of which may be derived from the tetragonal BaAl(4) structure type by a combination of internal deformation and multiple substitution. Compared to the structure of La(3)Al(11), in (I), a significant decrease of 11.9% in the unit-cell b axis and an increase in the other two directions, of 3.6% along a and 5.2% along c, are observed. Such an atypical deformation is caused by the closer packing of atoms in the unit cell due to atom shifts that reflect strengthening of metallic-type bonding. This structural change is also manifested in a significant difference in the coordination around the smaller atoms at the 8l Wyckoff position (site symmetry m). The Al atom in La(3)Al(11) is in a tricapped trigonal prismatic environment (coordination number 9), while the Zn atoms in (I) and (II) are situated in a tetragonal antiprism with two added atoms (coordination number 10).

4-Methoxy-1-naphthol: chains formed by O—H...O hydrogen bonds and π–π stacking interactions

The structure of 4-methoxy-1-naphthol, C(11)H(10)O(2), (I), contains an intermolecular O-H...O hydrogen bond which links the molecules into a simple C(2) chain running parallel to the shortest crystallographic b axis. This chain is reinforced by intermolecular pi-pi stacking interactions. Comparisons are drawn between the crystal structure of (I) and those of several of its simple analogues, including 1-naphthol and some monosubstituted derivatives, and that of its isomer 7-methoxy-2-naphthol. This comparison shows a close similarity in the packing of the molecules of its simple analogues that form pi-stacks along the shortest crystallographic axes. A substantial spatial overlap is observed between adjacent molecules in such stacks. In this group of monosubstituted naphthols, the overlap depends mainly on the position of the substituents carried by the naphthalene moiety, and the extent of the overlap depends on the substituent type. By contrast with (I), in the crystal structure of the isomeric 7-methoxy-2-naphthol there are no O-H...O hydrogen bonds or pi-pi stacking interactions, and sheets are formed by O-H...pi and C-H...pi interactions.