Facile Formation of Stable Neutral Radicals and Cations from [22]Smaragdyrin BF2 Complexes.

meso-Trimesityl-substituted [20]smaragdyrin freebase was synthesized by p-toluenesulfonic acid catalyzed reaction of 5-mesityldipyrromethane and 2,14-dibromodipyrrin in an improved yield of 63 %. Unexpectedly, treatment of the [20]smaragdyrin freebase with BF3 ⋅ OEt2 and triethylamine (TEA) gave a stable radical species, in which the BF2 unit is coordinated at the tripyrrin site, probably by ready release of a hydrogen atom of a [22]smaragdyrin BF2 complex. Similar treatment of [22]smaragdyrin free base produced another [22]smaragdyrin BF2 complex, in which the BF2 unit is coordinated at the dipyrrin site. The tripyrrin site coordinated neutral radical was oxidized with AgSbF6 to give a stable antiaromatic cation; this was reduced with NaBH4 to its 22π congener, which was easily oxidized back to the neutral radical in the air and rearranged to thermodynamically stable dipyrrin site coordinated [22]smaragdyrin BF2 complex upon treatment with BF3 ⋅ OEt2 and TEA. Further, the dipyrrin site coordinated [22]smaragdyrin BF2 complex was similarly oxidized to a stable neutral radical and a stable cation in a stepwise manner. This work demonstrates a rare ability of smaragdyrin BF2 complexes to exist in multiple redox states, particularly forming a stable neutral radical by facile release of a hydrogen atom.

Rearrangements of Internally-bridged Octaphyrin(1.1.1.1.1.1.1.1)s to Porphyrin Dimers.

Internally-bridged octaphyrin(1.1.1.1.1.1.1.1) underwent a rearrangement to meso-meso linked porphyrin dimer as a new metamorphosis. Extensive examination suggests that hydride-addition is a key step for the rearrangements to afford thermodynamically more stable porphyrin framework. Further, ß-tetrabromo[36]octaphyrin was transformed to meso-meso, ß-ß, ß-ß triply linked porphyrin dimer via a similar mechanism combined with Pd-mediated reductive homocoupling.

A Fully Conjugated Porphyrin-[36]Octaphyrin-Porphyrin Hybrid Tape Exhibiting Möbius Aromaticity.

Directly meso-meso linked porphyrin-tetrabromo[36]octaphyrin-porphyrin hybrid trimer 10 was successfully synthesized via acid-catalyzed condensation reaction and subsequent oxidation. ZnII -metalation of 10 induced transannular meso-meso bond formation to give Möbius aromatic bis-ZnII octaphyrin 11, which was oxidized by DDQ/Sc(OTf)3 to provide fully conjugated porphyrin-[36]octaphyrin-porphyrin hybrid tape 12 as the first example of porphyrin tape exhibiting Möbius aromaticity. Hybrid tape 12 displays significantly red-shifted absorption and small electrochemical HOMO-LUMO gap, indicating the effective conjugation through the whole chromophores.

Synthesis of meso-Free Decaphyrin(1.1.1.1.1.1.1.1.1.1) by a Hydrodebromination Protocol; Aromaticity and Solvent-Polarity Dependent Conformational Change.

A meso-free ß-bromodecaphyrin has been constructed by [2+3+2+3] type acid-catalyzed cross-condensation and subsequent oxidation. Hydrodebromination of this tetrabromodecaphyrin with NaBH4 in the presence of TMEDA and palladium catalyst afforded ß-unsubstituted doubly meso-free [46]decaphyrin(1.1.1.1.1.1.1.1.1.1) as the first example of ß-unsubstituted meso-free regular expanded porphyrins with the number of pyrrole units larger than eight. It exhibits distinct aromaticity originating from its 46π-conjugated electronic circuit and flexible conformational change between non-twisted and doubly twisted forms depending on the solvent-polarity. Their distinct conformations have been analyzed by combined experimental and theoretical investigations.

meso-Oxoisocorroles: Tunable Antiaromaticity by Metalation and Coordination of Lewis Acids as Well as Aromaticity Reversal in the Triplet Excited State.

The corrole derivative meso-oxoisocorrole has been theoretically predicted to be antiaromatic, despite its formally cross conjugated electronic system. In this study, this prediction has been experimentally proven by the facile preparation of meso-oxoisocorrole via the oxidation of a meso free corrole with MnO2 and its comprehensive characterization using NMR, UV/vis absorption, FT-IR, and transient-absorption spectroscopy, cyclic voltammetry, and X-ray diffraction analysis. Furthermore, the free base meso-oxoisocorrole was metalated by treatment with Ni(acac)2, PdCl2(PhCN)2, and Zn(OAc)2 to give the corresponding metal complexes. These complexes are more strongly antiaromatic, and their degree of paratropicity depends on their planarity. Thus, fine tuning of their antiaromaticity was achieved with concomitant modulation of their HOMO-LUMO gaps. In the presence of tris(pentafluorophenyl)borane, their antiaromaticity is significantly enhanced due to the elongation of the C═O bond, which promotes the polarized C+-O- resonance state. Furthermore, a distinct frequency shift of the C═O vibrational mode in the triplet state was observed in the time-resolved IR spectra in accordance with the Baird rule, which indicates aromaticity reversal in the excited state.

