Reversible isomerization of chromogenic dimers and the nature of azulene chromaticity

The spectra of azulene solutions in siloxane and heptadecane were studied. The VIS band (435–714 nm) associated with the color blue was shown to transform reversibly as a result of a temperature increase and to assume a likeness to the less intensive VIS band typical for solutions in polar ethanol and dibutyl phthalate. It was concluded that supramolecular dimers rather than individual molecules are the chromogens of azulene, just as in the case of phthalocyanine, triphenylmethane, xanthene, and thiazine dyes. Clar’s conclusions regarding the nature of the visible band of azulene absorption and the mechanism of reversible thermal discoloration of azulene solutions in high-boiling-point hydrocarbons are consequently wrong. It was established that the thermochromism of azulene solutions is actually not associated with the isomerization of azulene molecules into nonplanar nonaromatic molecules but with the reversible isomerization of dimeric structures, accompanied by a change in the positions of the aromatic molecules relative to one another. The corresponding equilibrium is somewhat endothermic: ΔH = 6.6 kJ/mol, ΔG ^o ≈ − 1.45 kJ/mol. Based on these results, it was concluded that light absorption changes the energetic state of the dimeric structures (transition S _D→ S _D^*) without leading to electron transfer in single molecules according to the scheme S ₀ →S ₁. That is, the traditional idea that Kasha’s law is violated when azulene fluoresces is incorrect, since the radiation comes from the S ₁ level and not from the S ₂ level, as is stated in the literature.     

Die Reduktion von Azulen mit Natrium zum Kontaktionen-Tripel [Dinatrium-(1,1′,6,6′-Tetrahydro-6,6′-bi(azulen)-1,1′-diid)–bis (diglyme)]∞

The Sodium Reduction of Azulene to the Contact-Ion Triple [Disodium-(1,1′,6,6′-Tetrahydro-6,6′-bi(azulene)-1,1′-diide)–bis(diglyme)]_∞ Colorless air-sensitive single crystals can be grown from a diglyme solution after the reduction of azulene by a Na-metal mirror. Structure determination at 150 K reveals a dimer dianion, in which the seven-membered rings are connected in 6,6′-positions and doubly diglyme-solvated Na⁺ counter cations η⁵-coordinate to the five-membered rings. Based on preceding cyclovoltammetric measurements in aprotic azulene solutions as well as on extensive MNDO enthalpy of formation calculations, a proposal is forwarded how possibly the contact ion triple is formed along a microscopic pathway.     

Similarities and differences in the structures of 5‐bromo‐6‐hydroxy‐7,8‐dimethylchroman‐2‐one and 6‐hydroxy‐7,8‐dimethyl‐5‐nitrochroman‐2‐one

The title compounds, C₁₁H₁₁BrO₃, (I), and C₁₁H₁₁NO₅, (II), respectively, are derivatives of 6‐hydroxy‐5,7,8‐trimethylchroman‐2‐one substituted at the 5‐position by a Br atom in (I) and by a nitro group in (II). The pyranone rings in both molecules adopt half‐chair conformations, and intramolecular O—H...Br [in (I)] and O—H...O_nitro [in (II)] hydrogen bonds affect the dispositions of the hydroxy groups. Classical intermolecular O—H...O hydrogen bonds are found in both molecules but play quite dissimilar roles in the crystal structures. In (I), O—H...O hydrogen bonds form zigzag C(9) chains of molecules along the a axis. Because of the tetragonal symmetry, similar chains also form along b. In (II), however, similar contacts involving an O atom of the nitro group form inversion dimers and generate R₂²(12) rings. These also result in a close intermolecular O...O contact of 2.686 (4) Å. For (I), four additional C—H...O hydrogen bonds combine with π–π stacking interactions between the benzene rings to build an extensive three‐dimensional network with molecules stacked along the c axis. The packing in (II) is much simpler and centres on the inversion dimers formed through O—H...O contacts. These dimers are stacked through additional C—H...O hydrogen bonds, and further weak C—H...O interactions generate a three‐dimensional network of dimer stacks.     

