[22]Pentaphyrins(2.0.1.1.0) Displaying N-Fusion, Pyrrole-Rearrangement, and Dimerization Reactions Upon Oxidation and Metalation.

Exploration of expanded porphyrins with unprecedented reactivities has remained important. Here [22]pentaphyrins(2.0.1.1.0) were synthesized as a constitutional isomer of sapphyrin by acid-catalyzed cyclization of 1,14-dibromo-5,10-diaryltripyrrin with 1,2-di(pyrro-2-ly)ethenes. These pentaphyrins display roughly planar structures and varying aromaticities depending upon the vinylene structures. The 19,20-ditolyl pentaphyrin gave an N-fused product and an unprecedented pyrrole-rearranged product, depending upon the oxidation conditions. Remarkably, upon the metalation with CuCl, the N-fused product and the pyrrole-rearranged product afforded an inner b-b coupled face-to-face CuII complex dimer and an outer b-b coupled lateral CuII complex dimer, respectively, in fairly good yields. Further, [22]pentaphyrin(2.0.1.1.0) fused with a NiII porphyrin was effectively dimerized upon oxidation with MnO2 to give a 16-16' directly linked dl-dimer.

Carbazole Based Smaragdyrins: Synthesis, Aromaticity Switching, and Formation of a Spiro-Dimer.

Carbazole-incorporated smaragdyrin BF2-complex 3 was synthesized by SNAr reaction of 3,5-dibromo-8-mesityl-BODIPY 1 with 3,6-di(tert-butyl)-1,8-di(pyrrol-2-yl)carbazole 2 as a nucleophile. Demetalation of 3 with ZrCl4 gave the corresponding smaragdyrin free base 4 in a good yield. Oxidations of 3 and 4 with MnO2 gave smaragdyrins 5 and 6, respectively, both followed by aromaticity switching, since the oxidized products showed a moderate paratropic ring current owing to their 20π-electronic circuits. Further, treatment of 4 with [RhCl(CO)2]2 in the presence of NaOAc gave RhI complex 7, and oxidation of 3 with RuCl3 in the presence of triethylamine led to the formation of a spiro dimer product, 8.

BIII-Subporphyrins Bearing Distorted Metal-Coordinating Straps: CuII-Assisted meso-Fabrications.

BIII-subporphyrins 4, 5, and 6 possessing metal-coordinating carbaporphyrin-like pockets were synthesized by Suzuki-Miyaura coupling reactions. Compounds 4 and 5 gave PdII complexes 4-Pd and 5-Pd upon metalation with Pd(OAc)2 but did not give either their NiII or CuII complexes. Conversely, 6 was expected to induce distorted square planar coordination because of its 2,5-di(pyrid-2-yl)pyrrole strap. Indeed reaction of 6 with Cu(OAc)2 did not give its CuII complex but produced meso-alkoxy and meso-phenoxy products in the presence of alcohols and phenol, possibly via CuII-mediated C-H bond functionalization, which was further extended to meso-C-C bond-forming fabrications by using organoboronic acids. These CuII-mediated C-H bond meso-fabrications are the first example for porphyrinoid substrates.

Copper(II) Carbaporphyrins: Oxygenation Reactivities Dependent upon Coordinating Structures.

CuII metalations of carbaporphyrins 1-4 gave the corresponding CuII complexes 1-Cu, 2-Cu, 3-Cu, and 4-Cu with varying degrees of distortions in CuII square-planar coordination. Upon treatment with Cu(OAc)2, 1-Cu was inert but 2-Cu and 3-Cu gave the respective O-atom-inserted complexes 2-OCu and 3-OCu. Further, 3-Cu and 4-Cu were converted to meso-methoxynickel(II) porphyrins 3-OMe and 4-OMe, respectively, via treatment with Cu(OAc)2 in methanol. meso-Hydroxynickel(II) porphyrin 3-OH was obtained by the treatment of 3-OCu by acetic acid. The treatment of 4-Cu with Cu(OAc)2 in the presence of acetic acid gave 5,15-diketoporphyrinogen 4-O. CuII complexes of carbaporphyrins became more reactive with an increased distortion in CuII square-planar coordination.

Di(p-dibenzi)[40]decaphyrin(1.0.0.0.0.1.0.0.0.0) PdII Complex: A Weakly Hückel 38π-Aromatic Macrocycle.

Di(p-benzi)[40]decaphyrin(1.0.0.0.0.1.0.0.0.0) BF2 complex and tris(p-benzi)[60]pentadecaphyrin(1.0.0.0.0.1.0.0.0.0.1.0.0.0.0) BF2 complex were synthesized by Suzuki-Miyaura coupling of α,α'-diborylated tetrapyrrole BF2 -complex with 1,4-diiodobenzene. Bis-BF2 complex was converted to bis-PdII complex via its free base. Macrocycles bis-BF2 and tris-BF2 complex take Möbius topology but are nonaromatic, since the macrocyclic conjugation is disrupted by the locally aromatic 1,4-phenylene units. In contrast, bis-PdII complex is a weakly Hückel 38π-aromatic macrocycle as evinced by its red-shifted, enhanced, and structured Q-like bands and a small electrochemical HOMO-LUMO gap. Interestingly, one 1,4-pheylene part of bis-PdII complex takes a quinonoidal distorted structure and the other takes a usual benzene structure in a figure-eight conformation with Hückel topology.

