Coronenohelicenes with Dynamic Chirality

The synthesis of a new type of chiral and dynamic nonplanar aromatics containing a combination of fused perylene-based coronenes and helicenes is reported. Either one or two helicene moieties were fused to the bay regions of an extended perylene core. The target compounds contain either identical or two different helicene building blocks. The combination with two helicene units leads to six different isomers, including two pairs of enantiomers and two meso forms. The experimental determination of the isomerization barriers the corresponding double [5]-helicenes revealed activation energies of E_a=24.81 and 25.38 kcal mol⁻¹, which is slightly above the barrier of the parent [5]-helicene. Resolution of all possible regio- and stereoisomers allowed for the systematic investigation of the chiroptical properties. They revealed remarkable dissymmetry factors Ig_absI of up to 1.2×10⁻², which mirror the synergy between the strong absorbing perylenes and the inherent chirality of helicenes.     

(BO)2-Doped Tetrathia[7]helicene: A Configurationally Stable Blue Emitter

Helicenes combine two central themes in chemistry: extended π-conjugation and chirality. Hetero-atom doping preserves both characteristics and allows modulation of the electronic structure of a helicene. Herein, we report the (BO)₂-doped tetrathia[7]helicene 1 , which was prepared from 2-methoxy-3,3′-bithiophene in four steps. 1 is formally derived by substituting two (Mes)B−O moieties in place of (H)C=C(H) fragments in two benzene rings of the parent tetrathia[7]helicene. X-ray crystallography revealed a dihedral angle of 50.26(9)° between the two terminal thiophene rings. The (P)-/(M)- 1 enantiomers were separated by chiral HPLC and are configurationally stable at room temperature. The experimentally determined enantiomerization barrier of 27.4±0.1 kcal mol⁻¹ is lower than that of tetrathia[7]helicene (39.4±0.1 kcal mol⁻¹). The circular dichroism spectra of (P)- and (M)- 1 show a perfect mirror-image relationship. 1 is a blue emitter (λ_em=411 nm) with a photoluminescence quantum efficiency of Φ_PL=6 % (cf. tetrathia[7]helicene: λ_em≈405 nm, Φ_PL=5 %).     

Supramolecular structural and spectral perspectives of novel ruthenium(III) azodye complexes

Five bis-[5-(4′-R-phenylazo)-8-hydroxyquinoline] ruthenium complexes [RuLn?·?Cl₂?·?OH₂]; where Ln?=?5-(4′-R-phenylazo)-8-hydroxyquinolinol, R?=?OCH₃ (n?=?1), CH₃(2), H(3), Cl(4), NO₂(5), have been prepared and characterized on the basis of elemental analyses, IR, ¹H NMR, ESR, thermal analysis and magnetic susceptibility measurements. The data show that these complexes exist in trans-isomeric solid form. Two inversion-related ligands and two Ru³⁺ atoms form a cage-like dimer. Both ligands of the dimer are bridged by a pair of inversion-related Ru–N (azodye) bonds. The octahedral coordination geometry of Ru³⁺ is made up of an N of pyridine, the deprotonated quinoline O atom, one of the azodye N atoms, two chlorides and one water. The ligands in the dimer are stacked over one another. In the solid state of azo-8-hydroxyquinoline, the dimers have inter-and intramolecular hydrogen bonds. Interactions between the ligands and the metal are discussed. The azo group was involved in chelation for all the prepared complexes. The effect of Hammet's constant on the ligand field parameters are also discussed and drawn.     

Cyclobishelicenes: Shape-Persistent Figure-Eight Aromatic Molecules with Promising Chiroptical Properties

Cyclobis[n]helicenes (n=3 or 5) are chiral D₂-symmetric π-conjugated macrocycles with stable lemniscular, or figure-eight, shapes. The conformational analysis of five different cyclobis[n]helicenes revealed that these molecules can only exist as their lemniscular conformers with high barriers to enantiomerization (>200 kJ mol⁻¹). The enantiomers of a cyclobis[5]helicene were resolved by HPLC and their unusual chiroptical properties were attributed to the inherent chirality of their macrocyclic figure-eight.     

