Synthesis, Theoretical and Experimental Investigation of Electronic Properties of New Fluoranthenyl-Based Compounds for OLEDs Applications.

Three novel conjugated molecules have been synthesized: 2-(fluoranthen-3-yliminomethyl)-3,4-ethylenedioxythio-phene (EIF), 2-(fluoranthen-3-yliminomethyl) thiophene (TIF), and 2-(fluoranthen-3-yliminomethyl) fluorene (FIF). Optical properties were obtained from electronic absorption and emission spectra in DMSO solution. The solvatochromic properties of the molecules have been studied in different solvents. Electrochemical properties were studied by cyclic voltammetry in a Bu4NBF4 (0.1 M)/MeCN organic solution. As part of investigations to explain the nature of electronic transition process, we have performed geometry optimization of both the ground and the vertical excitation states, using the DFT B3LYP/6-311G (d, p) and TD-DFT (CPCM)/B3LYP/6-311G (d, p) approaches, respectively. Theoretical calculations closely match the experimental findings. Results show that EIF, TIF and FIF are potential candidates to be used as electron transport layer in Organic Light-Emitting Diodes (OLEDs).

Crystal structure and Hirshfeld surface analysis of 1-[(E)-2-(3-nitro-phen-yl)diazen-1-yl]naphthalen-2-ol.

The title compound, C16H11N3O3, belongs to the family of azo dyes. In the light of a single-crystal X-ray study, it is evident that of the tautomeric forms (azo-hydrazone), the hydrazone form is the predominant form in the solid state, namely, (1E)-1-[2-(3-nitro-phen-yl)hydrazin-1-yl-idene]-1,2-di-hydro-naphthalen-2-one. The naphthol and benzene fragments attached to the -N=N- moiety adopt the s-trans conformation. Furthermore, the mol-ecules are nearly coplanar, subtending a dihedral angle of 2.63 (5)°. An intra-molecular N-H⋯O hydrogen bond occurs. There are only two types of inter-molecular inter-actions in the crystal structure: strong hydrogen-bonding C-H⋯O inter-actions and π-π stacking inter-actions. The importance of C-H⋯O inter-actions in the mol-ecular packing is reflected by the relatively high contributions (28.5%) made by O⋯H/H⋯O contacts to the Hirshfeld surface.

Synthesis, crystal structure and Hirshfeld surface analysis of aqua-(3-meth-oxy-cinnamato-κO)bis-(1,10-phenanthroline-κ2 N,N')cobalt(II) nitrate.

The title compound, [Co(C10H9O3)(C12H8N2)2(H2O)]NO3 (I), crystallizes in the triclinic space group P with a monomeric [Co(3-meo-cin)(phen)2(H2O)]+ cation and a nitrate anion (3-meo-cin = 3-meth-oxy cinnamic acid) in the asymmetric unit. The CoII ion is coordinated by four N atoms from two 1,10-phenanthroline ligands and two O atoms, the first from a meth-oxy cinnamate ligand and the second from a coordinated water mol-ecule, forming a distorted octa-hedral geometry. Discrete entities of the cation and nitrate anion are formed by water-nitrate O-H⋯O and phen-nitrate C-H⋯O hydrogen bonds. The components are further assembled into chains along the c-axis direction. Layers are than formed by slipped π-π stacking inter-actions parallel to the bc plane. The inter-molecular inter-actions in the crystal structure were qu-anti-fied and analysed using Hirshfeld surface analysis.

Crystal structure and Hirshfeld surface analysis of 2-(2-hy-droxy-phen-yl)quinoline-6-sulfonamide.