Synthesis of Pyrrole-Sharing Fused Porphyrinoid Hybrids by Post-fabrication of Ni(II) Porphyrins.

Pyrrole-sharing fused hybrids of NiII porphyrin with PdII N-confused(NC)-corrole and PdII NC-oxaporphyrin were synthesized by post-fabrication of NiII porphyrins. Specifically this consists of Friedel-Crafts type aromatic substitution reaction of meso-free NiII porphyrin with α,α'-dibromotripyrrin and Pd(OAc)2 assisted cyclization, and final heating to induce a Pd-C bond formation. NiII porphyrins fused with PdII NC-corrole and with PdII NC-oxaporphyrins show coplanar structures with a shared pyrrole unit. In these hybrids, the PdII NC-oxaporphyrin is aromatic and the PdII NC-corrole is moderately antiaromatic and these local electronic properties interact to influence the whole network.

Stable Antiaromatic [24]Hexaphyrin(1.1.0.0.1.0) and Its Metal Complexes.

5,10,23-Trimesityl-substituted [24]hexaphyrin(1.1.0.0.1.0) was synthesized as a stable antiaromatic molecule by base-catalyzed twofold SNAr reaction and was reduced to the corresponding [26]hexaphyrin, which was an unstable aromatic molecule because it easily oxidized to the [24]hexaphyrin. The [24]hexaphyrin served as a ligand to give the bis-PdII complex and tris-RhI complex with unique structures. The former complex has two square-planar-coordinated PdII ions bridged by an acetate anion and shows a strong paratropic ring current, while the latter complex has three RhI ions coordinated with two pyrrolic nitrogen atoms and two carbonyl groups, but one carbonyl group is shared with two RhI ions in a unique manner.

Heptagon/Octagon-Fused Diporphyrins or Spiro-Pentagon-Bridged Dichlorin from p-Terphenylene-Bridged Diporphyrin.

Intramolecular fusion reactions of a p-terphenylene-bridged NiII porphyrin dimer gave different products, depending upon reaction conditions. Oxidation with Fe(OTf)3 provided syn- and anti-doubly heptagon-fused NiII porphyrin dimers showing enlarged π-electronic networks, probably via a radical mechanism, while treatment with methanesulfonic acid provided a spiro-pentagon-bridged NiII chlorin dimer via acid-catalyzed Friedel-Crafts type cyclization. Further, a doubly octagon-fused NiII porphyrin dimer was synthesized via a sequence of double meso-formylation, reduction to corresponding diol, and BF3 -catalyzed cyclization.

A Quadruply Bridged Non-Offset Face-to-Face Porphyrin Dimer and Cross-Shaped Pentameric Porphyrin Tapes Based on 2,7,12,17-Tetrakis(pinacolatoboryl) NiII Porphyrin.

2,7,12,17-Tetrakis(pinacolatoboryl) NiII porphyrin 5 Ni was synthesized in 75 % yield by Ir-catalyzed borylation of porphine followed by NiII metalation and has been demonstrated to be a useful synthon, giving 2,7,12,17-tetraaryated NiII porphyrins 6 a-d, peripherally octaarylated NiII porphyrins 8 a-d, quadruply bridged face-to-face non-offset NiII -porphyrin dimer 12, and cross-shaped ß-meso singly linked porphyrin pentamers and nonamers. Oxidation of cross-shaped ß-meso singly linked porphyrin pentamers 14 Ni and 14 Zn gave fused pentameric tapes 15 Ni and 15 Zn. The structures of 12, 14 Zn, and 15 Ni have been revealed by X-ray diffraction analysis. Optical separation of 12 has been accomplished, showing a bisignate coupling pattern for exciton-coupled blue-shifted Soret band. Pentameric porphyrin tape 15 Zn exhibits a red-shifted absorption band at 1156 nm and seven reversible redox waves.

m-Benziporphyrin(1.1.0.0)s as a Rare Example of Ring-Contracted Carbaporphyrins with Metal-Coordination Ability: Distorted Coordination Structures and Small HOMO-LUMO Gaps.

m-Benziporphyrin(1.1.0.0) and m-pyreniporphyrin(1.1.0.0) were prepared as ring-contracted carbaporphyrins. While m-Benziporphyrin(1.1.0.0) was unstable, m-pyreniporphyrin(1.1.0.0) was fairly stable. Both of their PdII complexes showed distorted coordination structures with extremely short Pd-C bonds. As compared with the reported m-benziporphyrin PdII complexes, these PdII complexes showed considerably small HOMO-LUMO gaps, despite their smaller molecular size. PdII metalation of the m-pyreniporphyrin(1.1.0.0) dimer gave the corresponding PdII complex, which showed similar distorted coordination and a smaller HOMO-LUMO gap. Finally, PdII metalation of a pyrene-sharing formal p-benziporphyrin(1.1.1.1) dimer gave a nonaromatic PdII dimer, which rearranged to an aromatic PdII complex upon treatment with alumina.