Molecular complexes of dimethyl sulfoxide with tri‐ and dichloromethane

Crystals of molecular complexes of dimethyl sulfoxide with trichloromethane (chloroform), (CH₃)₂SO·2CHCl₃, (I), and dichloromethane, (CH₃)₂SO·CH₂Cl₂, (II), have been grown in situ. In both compounds, the components are linked together by (Cl)C—H...O interactions. The dimethyl sulfoxide molecules in (I) are bound into chains by C—H...O interactions. In (II), pairs of the components form centrosymmetric rings, linked into a three‐dimensional network by C—H...O contacts and dipole–dipole interactions between dimethyl sulfoxide molecules.     

Van der Waals complexes of polar aromatic molecules: unexpected structures for dimers of azulene

Full geometry optimizations at the dispersion corrected DFT-BLYP/TZV2P level of theory have been performed for dimers of azulene that may serve as a model system for the van der Waals complexes of polar pi systems. The structures and binding energies for 11 dimers are investigated in detail. The DFT-D interaction energies have been successfully checked against results from the accurate SCS-MP2/aug-cc-pVTZ approach. Out of the nine investigated stacked complexes, eight have binding energies larger than 7.4 kcal/mol (SCS-MP2) that exceed the value of 7.1 kcal/mol for the best naphthalene dimer. T-shaped arrangements (CH...pi) are significantly less stable. Two out of the three best structures have an antiparallel alignment of the monomer dipole moments in the complex, although the best ones with a parallel orientation are only about 0.5 kcal/mol less strongly bound which points to a minor importance of dipole-dipole interactions to binding. Quite surprisingly, the energetically lowest structure (DeltaE = -9.2 kcal/mol) corresponds to a situation where the two seven-membered rings are located almost on top of each other (7-7) and the long molecular axes are rotated against each other by 130 degrees. The 7-7 structural motif is found also in other energetically low-lying structures, and the expected 5-7 (two-side) arrangement is less strongly bound by about 2 kcal/mol. This can be explained by the electrostatic potential of azulene that only partially reflects the charge separation according to the common 4n + 2 pi electron rule. General rules for predicting stable van der Waals complexes of polar pi systems are discussed.     

Azulene-Indole Fused Polycyclic Heteroaromatics

Linear polycyclic systems are promising candidates in the area of organic electronics. Herein, we present the syntheses of three azulene-indole (AzIn) fused polycyclic heteroaromatics (PHAs), AzIn - 1 , AzIn - 2 and DGAzIn , which have nitrogens and nonhexagonal rings simultaneously. The chemical structures, optical and electrochemical properties of three AzIn-based PHAs have been investigated, as well as their protonation behaviors with trifluoroacetic acid (TFA). All three AzIn-based PHAs exhibit narrow optical band gaps with moderate to good air stability, anti-Kasha emission and reversible stimuli-responsiveness. Furthermore, these straightforward and simple synthetic routes would provide a new entry for constructing novel azulene-embedded π-conjugates, especially for the seven-membered ring of azulene unit, wherein the regioselective transformation is not well developed.     

Vibronic spectral behavior of molecules. XIII. Theoretical contribution to the vibronic coupling and the dushinsky effect on the S1 ← S0 absorption and the S1 → S0, S2 → S1, and S2 → S0 fluorescences of azulene

Based on the completely optimized S₀, S₁, and S₂ molecular geometries of azulene, the vibronic structure of the S₁ ← S₀ absorption as well as of the S₁ → S₀, S₂ → S₁, and S₂ → S₀ fluorescences is investigated theoretically within the adiabatic approximation. By means of theory-experiment comparisons, the influence of non-Condon terms and of the Dushinsky effect on the vibronic structure of azulene spectral behavior is discussed. Typical for the S₁ ← S₀ absorption and the S₁ → S₀ fluorescence are vibronic transition moment contributions of Condon type, whereas the interpretation of azulene S₂ → S₁ and S₂ → S₀ fluorescences is successful only within the scope of the Herzberg–Teller approach by taking into account vibronic coupling terms and, additionally, the Dushinsky effect in the latter case. An analysis of the relevant vibrational modes is given.     