In the title compound, C15H12N2O3S, there are two mol-ecules (A and B) in the asymmetric unit. The attached phenol and quinoline moieties of each mol-ecule are almost coplanar with a dihedral angle of 6.05 (15)° for mol-ecule A and 1.89 (13)° for mol-ecule B. The crystal structure features N-H⋯O and C-H⋯O hydrogen bonds, C-H⋯π inter-actions and π-π stacking inter-actions. Hirshfeld surface analysis indicates that the most significant contacts in the crystal packing are C⋯H/H⋯C (29.2%), O⋯H/H⋯O (28.6%) and H⋯H (28.5%).

Synthesis, crystal structure and Hirshfeld surface of bis-(2-amino-pyridinium) hexa-chlorido-stannate(IV).

In the title mol-ecular salt, (C5H7N2)2[SnCl6], the cation is protonated at the pyridine N atom and the complete dianion is generated by a crystallographic centre of symmetry. In the crystal, N-H⋯Cl hydrogen bonds link the components into a three-dimensional network built up from the stacking of alternate cationic and anionic layers. The nature of the inter-molecular inter-actions has been analysed in terms of the Hirshfeld surfaces of the cations and the anions. The thermal behaviour and the Raman spectrum of the title compound are reported.

Crystal structure, characterization and Hirshfeld analysis of bis-{(E)-1-[(2,4,6-tri-bromo-phen-yl)diazen-yl]naphthalen-2-olato}copper(II) dimethyl sulfoxide monosolvate.

In the title compound, [Cu(C16H8Br3N2O)2]·C2H6OS, the CuII atom is tetra-coordinated in a square-planar coordination, being surrounded by two N atoms and two O atoms from two N,O-bidentate (E)-1-[(2,4,6-tri-bromo-phen-yl)diazen-yl]naphthalen-2-olate ligands. The two N atoms and two O atoms around the metal center are trans to each other, with an O-Cu-O bond angle of 177.90 (16)° and a N-Cu-N bond angle of 177.8 (2)°. The average distances between the CuII atom and the coordinated O and N atoms are 1.892 (4) and 1.976 (4) Å, respectively. In the crystal, complexes are linked by C-H⋯O hydrogen bonds and by π-π inter-actions involving adjacent naphthalene ring systems [centroid-centroid distance = 3.679 (4) Å]. The disordered DMSO mol-ecules inter-act weakly with the complex mol-ecules, being positioned in the voids left by the packing arrangement of the square-planar complexes. The DMSO solvent mol-ecule is disordered over two positions with occupancies of 0.70 and 0.30.

Coordination polymer chains built from Cu(II) and adipate ions linked by hydrogen bonds to form a three-dimensional framework structure.

In the title compound, catena-poly[bis[(2,2'-bipyridine-κ(2)N,N')(1,1,3,3-tetracyano-2-ethoxypropenido-κN)copper(II)]-µ4-hexanedioato-κ(6)O(1),O(1'):O(1):O(6),O(6'):O(6)], [Cu2(C9H5N4O)2(C6H8O4)(C10H8N2)2]n, the adipate (hexanedioate) dianion lies across a centre of inversion in the space group P1. The Cu(II) centre adopts a distorted form of axially elongated (4+2) coordination, and the Cu(II) and adipate components form a one-dimensional coordination polymer from which the 2,2'-bipyridine and 1,1,3,3-tetracyano-2-ethoxypropenide components are pendent, and where each adipate dianion is bonded to four different Cu(II) centres. The coordination polymer chains are linked into a three-dimensional framework structure by a combination of C-H···N and C-H···O hydrogen bonds, augmented by a π-π stacking interaction.

A new polymorph of aqua-bis-(1,10-phenanthroline-κ(2) N,N')copper(II) dinitrate.

The title mol-ecule, [Cu(C12H8N2)2(H2O)](NO3)2, is a new polymorph of a compound which up to now has been reported to crystallize space groups in C2/c and Cc. The crystal studied was twinned by non-merohedry (final BASF factor of 0.40043) with the structure being solved and refined in P-1. The Cu(II) atom is coordinated by four N atoms from two 1,10-phenanthroline ligands and an O atom from a water mol-ecule in an approximate trigonal-bipyramidal geometry. Discrete entities of one cation and two nitrate anions are formed by water-nitrate O-H⋯O hydrogen bonds. The components are further assembled into a three-dimensional network by C-H⋯O hydrogen bonds.

