Bowl-Shaped Kekulene Analogues: Cycloarenes with two Five-Membered Rings.

Kekulene, a cycloarene composed of 12 fused benzene rings in a circular arrangement, exhibits a highly planar and robust structure. Kekulene has been the subject of investigation into its aromaticity and electronic structure, particularly in relation to the cyclic benzenoid. We have successfully synthesized novel bowl-shaped kekulene analogues with five-membered rings incorporated into the kekulene structure. The results of DFT calculations and VT-NMR spectra indicate that inversion of their concave-convex structures occurs at room temperature. The NICS and AICD plots predict that the Clar's type resonance structure is found in a manner analogous to the pristine kekulene, albeit with the interruption of the π-conjugation on the sp3 carbons at the five-membered rings. Despite the presence of the Clar's resonance structure, the Diels-Alder reaction proceeded smoothly with a dienophile, in contrast to the behavior of planar kekulene derivatives. This study will lead to the creation of novel bowl-shaped compounds and development of reactivity in aromatic compounds.

Synthesis of Hetero-Trimetal Porphyrin Nanobelts.

This work reported "trinitarian" porphyrin nanobelts, contained hetero-trimetal ions. The high-resolution mass spectrometry and X-ray crystallography proved PNBNiCuPd consisting of three different bent porphyrin(2.1.2.1) metal complex moieties. The redox properties indicate porphyrin nanobelts demonstrate the multielectron donating and accepting properties, more than nine redox processes.

Conflicting Aromaticity in Trirhodium(I) Rosarin.

Aromaticity is one of the most important and widely used concepts in chemistry. Among the various experimentally discovered and theoretically predicted compounds that possess different types of aromaticity, conflicting aromaticity, where aromatic and antiaromatic electron delocalization is present in one molecule simultaneously, remains one of the most controversial and elusive concepts, although theoretically predicted 15 years ago. In this work, we synthesized a novel conflicting aromatic trirhodium complex that contains a σ-aromatic metal fragment surrounded by the π-antiaromatic organic ligand and characterized it by nuclear magnetic resonance spectroscopy, high-resolution mass spectrometry, and X-ray single crystal structure analysis. Experimental characterization and quantum chemical calculations confirm the unique conflicting aromaticity of the synthesized trirhodium molecule. Thus, this novel conflicting aromatic molecule expands the family of aromatic compounds. This discovery will enable researchers to develop and understand the phenomena of conflicting aromaticity in chemistry.

Enhanced Four-Electron Oxygen Reduction Selectivity of Clamp-Shaped Cobalt(II) Porphyrin(2.1.2.1) Complexes.

The molecular structure, electrochemistry, spectroelectrochemistry and electrocatalytic oxygen reduction reaction (ORR) features of two CoII porphyrin(2.1.2.1) complexes bearing Ph or F5 Ph groups at the two meso-positions of the macrocycle are examined. Single crystal X-ray analysis reveal a highly bent, nonplanar macrocyclic conformation of the complex resulting in clamp-shaped molecular structures. Cyclic voltammetry paired with UV/Vis spectroelectrochemistry in PhCN/0.1 M TBAP suggest that the first electron addition corresponds to a macrocyclic-centered reduction while spectral changes observed during the first oxidation are consistent with a metal-centered CoII /CoIII process. The activity of the clamp-shaped complexes towards heterogeneous ORR in 0.1 M KOH show selectivity towards the 4e- ORR pathway giving H2 O. DFT first-principle calculations on the porphyrin catalyst indicates a lower overpotential for 4e- ORR as compared to the 2e- pathway, consistent with experimental data.

Synthesis, Characterization, and Electrochemistry of Copper Dibenzoporphyrin(2.1.2.1) Complexes.