The structure and magnetic properties of the di-μ-pyrazolate complex [Cu2(PEAH2)2(NO3)(H2O)](NO3)[PEAH3 = 3,5-bis-(N-ethylamido) pyrazole]

Summary A complex of the formula[Cu₂(PEAH₂)₂(NO₃)(H₂O)]-(NO₃)[PEAH₃ = 3,5-bis(N-ethylamido) pyrazole] was synthesized and its crystal structure determined by XRD methods. It consists of a dimeric cation with two bridging pyrazolate groups and a NO ₃ ^– anion. The geometries of the coordination polyhedra around the copper(II) ions are distorted square pyramidal. The variable temperature (20–300 K) magnetic susceptibility data gave the antiferromagnetic interaction constant as J=-191cm^–1, showing that the pyrazole molecule is very effective in transmitting the exchange interaction.     

The synthesis of new azoniathiahelicenes

Synthesis of new azonia derivatives of thia[6]helicene ( 1 ) and thia[7]helicene ( 2 ) is described. The Knoevenagel condensation of 2‐methylbenzothieno[3,2‐a]quinolizinium salt ( 8 ) with appropriate arylaldehydes yielded 2‐(arylvinyl)benzothieno[3,2‐a]quinolizinium salts ( 9 and 10 ), respectively. Photocyclization of 2‐styrylbenzothieno[3,2‐a]quinolizinium salt ( 8 ) gave 7a‐azonia‐5‐thia[6]helicene ( 1 ) in 63% yield. Similarly, 2‐[2‐(2‐naphthyl)vinyl]benzothieno[3,2‐a]quinolizinium salt ( 10 ) afforded 7a‐azonia‐5‐thia[7]helicene ( 2 ) in 56% yield. The complete and unambiguous assignment of their ¹H‐ and ¹³C‐nmr spectra was performed by utilizing two‐dimensional nmr spectroscopic methods.     

Synthesis and physiochemical studies on binuclear Cu(II) complexes derived from 2,6-[(N-phenylpiperazin-1-yl)methyl]-4-substituted phenols

Preparation of the ligands HL¹ = 2,6-[(N-phenylpiperazin-1-yl)methyl]-p-ethylphenol; HL² = 2,6-[(N-phenylpiperazin-1-yl)methyl]-p-methoxyphenol and HL³ = 2,6-[(N-phenylpiperazin-1-yl)methyl]-p-nitrophenol are described together with their Cu(II) complexes with different bridging units. The exogenous bridges incorporated into the complexes are: hydroxo [Cu₂L(OH)(H₂O)₂](ClO₄)₂.H₂O (L¹=1a, L² =1b, L³ =1c), acetato [Cu₂L(OAc)₂]ClO₄.H₂O (L¹ =2a, L² =2b, L³ =2c) and nitrito [Cu₂L¹(NO₂)₂(H₂O)₂]ClO₄.H₂O (L¹=3a, L² =3b, L³ =3c). Complexes1a,1b,1c and2a,2b,2c contain bridging exogenous groups, while3a,3b,3c possess only open μ-phenolate structures. Both the ligands and complexes were characterized by spectral studies. Cyclic voltammetric investigation of these complexes revealed that the reaction process involves two successive quasireversible one-electron steps at different potentials. The first reduction potential is sensitive to electronic effects of the substituents at the aromatic ring of the ligand system, shifting to positive potentials when the substituents are replaced by more electrophilic groups. EPR studies indicate very weak interaction between the two copper atoms. Various covalency parameters have been calculated.     