2‐[2‐(Pyrrolidin‐2‐yl)propan‐2‐yl]‐1H‐pyrrole and its amide derivative 1‐{2‐[2‐(1H‐pyrrol‐2‐yl)propan‐2‐yl]pyrrolidin‐1‐yl}ethanone

In the title compounds, C₁₁H₁₈N₂, (II), and C₁₃H₂₀N₂O, (III), the pyrrolidine rings have twist conformations. Compound (II) crystallizes with two independent molecules (A and B) in the asymmetric unit. The mean planes of the pyrrole and pyrrolidine rings are inclined to one another by 89.99 (11) and 89.35 (10)° in molecules A and B, respectively. In (III), the amide derivative of (II), the same dihedral angle is much smaller, at only 13.42 (10)°. In the crystal structure of (II), the individual molecules are linked via N—H...N hydrogen bonds to form inversion dimers, each with an R²₂(12) graph‐set motif. In the crystal structure of (III), the molecules are linked via N—H...O hydrogen bonds to form inversion dimers with an R²₂(16) graph‐set motif.     

Models of Molecular Structures of “Template” (5676)Macrotetracyclic 3<Emphasis Type="Italic">d</Emphasis> M(II) Chelates with a 16-Membered Macrocyclic Ligand according to Density Functional Theory Data

The geometries of (5676)macrotetracyclic Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with the (NNNN) coordination of the chelant donor sites, formed through template processes in the M(II)–3,3,8,8-tetramethyl-4,7-diazadecanedihydrazone-1,10-butanedione-2,3 systems have been calculated by the DFT OPBE/TZVP method with the Gaussian 09 program package. The bond lengths and angles and selected nonbonded angles in these complexes with the MN₄ chelate core have been determined. It has been demonstrated that none of the chelate rings is planar: the smallest deviation from coplanarity is always observed for the five-membered rings and the largest, for the six-membered rings not identical to each other. The seven-membered ring resulting from the template cross-linking exhibits deviations from coplanarity intermediate between those for the five- and six-membered rings.     

A new polymorph of 1‐ferrocenyl‐3‐(3‐nitroanilino)propan‐1‐one

Recrystallization of the title compound, [Fe(C₅H₅)(C₁₄H₁₃N₂O₃)], from a mixture of n‐hexane and dichloromethane gave the new polymorph, denoted (I), which crystallizes in the same space group (P) as the previously reported structure, denoted (II). The Fe—C distances in (I) range from 2.015 (3) to 2.048 (2) Å and the average value of the C—C bond lengths in the two cyclopentadienyl (Cp) rings is 1.403 (13) Å. As indicated by the smallest C—Cg1—Cg2—C torsion angle of 1.4° (Cg1 and Cg2 are the centroids of the two Cp rings), the orientation of the Cp rings in (I) is more eclipsed than in the case of (II), for which the value was 15.3°. Despite the pronounced conformational similarity between (I) and (II), the formation of self‐complementary N—H...O hydrogen‐bonded dimers represents the only structural motif common to the two polymorphs. In the extended structure, molecules of (I) utilize C—H...O hydrogen bonds and, unlike (II), an extensive set of intermolecular C—H...π interactions. Fingerprint plots based on Hirshfeld surfaces are used to compare the packing of the two polymorphs.     