Three copper dibenzoporphyrin(2.1.2.1) complexes having two dipyrromethene units connected through o-phenylen bridges and 4-MePh, Ph, or F5Ph substituents at the meso positions of the dipyrrins were synthesized and characterized according to their spectral, electrochemical, and structural properties. As indicated by the single-crystal X-ray structures, all three derivatives have highly bent molecular structures, with angles between each planar dipyrrin unit ranging from 89° to 85°, indicative of a nonaromatic molecule. The insertion of copper(II) into dibenzoporphyrins(2.1.2.1) induced a change in the macrocyclic cavity shape from rectangular in the case of the free-base precursors to approximately square for the metalated copper derivatives. Solution electron paramagnetic resonance (EPR) spectra at 100 K showed hyperfine coupling of the Cu(II) central metal ion and the N nucleus in the highly bent molecular structures. Electrochemical measurements in CH2Cl2 or N,N-dimethylformamide (DMF) containing 0.1 M tetrabutylammonium perchlorate (TBAP) were consistent with ring-centered electron transfers and, in the case of reduction, were assigned to electron additions involving two equivalent π centers on the bent nonaromatic molecule. The potential separation between the two reversible one-electron reductions ranged from 230 to 400 mV in DMF, indicating a moderate-to-strong interaction between the equivalent redox-active dipyrrin units of the dibenzoporphyrins(2.1.2.1). The experimentally measured highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps ranged from 2.14 to 2.04 eV and were smaller than those seen for the planar copper tetraarylporphyrins(1.1.1.1), (Ar)4PCu.

Binuclear Rhodium(I) Complex of a Dimethylvinylene-Bridged Distorted Hexaphyrin(2.1.2.1.2.1).

A highly distorted binuclear rhodium(I) complex, 2Rh, was successfully synthesized from hexaphyrin(2.1.2.1.2.1) containing dimethylvinylene-bridges between dipyrrin units. IR spectroscopy, 1H NMR spectroscopy, and X-ray crystallography revealed that the complex 2Rh consists of two rhodium(I) ions coordinated to two dipyrrin units. Rh complexation induced a transformation from a trans-/cis-/trans- to trans-/cis-/cis-conformation on the dimethylvinylene-bridges. This is the first example of rhodium(I)-ion-induced cis-/trans-isomerization in the porphyrin derivatives. Theoretical calculations of 2Rh predicted the presence of intramolecular charge-transfer absorption due to the distorted molecular structure.

Vinylene-Bridged Cyclic Dipyrrin and BODIPY Trimers.

Vinylene-bridged cyclic boron-difluoride complex of dipyrrin (BODIPY) trimers were successfully prepared from expanded dimethyl-vinylene bridged hexaphyrin(2.1.2.1.2.1) Me-Hex that has the structure of alternate dipyrrins and vinylene bridges. The hexaphyrin(2.1.2.1.2.1) Me-Hex can coordinate with boron ions to afford five kinds of cyclic BODIPYs given by step-by-step boron complexations. Crystal structures of all cyclic BODIPYs except for 3BF2-Me-Hex(b) formed non-planar structures. The theoretical calculation predicted that mono-/bis-boron cyclic BODIPYs show the intramolecular charge transfer (ICT) characteristics, whereas tri-boron cyclic BODIPYs have no ICT characteristics. Reflecting these electronic properties, tri-boron cyclic BODIPYs exhibit weak fluorescence in the red region, but mono-/bis-boron cyclic BODIPYs exhibit no emission. Vinylene bridged cyclic dipyrrin trimer Me-Hex is the novel porphyrinoid ligand allowed to control the boron coordination under different reaction conditions to form various boron complexes.

Control of Aromaticity and cis-/trans-Isomeric Structure of Non-Planar Hexaphyrin(2.1.2.1.2.1) and Metal Complexes.