Interactions intramoléculaires. XXVI—Constantes de couplage et hétérogénéités conformationnelles dans une série de R-3 et R-5 cyano-4 cyclohexènes deutériés (R=méthyl ou t-butyl)

For trans-3-R- and 5-R-1-acetoxy-4-cyanocyclohexene-6,6-d₂ the molar fractions of diequatorial conformers are 0.83 (3-methyl), 0.68 (5-methyl), 0.57 (3-tert-butyl) and 0.55–0.69 (5-tert-butyl). For the last two compounds the values of the coupling constants are in agreement with the hypothesis of an ee?aa equilibrium. For the cis isomers, the molar fractions of equatorial alkyl conformers are 0.76 (3-methyl and 5-methyl) and 1.0 (3-tert-butyl and 5-tert-butyl). The cis-1-acetoxy-3-tert-butyl-4-methoxycarbonyl-cyclohexene presents a conformational heterogeneity. The conformational free energy of the methyl group in position 4 has been evaluated as ?0.6 kcal mol^?1 (2.5 kJ mol^?1).     

Zinc(II) and cadmium(II) complexes having racemic and enantiomeric ligands: [Zn(La)2](NO3)2 · CH3CH2OH and [Cd(Lb)2Cl](ClO4) (La = D,L and Lb = D-(+)-1,2, 2-trimethylcyclopentane-1,3-diamine)

Two d¹⁰ transition-metal complexes having racemic and enantiomeric 1,2,2-trimethylcyclopentane-1,3-diamine ligands, [Zn(L_a)₂](NO₃)₂ · CH₃CH₂OH (1) and [Cd(L_b)₂Cl](ClO₄) (2) (L_a = D,L-1,2,2-trimethylcyclopentane-1,3-diamine, L_b = D-(+)-1,2,2-trimethylcyclopentane-1,3-diamine or (1R,3S)-1,2,2-trimethylcyclopentane-1,3-diamine), were synthesized and characterized by X-ray single-crystal diffraction. They crystallize in the Pbca and P2₁2₁2₁ space groups, respectively, and have different coordination numbers and coordination geometry (four-coordinate tetrahedron for Zn(II) in 1 and five-coordinate square-based pyramid for Cd(II) in 2) mainly due to their different ionic radii.     

Structural and Spectroscopic Investigations of the 1:1 Complex between Europium Nitrate and a Tetraoxadiaza Macrocycle

The crystal and molecular structure of dinitrato(1,7,10,16-tetraoxa-4,13-diazacyclooctadecane)europium(III) nitrate, ([Eu(NO₃)₂(C₁₂H₂₆N₂O₄)]NO₃) has been determined from single-crystal X- ray diffraction: a = 12.567(3), b = 11.585(3), c = 16.354(5) Å, β = 112.45(2)°, space group P2₁/n, Z = 4. The structure consists of discrete dinitrato complex cations and of nitrate anions. The Eu(III) ion is 10-coordinate, bonding to the six donor atoms of the macrocycle and to four O-atoms of the two bidentate nitrates. The mean distances are Eu? O(ether) = 2.60(2), Eu? O(NO₃) = 2.47(3) and Eu? N = 2.62(2) Å. The metal site has an approximate C₂ symmetry. The IR and Raman spectra show the presence of an ionic and of two bonded bidentate nitrates. These latter have a different v₁-v₄ splitting, which reflects their dissymmetrical bonding. Luminescence spectra have been recorded at 296, 77, and 4 K by laser-excitation techniques. One sharp ⁵D₀←⁷F₀ transition was observed and almost all the sublevels of the ⁷F_J manifold could be identified. The interaction between a sharp distribution of the phonon states (especially between 950 and 1200 cm^?1) and the electronic ⁷F₂ sublevels results in the presence of several satellite lines accompanying the ⁵D₀→⁷F₂ transition. In MeCN solutions, both luminescence and conductivity data point to the presence of the [Eu(NO₃)₂(2,2)]⁺ cation.     