Constructive Quantum Interference in Single-Molecule Benzodichalcogenophene Junctions

Heteroatom substitution into the cores of alternant, aromatic hydrocarbons containing only even-membered rings is attracting increasing interest as a method of tuning their electrical conductance. Here, the effect of heteroatom substitution into molecular cores of non-alternant hydrocarbons, containing odd-membered rings, is examined. Benzodichalcogenophene (BDC) compounds are rigid, planar π-conjugated structures, with molecular cores containing five-membered rings fused to a six-membered aryl ring. To probe the sensitivity or resilience of constructive quantum interference (CQI) in these non-bipartite molecular cores, two C₂-symmetric molecules (I and II) and one asymmetric molecule (III) were investigated. I (II) contains S (O) heteroatoms in each of the five-membered rings, while III contains an S in one five-membered ring and an O in the other. Differences in their conductances arise primarily from the longer S−C and shorter O−C bond lengths compared with the C−C bond and the associated changes in their resonance integrals. Although the conductance of III is significantly lower than the conductances of the others, CQI was found to be resilient and persist in all molecules.     

X‐(Diiodoarsanyl)benzoic acid (X = 3 and 4)

The title compounds, 4‐(diiodoarsanyl)benzoic acid, (I), and 3‐(diiodoarsanyl)benzoic acid, (II), both [As(C₇H₅O₂)I₂], which possess a –COOH coordinating group, form molecular crystal structures composed of hydrogen‐bonded dimers, the packing differences of which are caused by the relative position of the diiodoarsanyl groups. The para isomer, with Z′ = 1, crystallizes in a layered structure with shortened contacts of the As atoms to only the arene rings of adjacent molecules. In contrast, the meta isomer, with Z′ = 3, forms separate rectangular blocks of three ribbons, each composed of dimeric molecular units positioned almost directly above each other and with the As atoms possessing only two As...I contacts to the I atoms of neighbouring molecules.     

Three 1‐phenylindolin‐2‐one derivatives displaying different molecular dipole moments and different crystallographic symmetries

Three 1‐phenylindolin‐2‐one derivatives, namely 1‐phenylindolin‐2‐one, C₁₄H₁₁NO, (I), 5‐bromo‐1‐phenylindolin‐2‐one, C₁₄H₁₀BrNO, (II), and 5‐iodo‐1‐phenylindolin‐2‐one, C₁₄H₁₀INO, (III), have been synthesized and their structures determined. Compounds (I) and (II) crystallized in the centrosymmetric space groups Pbca and P2₁/c, respectively, while compound (III) crystallized in the polar space group Aea2. Density functional theory (DFT) calculations show that the molecular dipole moment gradually decreases in the order (I) > (II) > (III). The relatively smaller dipole moment of (III) and the larger non‐electrostatic intermolecular interactions may be the main reasons for the noncentrosymmetric and polar structure of (III).     

Two isomeric butadiene–N‐(acetoxy­phenyl)maleimide Diels–Alder adducts: supramolecular structure directed by C—H⋯X (X = O and π) hydrogen bonds and perpendicular dipole carbonyl–carbonyl inter­actions

The mol­ecular and supramolecular structures of 2‐(1,3‐dioxo‐2,3,3a,4,7,7a‐hexa­hydro‐1H‐isoindol‐2‐yl)phenyl acetate, C₁₆‐H₁₅NO₄, (I), and its para isomer, 4‐(1,3‐dioxo‐2,3,3a,4,7,7a‐hexa­hydro‐1H‐isoindol‐2‐yl)phenyl acetate, (II), are reported. The torsion angle between the succinimide and benzene rings depends on the position of the acet­oxy substitution [89.7 (1) and 61.9 (1)° for (I) and (II), respectively]. The twist of the acet­oxy group relative to the mean plane of the benzene ring is almost independent of the acet­oxy position [66.0 (1) and 70.0 (1)°]. Packing inter­actions for both compounds include soft C—H⋯X (X = O and Ph) inter­actions, forming chains of centrosymmetric dimers and inter­linked chains for (I) and (II), respectively. In addition, three perpendicular dipole C=O⋯C=O inter­actions contribute to the supramolecular structure of (II).     