Bis(2,2'-bipyridyl-κ(2) N,N')chloridonickel(II) nitrate trihydrate.

In the title hydrated salt, [NiCl(C10H8N2)2](NO3)·3H2O, the Ni(2+) ion is coordinated by two 2,2'-bipyridyl (2,2'-bpy) ligands and a chloride ion in a trigonal-bipyramidal geometry. The chloride ion occupies an equatorial site and the dihedral angle between the 2,2'-bpy ring systems is 72.02 (6)°. In the crystal, the components are linked by C-H⋯O and O-H⋯O hydrogen bonds and aromatic π-π stacking inter-actions [shortest centroid-centroid separation = 3.635 (2) Å], generating a three-dimensional network.

Poly[[diaqua-bis-(µ2-4,4'-bipyrid-yl)cobalt(II)] dinitrate tetra-hydrate].

The title compound, {[Co(C10H8N2)2(H2O)2](NO3)2·4H2O} n , (C10H8N2 = 4,4'-bipyridine = 4,4'-bpy) is a layered coordination polymer built up from a cationic square grid extending in (101) enclosing uncoordinating nitrate ions and water mol-ecules. The Co(II) ion has site symmetry 2 and one of the 4,4'-bpy ligands is generated by twofold symmetry [two N atoms and two C atoms lie on the rotation axis and the dihedral angle between the pyridine rings is 45.66 (5)°]. The other 4,4'-bpy ligand is generated by a crystallographic inversion center. The Co(II) ion exhibits a slightly distorted octa-hedral coordination geometry defined by two O atoms of two coordinating water mol-ecules and four N atoms from four bridging 4,4'-bpy ligands. The structure is consolidated by O-H⋯O, C-H⋯O and C-H⋯N hydrogen bonds.

Bis(acetyl-acetonato-κ(2)O,O')bis-(pyridine-κN)nickel(II) dihydrate.

The title compound, [Ni(C(5)H(7)O(2))(2)(C(5)H(5)N)(2)]·2H(2)O, crystallizes with two half-mol-ecules in the asymmetric unit. The Ni(II) ion of each unique complex mol-ecule lies on an inversion centre and has an octa-hedral coordination geometry. The crystal structure features weak O-H⋯O hydrogen bonds, which form chains running parallel to the a axis.

N,N,N',N'-Tetra-methyl-phthalamide.

The title compound, C(12)H(16)N(2)O(2), crystallized from toluene with two independent mol-ecules in the asymmetric unit. The dihedral angles between the amide groups and the benzene ring are 60.87 (11) and 54.08 (11)° in one independent molecule and 60.13 (11) and 64.64 (11) in the other. The crystal structure features weak C-H⋯O hydrogen bonds and C-H⋯π inter-actions.

Aqua-bis-[N'-(1,3-dithio-lan-2-ylidene)-2-hy-droxy-benzohydrazidato(0.5-)-κ(2)N',O]sodium(I).

The title compound, [Na(C(10)H(9.5)N(2)O(2)S(2))(2)(H(2)O)], is a mol-ecular sodium complex with N'-(1,3-dithio-lan-2-yl)-2-hy-droxy-benzohydrazide ligands with the negative charge spread evenly over both, and a water mol-ecule. The Na(I) ion coordination is distorted trigonal-bipyramidal, formed by two N and three O atoms, with the Na(I) ion lying on a twofold rotation axis. Intra-molecular N-H⋯O hydrogen bonds occur. Mol-ecules pack as discrete units and the crystal packing is stabilized by strong O-H⋯O hydrogen bonds, which give rise to chains along [010]; the chains are inter-linked by strong O-H⋯O hydrogen bonds.