Vinylene-bridged hexaphyrin(2.1.2.1.2.1) was synthesized from dipyrrolyl diphenylethenes by acid-catalyzed condensation reactions. Freebase hexaphyrin(2.1.2.1.2.1) forms a distorted structure with non-aromatic characteristics. The aromaticity and molecular configuration of non-planar hexaphyrin(2.1.2.1.2.1) can be controlled by insertion of metal ions. Freebase and zinc complexes show a distorted structure without macrocyclic aromaticity, whereas copper complexes show a figure-of-eight structure with macrocyclic aromaticity. It is the first example of aromaticity conversion of a distorted expanded porphyrin involving vinylene bridges.

[30]Hexaphyrin(2.1.2.1.2.1) as Aromatic Planar Ligand and Its Trinuclear Rhodium(I) Complex.

Expanded porphyrins are attractive research targets because of their large and flexible structures, optical and electrochemical properties, and diverse coordination abilities. We are interested in the use of double bonds within expanded porphyrins because double bonds could conduct isomerization, expansion of π-conjugation, and giving different molecular geometry. We, thus, report [30]hexaphyrin(2.1.2.1.2.1) 3H-1, which was synthesized by a simple condensation reaction of 1,2-di(pyrrol-2-yl)ethene and pentafluorobenzaldehyde under an acidic condition. The compound 3H-1 exhibited 30π aromatic property with a highly planar structure, displaying intense Soret- and weak Q-like absorption bands. The compound 3H-1 has a sufficient space and dipyrrin-like coordination sites in its cavity. Trinuclear rhodium(I) complex 3Rh-1 was obtained with [Rh(CO)2Cl]2 and exhibited six redox potentials.

Synthesis, Characterization and Protonation Behavior of Quinoxaline-Fused Porphycenes.

9,10-Quinoxaline-fused porphycenes 1a-H2 and 1b-H2 were synthesized by intramolecular McMurry coupling. As a result of the annulation of the quinoxaline moiety on the porphycene skeleton, 1a-H2 and 1b-H2 display absorption and fluorescence in the near infra-red (NIR) region. Additionally, the quinoxaline moieties of 1a-H2 and 1b-H2 act as electron-withdrawing groups, introducing lower reduction potentials than for pristine porphycene. The protonation occurred at the nitrogen atoms in the cavity of freebase porphycenes and at the quinoxaline moieties for their nickel complexes to give diprotonic species.

Synthesis and Metalation of Doubly o-Phenylene-Bridged Cyclic Bis(dipyrrin)s with Highly Bent Skeleton of Dibenzoporphyrin(2.1.2.1).

Facile synthesis of dibenzoporphyrins(2.1.2.1) has been successfully reported by the simple condensation reaction of o-dipyrrolylbenzene with various aldehydes in the presence of a Lewis acid. This reaction enables the preparation of various dibenzoporphyrin(2.1.2.1) derivatives with p-substituted phenyl groups, five-membered heterocycles, and ethynyl groups at the meso-positions. Dibenzoporphyrins(2.1.2.1) consist of two dipyrrin units that are connected by o-phenylene bridges, which adopt highly bent saddle-shaped structures; this was confirmed by X-ray diffraction analysis. We found that dibenzoporphyrin(2.1.2.1) can be described as a 20π antiaromatic conjugated system, but practically, it is not an antiaromatic macrocycle, which we revealed by (1) H NMR spectroscopy. The redox potentials had good correlations with Hammett substituent constant (σp ) of the substituents at the meso-positions. The free-base dibenzoporphyrin(2.1.2.1) was able to form the metal complexes with nickel(II), copper(II), palladium(II), platinum(II), and tin(IV) ions. These results suggested that dibenzoporphyrin(2.1.2.1) derivatives can be utilized as novel macrocyclic dianionic tetradentate ligands for various metal ions to give complexes with varying optical and electrochemical properties.

Aromaticity Relocation in Perylene Derivatives upon Two-Electron Oxidation To Form Anthracene and Phenanthrene.

We prepared perylene dications 1(2+) and 2(2+) by using "capped" perylene derivatives, and for the first time, successfully obtained single crystals of a perylene dication 1(2+) that enabled us to perform its structural analysis. We realized that the substituted aryl groups on perylene control the positions of positive charges, thus the remaining electronic system satisfies Clar's sextet rule toward the highest number of localized sextets. Experimental and theoretical evidence proved that Clar's aromatic π-sextet rule could be applied even for the dicationic perylenes in a very simple way.