Synthesis and spectroscopic characterization of palladium(II) complexes with 6,8-dimethylimidazo[1,5- a ]-1,3,5-triazin-4( 3H )-one and 6,8-dimethyl-2-thioxo-2,3-dihydroimidazo-[1,5- a ]-1,3,5-triazin-4( 1H )-one

The preparation and spectroscopic study (¹H, ¹³C, ¹⁵NNMR, ¹³CP MAS NMR, IR) of new Pd^II complexes with 6,8-dimethylimidazo[1,5-a]-1,3,5-triazin-4(3H)-one (6,8-DiMe-4-O-IMT) (1) and 6,8-dimethyl-2-thioxo-2,3-dihydroimidazo[1,5-a]-1,3,5-triazin-4(1H)-one (6,8-DiMe-4-O-2-S-IMT) (2) is reported. The spectroscopic data indicate a square planar geometry with two N(7) bonded heterocycles and two cis-chloride anions. The final product of the thermal decomposition of cis-PdCl₂(6,8-DiMe-4-O-IMT)₂ (3) is metallic Pd, whereas for cis-PdCl₂(6,8-DiMe-4-O-2-S-IMT)₂ (4) it is metallic Pd plus C.     

Crystal and molecular structure of 1,1′-<Emphasis Type="Italic">bis</Emphasis>-(acetoacetyl)ferrocene

Using physicochemical methods, the crystal and molecular structure of 1,1-bis-(acetoacetyl)ferrocene is studied. The compound crystallizes in the form of two crystallographically independent molecules with slightly different conformations and mutually perpendicular orientation. Crystals are monoclinic, C₁₈H₁₈FeO₄, a = 35.68(1) ?, b = 5.733(2) ?, c = 30.30(1) ?; β = 96.831(5)°; V= 6154(3) ?³, Z= 16, d_x = 1.529 g/cm³, C2/c space group. The molecule consists of the ferrocene fragment and two acetylacetonyl substituents.     

Synthesis, Conformational Studies and Inclusion Properties of Tetrakis[(2-pyridylmethyl)oxy]thiacalix[4]arenes

An attempted O-alkylation of the flexible macrocycle 1with 2-(chloromethyl)pyridine in the presence of Cs₂CO₃ under THF reflux afforded a mixture of twoconformers of tetra-O-alkylated product 4a in a ratio of 91:9 (cone-4a:1,2-alternate-4a)in 70% yield, while other possible isomers were not observed. In the case of Na₂CO₃, there was no reaction product,only the starting compound 1, whereasonly monoalkylated compound 3 was obtained when usingK₂CO₃ as the base. The distribution of cone conformer decreased in the case of O-alkylation of tetraol 1with 4-(chloromethyl)pyridine or benzyl bromide in the presence of Cs₂CO₃ in comparison with that ofO-alkylation with 2-(chloromethyl)pyridine, while the 1,2-alternate conformer increased in the same sequence. The larger Cs⁺might increase the contribution of the metal template effect, which can hold the 2-pyridylmethyl group(s) and theoxide group(s) on the same side of the tetrathiacalix[4]arene 1 through the cation-O^- and -N-interaction in the caseof O-alkylation of tetraol 1 with 2-(chloromethyl)pyridine.Only when the template metal can hold the 2-pyridyl group(s) andthe oxide group(s) on the same side of the tetrathiacalix[4]arene is the conformation immobilized to thecone. The template effect of the cesium cation plays an important role in this alkylation reaction. The structuralcharacterization of these products is also discussed.The two-phase solvent extraction data indicated thattetrakis[(2-pyridylmethyl)oxy]thiacalix[4]arenes 4a show strong Ag⁺ affinity and a high Ag⁺ selectivity wasobserved for cone-4a. A good Job plot proves 1:1 coordination of cone-4a with Ag⁺ cation.¹H-NMR titration of cone-4a with AgSO₃CF₃ also clearly demonstrates that a 1:1complex is formed with retention of the original symmetry. In contrast, the 1,2-alternate-4a can form a 2:1 metal/thiacalix[4]arene complex and the two metal-binding sites display positive allostericity. The conformational changes ofpyridine moiety from the original outward orientation of the ring nitrogen to the inside orientation toward thethiacalixarene cavity were observed in the processof Ag⁺ complexation.     