Tetrabromo[36]octaphyrin: A Promising Precursor of Directly Fused Porphyrin(2.1.1.1) Dimer and meso-α Fused N-Confused Porphyrin Dimer.

3,7,23,27-Tetrabromo[36]octaphyrin 2 was synthesized as a novel octaphyrin bearing two meso-free positions. Surprisingly, its ZnII and NiII complexation reactions produced a directly fused porphyrin(2.1.1.1) dimer 6, and a meso-α fused N-confused porphyrin (NCP) dimer 7, as the first example of NCP tape, respectively, via transannular C-C bond formation. While 6 exhibits a diatropic ring-current effect owing to the global 36π Möbius aromaticity, 7 shows a paratropic ring-current effect due to the global Hückel 36π antiaromaticity. In addition, the oxidation of 7 with PbO2 allowed for formation of its two-electron oxidized species 9 that exhibited a diatropic ring-current effect due to the global Hückel 34π aromaticity. This work has demonstrated that meso-free large expanded porphyrins can be a promising platform to produce novel fused porphyrinoids.

A Robust Porphyrin-Stabilized Triplet Carbon Diradical.

The synthesis of robust high-spin carbon radicals is an important topic in organic chemistry. Toward this end, several porphyrin-stabilized radicals have been systematically explored. A singly naphthalene-fused porphyrin radical was synthesized by a reaction sequence consisting of a Suzuki-Miyaura coupling of ß-borylated porphyrin with 2-bromobenzaldehyde, addition of mesityl Grignard reagent, intramolecular Friedel-Crafts alkylation, and final oxidation with DDQ or tBuOK/O2 . This strategy was also used to synthesize doubly naphthalene-fused porphyrins and syn- and anti-fused-anthracene-bridged porphyrin dimers. While singly naphthalene-fused porphyrin radical has been shown to be a stable monoradical, doubly naphthalene-fused porphyrins and anti-fused-anthracene-bridged porphyrin dimers have been shown to be closed-shell molecules. Finally, the syn-dimer was characterized as a surprisingly stable radical (t1/2 =28 days under ambient air and at 80 °C) that is storable for more than several months, despite its high-spin triplet ground-state carbon diradical.

Oxidation-Induced Detachment of Ruthenoarene Units and Oxygen Insertion in Bis-Pd(II) Hexaphyrin π-Ruthenium Complexes.

Two types of new bis-Pd(II) hexaphyrin π-ruthenium complexes are reported. A double-decker bis-Pd(II) hexaphyrin π-ruthenium complex 4 was obtained by oxidation-induced detachment of a ruthenoarene unit from the triple-decker complex 3 and oxygen-inserted triple-decker bis-Pd(II) hexaphyrin π-ruthenium complex 6 was obtained upon treatment of bis-Pd(II) [26]hexaphyrin 5 with [RuCl2(p-cymene)]2 under aerobic conditions. Although π-metal complexation of porphyrinoids often results in decreased global aromaticity due to the enhancement of local 6π aromatic segments, distinct aromatic characters were indicated for 4 and 6 by 1H-NMR spectral and theoretical calculations. These results are accounted for in terms of possible resonance contributors of hexaphyrin di- and tetraanion ligands. Thus, π-metal coordination has been shown to be effective for modulation of the overall aromaticity.

π-Ruthenium Complexes of Hexaphyrins(1.1.1.1.1.1): A Triple-Decker Complex Bearing Two Ruthenoarene Units.

Ruthenium(II) π-coordination onto [28]hexaphyrins(1.1.1.1.1.1) has been accomplished. Reactions of bis-AuIII and mono-AuIII complexes of hexakis(pentafluorophenyl) [28]hexaphyrin with [RuCl2 (p-cymene)]2 in the presence of NaOAc gave the corresponding π-ruthenium complexes, in which the [(p-cymene)Ru]II fragment sat on the deprotonated side pyrrole. A similar reaction of the bis-PdII [26]hexaphyrin complex afforded a triple-decker complex, in which the two [(p-cymene)Ru]II fragments sat on both sides of the center of the [26]hexaphyrin framework.

Microencapsulation of Ascorbic Acid for Cosmetic by Utilizing Self-assembly of Phase Separated Polymer.