Synthesis and Characterization of an Iridium Triphyrin Complex.

A sandwich complex of iridium(III) benzotriphyrin (2) has been synthesized from free-base benzotriphyrin (1) and [IrCl(cod)]2 (COD = 1,5-cyclooctadiene). The COD ring was transformed from 1,5-COD to an η1,η3-C8H12 unit as a π-allyl ligand associated with the valence change of iridium from IrI to IrIII, as revealed by X-ray diffraction analysis. The Soret-like band of 2 was blue-shifted and broadened compared with that of 1, indicating strong electronic interactions between triphyrin and the iridium ion. Compound 2 also showed very broad absorption in the range of 500-800 nm, which can be assigned to a mixture of Q and metal-to-ligand charge-transfer bands.

An optically and thermally switchable electronic structure based on an anthracene-BODIPY conjugate.

An optically and thermally responsive boron dipyrromethene (BODIPY) dye, namely, meso-2-(9,10-dihydro-9,10-ethanoanthracene-11,12-dione) (DK)-linked, bicyclo[2.2.2]octadiene (BCOD)-fused BODIPY (BCOD-DK), was synthesized. The weakly luminous structure of BCOD-DK can be changed quantitatively to that of the strongly fluorescent BODIPY BCOD-Ant by optical excitation at the DK unit, which induces double decarbonylation of the DK unit to give an anthracene unit. The solvent effect on the fluorescence properties of BCOD-DK suggests that the dramatic change in fluorescence intensity is controlled by intramolecular electron transfer from the BODIPY moiety to the meso-DK substituent. BCOD-DK is converted to meso-DK benzene-fused BODIPY (Benzo-DK) by heating at 220 °C with 64-70 nm redshift of absorption and fluorescence peaks without changing the fluorescence quantum yield of ΦF =0.08 in dichloromethane. Benzo-DK can be converted to strongly fluorescent meso-anthracene benzene-fused BODIPY Benzo-Ant by optical excitation. Thus, BCOD-DK can show four different optical performances simply by irradiation and heating, and hence may be applicable for optical data storage and security data encryption.

Tetrabenzoperipentacene: Stable Five-Electron Donating Ability and a Discrete Triple-Layered ß-Graphite Form in the Solid State.

An oxidative ring-closure reaction of a tetranaphthylpyrene derivative led to the synthesis of a 56 all-carbon conjugated tetrabenzoperipentacene. In the single-crystal X-ray structure, three molecules make a triple-layered cluster by π-stacking, wherein each layer rotates by 120°, and is thus considered a petit ß-graphite. As for the optical properties, the Stokes shift is extremely small (10 cm(-1) ), thus indicating its remarkably rigid framework. The tetrabenzoperipentacene exhibits reversible five-electron oxidation waves in cyclic voltammetry, and is regarded as a counterpart to the fullerene C60 in terms of stable multicharge-storage nanocarbon materials.

Synthesis and solid-state structures of a tetrathiafulvalene-conjugated bistetracene.

A tetrathiafulvalene (TTF)-conjugated bistetracene was synthesized and characterized in the molecular electronic structures based on the spectroscopic measurements and the single-crystal X-ray diffraction analysis. UV/Vis absorption and electrochemical measurements of 5 revealed the considerable electronic communication between two tetracenedithiole units by through-bond and/or through-space interactions. The difference in the crystal-packing structures of 5, showing polymorphism, results in a variety of intermolecular electronic-coupling pattern. Of these, the π-stacking structure of 5 A gave a large transfer integral of HOMOs (97 meV), which value is beyond hexacene and rubrene, thus, quite beneficial to achieve the high hole mobility.

New 2,6-distyryl-substituted BODIPY isomers: synthesis, photophysical properties, and theoretical calculations.