Micellar Exchange Kinetics of Quaternary Ammonium Type Gemini Surfactants Monitored by Nuclear Magnetic Resonance

The dynamic NMR (DNMR) method was used to detect kinetic parameters of the molecular exchange process between monomers in bulk solution and those in the micelle for Gemini surfactants, 12-s-12 and 14-s-14(s=2, 3 and 4).The escape rate constant, k^-, was derived based on the simplified equations of DNMR theory, and the apparent activation energy of escape, E_a^-, was obtained based on the Arrhenius equation through temperature variation experiments.Results show that the orders of magnitude of k^- for 14-s-14 and 12-s-12 are respectively 10 and 10³ s^-1, E_a^- of 14-s-14 and 12-s-12 are respectively 54.04-73.64 and 33.42-47.09 kJ/mol.Furthermore, increases and E_a^- decreases with the spacer length growing.In combination with the micro-polarity measurements, it was revealed that molecules of 14-s-14 and 12-s-12 have to experience conformation changes when escaping from the micelles.The two-step molecular exchange mechanism for Gemini surfactants was therefore supported.     

New results in the ammonolysis of hexafluoro-cyclo-triphosphazene: Crystal structure of P3N3F5–NH–P3N3F4NH2

The reaction of hexafluoro-cyclo-triphosphazene P₃N₃F₆ with ammonia in acetonitrile has been studied. New compounds, (2-imino-2,4,4,6,6-pentafluoro-2λ⁵,4λ⁵,6λ⁵-cyclo-triphosphaza-1,3,5-trienyl)-2-amino-4,4,6,6-tetrafluoro-2λ⁵,4λ⁵,6λ⁵-cyclo-triphosphaza-1,3,5-triene, P₃N₃F₅–NH–P₃N₃F₄NH₂ (2) and cis and trans isomers of non-gem-2,4-diamino-2,4,6,6-tetrafluoro-2λ⁵,4λ⁵,6λ⁵-cyclo-triphosphaza-1,3,5-triene, P₃N₃F₄(NH₂)₂ (4, 5)_, were detected by GC/MS, and ³¹P NMR spectroscopy in reaction mixtures. X-ray diffraction analysis of P₃N₃F₅–NH–P₃N₃F₄NH₂ (2) revealed two conformational polymorphs, 2A and 2B, the latter being built up of two different conformers that were further denoted as 2B_a (the same as the single conformer in 2A) and 2B_b. The compound 2 was characterized by spectroscopic methods and its 2D potential energy surface (PES) was described by density functional theory computations depending on two dihedral angles. The calculated PES spans over 30 kJ/mol in energy including 8 local minima and all first and second order saddle points. The occurrence of the two experimentally observed conformers 2B_a and 2B_b seems to be governed by crystal packing effects.     

Chemistry of Ruthenium Polypyridine Complexes: VI. Synthesis and Photochemistry of cis-[Ru(bpy)2(bipy)X]q Complexes

Complexes cis-[Ru(bpy)₂(bipy)(X)] ^{n +} [bpy = 2,2'-bipyridyl, bipy = 4,4'-bipyridyl, X = Br^-, ONO^-, CN^- (n = 1); MeCN, PPh₃ (n = 2), and NO⁺ (n = 3)] were synthesized. Irradiation of acetonitrile solutions of the complexes with X = Cl^-, Br^-, ONO^-, NO₂-, CN^-, NH₃, MeCN, and PPh₃ by visible light results in photosubstitution of 4,4'-bipyridyl by a solvent molecule. The electronic absorption spectra of the complexes were assigned on the basis of quantum-chemical calculations. A correlation was revealed between photolysis quantum yields and charges transferred from ligands X upon their coordination.     