Micrometer-sized polymer particles encapsulated ascorbic acid (vitamin C; VC) were successfully prepared by the three types of the self-assembling method, those are, phase separation and self-assembly of added polymer at the oil-water interface in emulsion, microsuspension polymerization utilizing the self-assembling of phase separated polymer (SaPSeP) method, and their hybrid method. In the stability study at 50°C for 2 months, the three kinds of capsule particles exhibited effective protection of VC from the interaction with other components in cosmetic consisting of water-in-oil (W/O) emulsion. The encapsulated VC was easily released from the capsule particles by an excess of water. These encapsulation methods will be useful for the stabilization of water-soluble substances in cosmetic consisting of W/O emulsion.

Synthesis of NiII porphyrin-NiII 5,15-diazaporphyrin hybrid tapes.

NiII porphyrin (P) and NiII 5,15-diazaporphyrin (DAP) hybrid tapes were synthesized by Suzuki-Miyaura cross-coupling reactions of meso- or ß-borylated P with ß-brominated DAP followed by intramolecular oxidative fusion reactions. Meso-ß doubly linked hybrid tapes were synthesized by oxidation of singly linked precursors with DDQ-FeCl3. Synthesis of triply linked hybrid tapes was achieved by oxidation with DDQ-FeCl3-AgOTf with suppression of peripheral ß-chlorination. In these tapes, DAP segments were present as a 20π-electronic unit, but their local antiaromatic contribution was trivial. Remarkably, these hybrid tapes were stable and exhibited extremely enhanced absorption bands in the NIR region and multiple reversible redox waves. A pentameric hybrid tape showed a remarkably sharp and red-shifted band at 1168 nm with ε = 5.75 × 105 M-1 cm-1. Singly linked P-DAP dyads were oxidized with DDQ-FeCl3 to give stable radicals, which were oxidized further to afford dimeric hybrid tapes possessing a nitrogen atom at the peripheral-side meso-position.

Synthesis of 8,12-Dibromocorrole and Its Transformation to Antiaromatic 8,10-Fused Iminoisocorrole with a Polarized Resonance Contribution.

8,12-Dibromo-5,15-bis(pentafluorophenyl)corrole and its Ag(III) complex were prepared via intramolecular oxidative coupling of a 8,12-dibromobilane precursor. The Ag(III) complex was allowed for further transformation via Suzuki coupling reaction. Thus, 2-aminophenyl group was coupled at one of the ß-positions, and subsequent demetalation followed by oxidation with MnO2 afforded 8,10-fused iminoisocorrole in good yields. The iminoisocorrole exhibited weak antiaromaticity due to the C(+)-N(-) polarized resonance contribution as evidenced by 1 H NMR spectrum, UV/vis absorption spectra, cyclic voltammetry, and theoretical calculations.

PdII insertion-triggered meso-carbon extrusion of N-fused pentaphyrin to form N-fused sapphyrin PdII complexes.

meso-Carbon extrusion of N-fused [22]pentaphyrin(1.1.1.1.1) occurred upon its PdII complexation, giving N-fused [22]pentaphyrin (1.1.1.1.0) ([22]sapphyrin) PdII complexes 5 and 6 as 22π aromatic compounds. Oxidation of 5 with DDQ and Sc(OTf)3 gave directly C-N linked dimer 7.

5,20-Bis(ethoxycarbonyl)-Substituted Antiaromatic [28]Hexaphyrin and Its Bis-NiII and Bis-CuII Complexes.

5,20-Bis(ethoxycarbonyl)-[28]hexaphyrin was synthesized by acid catalyzed cross-condensation of meso-diaryl-substituted tripyrrane and ethyl 2-oxoacetate followed by subsequent oxidation. This hexaphyrin was found to be a stable 28π-antiaromatic compound with a dumbbell-like conformation. Upon oxidization with PbO2 , this [28]hexaphyrin was converted into an aromatic [26]hexaphyrin with a rectangular shape bearing two ester groups at the edge side. The [28]hexaphyrin can incorporate two NiII or CuII metals by using the ester carbonyl groups and three pyrrolic nitrogen atoms to give bis-NiII and bis-CuII complexes with essentially the same dumbbell-like structure. The antiaromatic properties of the [28]hexaphyrin and its metal complexes have been well characterized.

Aromatic and Antiaromatic Cyclophane-type Hexaphyrin Dimers.

A peripherally strapped [28]hexaphyrin takes a rectangular conformation and exhibits antiaromatic character. A cyclophane-type dimer consisting of such [28]hexaphyrins was synthesized from hexakis(pentafluorophenyl) [26]hexaphyrin via SN Ar reaction with allyl alcohol, one-pot intra- and intermolecular olefin metathesis under improved Hoveyda-Grubbs catalysis, and final reduction with NaBH4 . The cyclophane-type structures of [26]- and [28]hexaphyrin dimers have been revealed by X-ray analysis. Studies on the structural, optical, and electronic properties have led to a conclusion that there is no favorable electronic interaction between the two [28]hexaphyrin segments and thus no indication of 3D aromaticity.