Dipole‐Induced Band‐Gap Reduction in an Inorganic Cage

Metal‐doped polyoxotitanium cages are a developing class of inorganic compounds which can be regarded as nano‐ and sub‐nano sized molecular relatives of metal‐doped titania nanoparticles. These species can serve as models for the ways in which dopant metal ions can be incorporated into metal‐doped titania (TiO₂), a technologically important class of photocatalytic materials with broad applications in devices and pollution control. In this study a series of cobalt(II)‐containing cages in the size range ca. 0.7–1.3 nm have been synthesized and structurally characterized, allowing a coherent study of the factors affecting the band gaps in well‐defined metal‐doped model systems. Band structure calculations are consistent with experimental UV/Vis measurements of the Ti_xO_y absorption edges in these species and reveal that molecular dipole moment can have a profound effect on the band gap. The observation of a dipole‐induced band‐gap decrease mechanism provides a potentially general design strategy for the formation of low band‐gap inorganic cages.     

Two N‐(2‐phenylethyl)nitroaniline derivatives as precursors for slow and sustained nitric oxide release agents

Notwithstanding its simple structure, the chemistry of nitric oxide (NO) is complex. As a radical, NO is highly reactive. NO also has profound effects on the cardiovascular system. In order to regulate NO levels, direct therapeutic interventions include the development of numerous NO donors. Most of these donors release NO in a single high‐concentration burst, which is deleterious. N‐Nitrosated secondary amines release NO in a slow, sustained, and rate‐tunable manner. Two new precursors to sustained NO‐releasing materials have been characterized. N‐[2‐(3,4‐Dimethoxyphenyl)ethyl]‐2,4‐dinitroaniline, C₁₆H₁₇N₃O₆, (I), crystallizes with one independent molecule in the asymmetric unit. The adjacent amine and nitro groups form an intramolecular N—H…O hydrogen bond. The anti conformation about the phenylethyl‐to‐aniline C—N bond leads to the planes of the arene and aniline rings being approximately perpendicular. Molecules are linked into dimers by weak intermolecular N—H…O hydrogen bonds such that each amine H atom participates in a three‐center interaction with two nitro O atoms. The dimers pack so that the arene rings of adjacent molecules are not parallel and π–π interactions do not appear to be favored. N‐(4‐Methylsulfonyl‐2‐nitrophenyl)‐l ‐phenylalanine, C₁₆H₁₆N₂O₆S, (II), with an optically active center, also crystallizes with one unique molecule in the asymmetric unit. The l enantiomer was established via the configuration of the starting material and was confirmed by refinement of the Flack parameter. As in (I), there is an intramolecular N—H…O hydrogen bond between adjacent amine and nitro groups. The conformation of the molecule is such that the arene rings display a dihedral angle of ca 60°. Unlike (I), molecules are not linked via intermolecular N—H…O hydrogen bonds. Rather, the carboxylic acid H atom forms a classic, approximately linear, O—H…O hydrogen bond with a sulfone O atom. Pairs of molecules related by twofold rotation axes are linked into dimers by two such interactions. The packing pattern features a zigzag arrangement of the arene rings without apparent π–π interactions. These structures are compared with reported analogues, revealing significant differences in molecular conformation, intermolecular interactions, and packing that result from modest changes in functional groups. The structures are discussed in terms of potential NO‐release capability.     

Laser-induced fluorescence studies of HfF+ produced by autoionization

Autoionization of Rydberg states of HfF, prepared using the optical-optical double resonance technique, holds promise to create HfF(+) in a particular Zeeman level of a rovibronic state for an electron electric dipole moment search. We characterize a vibronic band of Rydberg HfF at 54 cm(-1) above the lowest ionization threshold and directly probe the state of the ions formed from this vibronic band by performing laser-induced fluorescence on the ions. The Rydberg HfF molecules show a propensity to decay into only a few ion rotational states of a given parity and are found to preserve their orientation qualitatively upon autoionization. We show empirically that we can create 30% of the total ion yield in a particular ∣J(+), M(+) state and present a simplified model describing autoionization from a given Rydberg state that assumes no angular dynamics.