Structure,Magnetic and Spectral Properties of Ethyl Phosphite Nitrate Tri(1,10-phenanthroline) Nickel(II) Solvate Trihydrate: [Ni(phen)3]NO3·C2H5OP(O)O·3H2O

The compound, [Ni(phen)₃]NO₃ · C₂H₅OP(O)O · 3H₂O, was obtained by the reaction of Ni(NO₃)₂, C₂H₅OP(OH)₂ and 1,10-phenanthroline in 95% EtOH solution, and was characterized using IR and UV spectra and magnetic susceptibility measurements over the temperature range 75-300 K. The red crystal is triclinic of space group P&1macr;, with lattice parameters a = 12.462(3), b = 13.416(3), c = 13.422(3) Å, f = 75.88(3), g = 64.75(3), n = 65.87(3)°, and Z = 2. The coordinated cation contains a six-coordinate nickel atom chelated by three phenanthroline ligands, resulting in a distorted octahedral arrangement with the six Ni-N distances ranging from 2.086(2) to 2.113(3) Å. In addition to the nickel coordination complex, there are two anions, NO₃ and C₂H₅OP(O)O^-, and three water molecules which complete the crystal structure. In the solid state, the title compound forms a three dimensional network structure through hydrogen bonds. The intermolecular hydrogen bonds connect the [Ni(phen)₃]²⁺, NO₃, C₂H₅OP(O)O^- and H₂O molecules.     

Conformational analysis of 2-halocyclopentanones by NMR and IR spectroscopies and theoretical calculations

The conformational isomerism of 2-chlorocyclopentanone and 2-bromocyclopentanone has been determined through the solvent dependence of the ¹H NMR ³J_HH coupling constants, theoretical calculations and infrared data, using the solvation theory for the treatment of NMR data. In 2-chlorocyclopentanone, the energy difference (E_Ψ-e − E_Ψ-a), in the isolated molecule at B3LYP level of theory, between the pseudo-equatorial (Ψ-e) and pseudo-axial (Ψ-a) conformers is 0.42 kcal mol⁻¹, which decreases in CCl₄ and in acetonitrile solutions, in good agreement with infrared data (ν_CO), despite the uncertainties of the latter method. The conformational equilibrium for 2-bromocyclopentanone is also between the Ψ-e and Ψ-a conformations, with an energy difference (E_Ψ-e − E_Ψ-a), in the isolated molecule at B3LYP level of theory, is 0.85 kcal mol⁻¹ which decreases in CCl₄ and in acetonitrile solutions, also in good agreement with infrared data.     

Structural and Luminescence Study of the 3:2 Complex between Europium Nitrate and the B Isomer of Dicyclohexyl-18-crown-6

The crystal and molecular structure of bis[dinitrato-(2,4,8,15,18,21-hexaoxatricyclo[20.4.0.0^9,14]hexacosane)europium(III)]pentakis(nitrato)europiate(III) [Eu(NO₃)₂L_B]₂([Eu(NO₃)₅]), has been determined at 170 K from single-crystal X-ray diffraction. The complex crystallizes in the monoclinic space group P2₁/n (ITC No. 14): a = 16.338(3) Å, b = 15.704(3) Å, c = 24.474(4) Å, β = 97.73(1)°, Z = 4. The structure was refined to a final R value of 0.058 (R_w = 0.060). The asymmetric unit contains three independent ions lying on general positions: [Eu(NO₃)₅]^2? and two distinct [Eu(NO₃)₂L_B]⁺ cations with the macrocyclic ligand in the cis-anti-cis conformation (B-isomer). The Eu^IIIions are 10-coordinate with the following mean bond lengths: Eu–O(nitrate) = 2.48(2) Å in the anion and 2.45(2) Å in the two cations, Eu–O(ether) = 2.56(8) and 2.55(5) Å. Small but significant differences are observed between the two complex cations, especially with respect to the positions of the cyclohexyl substituent. A conformational analysis performed on the six O-atoms of the complex cations confirms the predictions of a simple model. The metal ion sites of the complex have been probed by high-resolution excitation and emission spectra at 296 and 77 K. The ⁵D₀←⁷F₀ excitation spectrum displays two main bands along with several other minor components. A detailed analysis of the corresponding and selectively excited emission spectra leads to the observation of three types of spectra corresponding to the three crystallographically different Eu^III ions. Moreover, three minor sites are identified, one anionic and two cationic, with a population equal to ca. 10% of the population of the main sites. We interpret this finding as reflecting the presence of molecules with slightly different conformations.