A 2,6-distyryl-substituted boradiazaindacene (BODIPY) dye and a new series of 2,6-p-dimethylaminostyrene isomers containing both α- and ß-position styryl substituents were synthesized by reacting styrene and p-dimethylaminostyrene with an electron-rich diiodo-BODIPY. The dyes were characterized by X-ray crystallography and NMR spectroscopy and their photophysical properties were investigated and analyzed by carrying out a series of theoretical calculations. The absorption spectra contain markedly redshifted absorbance bands due to conjugation between the styryl moieties and the main BODIPY fluorophore. Very low fluorescence quantum yields and significant Stokes shifts are observed for 2,6-distyryl-substituted BODIPYs, relative to analogous 3,5-distyryl- and 1,7-distyryl-substituted BODIPYs. Although the fluorescence of the compound with ß-position styryl substituents on both pyrrole moieties and one with both ß- and α-position substituents was completely quenched, the compound with only α-position substituents exhibits weak emission in polar solvents, but moderately intense emission with a quantum yield of 0.49 in hexane. Protonation studies have demonstrated that these 2,6-p-dimethylaminostyrene isomers can be used as sensors for changes in pH. Theoretical calculations provide strong evidence that styryl rotation and the formation of non-emissive charge-separated S1 states play a pivotal role in shaping the fluorescence properties of these dyes. Molecular orbital theory is used as a conceptual framework to describe the electronic structures of the BODIPY core and an analysis of the angular nodal patterns provides a reasonable explanation for why the introduction of substituents at different positions on the BODIPY core has markedly differing effects.

Yellow NIR dye: π-fused bisbenzoBODIPYs with electron-withdrawing groups.

Bicyclo[2.2.2]octadiene-fused (BCOD-fused) bis(benzoborondipyrromethene)s (bisbenzoBODIPYs) bearing electron-withdrawing groups such as fluorine and cyano groups were prepared either by incorporating tetrafluoroisoindole moieties into BODIPY chromophores or by introducing cyano or ethoxycarbonyl groups at the 3,5-positions. The BCOD-fused bisbenzoBODIPYs were quantitatively converted to the corresponding benzene-fused bisbenzoBODIPYs by a retro-Diels-Alder reaction. The π-fused bisbenzoBODIPYs were found to have intense absorption in the near-infrared region and not to have any strong absorption bands in the visible region. Moreover, the bisbenzoBODIPYs were stable under atmospheric conditions.

Time-resolved fluorescence spectroscopy study of excited state dynamics of alkyl- and benzo-substituted triphyrin(2.1.1).

We have investigated the photophysical properties of alkyl-substituted triphyrin(2.1.1) (ATp) and benzotriphyrin(2.1.1) (BTp) by steady-state and time-resolved fluorescence spectroscopy. We focused on the effect of NH proton tautomerization, planarity of the macrocycles, and substituents on these properties. The fluorescence quantum yields (Φy) of ATp did not depend on solvent viscosity, whereas those of BTp increased with solvent viscosity, reaching a maximum value of 0.17 in paraffin. Interestingly, analyzing Φy showed that the non-radiative rate constant of BTp decreased sharply as the solvent viscosity increased. These results suggest that the substituted phenyl groups play a crucial role in suppressing molecular distortion, thus leading to decreased non-radiative relaxation in triphyrin(2.1.1). The hydrogen bond formed in the inner cavity potentially contributes to the suppression of the structural distortion, whereas the pyrrole rings in the macrocycle are close, as in porphycene.

Covalent modular approach for dimension-controlled self-organization of perylene bisimide dyes.

Organogels: Dimerization of perylene bisimide dyes through an oligomethylene linker enabled the facile control over columnar and lamellar self-organized architectures by an odd/even effect with respect to the number of methylene groups. The difference in the self-organized architectures was shown to have an impact on their material morphologies, as well as charge-carrier mobilities (see scheme).