Synthesis of Subporphyrin Free Bases.

BIII subporphyrins are the legitimate ring-contracted porphyrins consisting of three pyrroles and three meso-carbons and their chemistry has been extensively developed since the first synthesis in 2006. However, subporphyrin free bases have never been synthesized, despite tremendous attempts to remove the BIII ion. Here we report that Suzuki-Miyaura coupling between α,α'-diborylated tripyrrane 1 and tetrabromide 5 gave subporphyrin free bases 6, 6 A, and free base dimer 7 in 6 %, 4 %, and 2 % yields as the first examples. Subporphyrin free bases exhibit curved bowl-like structures and distinct 14π-aromaticity. Steady-state and time-resolved spectroscopy revealed that the excited-state behaviors of the subporphyrin free bases are comparable with those of the corresponding BIII subporphyrins. Rotational relaxation processes in the excited states have been revealed, which enhance the electronic interactions with the meso-aryl substituents and between the two subporphyrins.

Porphyrinatonickel(II)-Cyclopentene and Porphyrinatonickel(II)-Cyclopentadiene Hybrids: Zirconacyclopentadiene-Mediated Syntheses, Structures, and Mechanistic Study.

The reaction of meso-formyl Ni(II) porphyrin 1 with zirconacyclopentadiene 2 in the presence of AlCl3 afforded four products 3, 4, 5, and 6 with a total yield of over 85%. The structures of these compounds are well-characterized by 1H NMR an d13C NMR spectroscopy, HRMS, and X-ray single-crystal diffraction. The mechanism is proposed mainly on the basis of isotopic labeling experiments, which showed that a Friedel-Crafts-type reaction and ß-H shift may be critical during the formation of 5 and 6.

Efficient Synthesis of Multiply Seven-Membered-Ring Fused Porphyrins by Rhodium-Catalyzed [5+2] Annulation.

Rhodium-catalyzed reaction of meso-pyrrol-2-yl NiII porphyrins with internal alkynes proceeded smoothly to give singly, doubly, and quadruply seven-membered-ring fused NiII porphyrins as the first example of [5+2] annulation reaction for porphyrin substrates, where the meso-appended pyrrole unit serves as a directing group. These reactions are operationally quite simple and easy. A plausible reaction mechanism was proposed on the basis of the isolation of a key intermediate. The structures of the representative products have been revealed to be considerably bent owing to the implemented seven-membered rings. Doubly fused ZnII and NiII porphyrins possessing an unsubstituted meso-position were dimerized to meso-meso linked dimers by aerobic oxidation with Zn(OAc)2 ⋅2 H2 O and electrochemical oxidation, respectively. The optical and electrochemical highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps, as well as the aromatic characters of the fused porphyrins decrease as the fusion parts increases.

Expanded Azaporphyrins Consisting of Multiple BODIPY Units: Global Aromaticity and High Affinities Towards Alkali Metal Ions.

The one-pot self-coupling reaction of 3-amino-5-bromo-BODIPY 9 under Buchwald-Hartwig amination conditions gave nitrogen-bridged cyclic BODIPY tetramer 10, pentamer 11, and hexamer 12. Oxidation of 10, 11, and 12 in the presence of alkali metal ions provided 13, 15, and 16, respectively, as the first examples of expanded azaporphyrins possessing more than six pyrrole rings. Curiously, the oxidation even in the absence of alkali metal ions gave the same complexes as a result of spontaneous complexation. 10-12 showed large association constants (104 -106  M-1 ) with K+ and Na+ , but the spontaneous complexations were not observed, indicating the extremely high affinities of 13-16 toward alkali metal ions, which can be ascribed to the multiple and effective ion-dipole interaction of the alkali metal ion with the negatively polarized F atoms of the BF2 walls surrounding the cavity. Importantly, 13, 14, and 15 show diatropic ring currents as a result of global aromaticity.

Low-Valent Zirconocene-Mediated Synthesis of Porphyrin(2.1.2.1)s and Its Extension to Synthesis of a Porphyrin(2.1.2.1) Nanobarrel.

Rosenthal's-reagent-mediated intramolecular cyclometallation of α,α-dialkynyldipyrrin nickel(II) complex and subsequent acid treatment afforded a 1,3-butadiene-embedded porphyrin(2.1.2.1), 6, which served as a reactive diene towards dienophiles such as dimethyl acetylenedicarboxylate (DMAD) and benzyne to give corresponding Diels-Alder adducts. Diels-Alder reaction of 6 and benzdiyne gave adducts 14, 15 a, and 15 b along with a trace amount of porphyrin(2.1.2.1) barrel 13. Stepwise routes using 14 or 15 a/15 b as a substrate allowed for the synthesis of 13 as a single stereoisomer. The nanobarrel structure for 13 was revealed by X-ray diffraction, where its cavity held two chloroform molecules via C-H⋅⋅⋅π interaction. DFT calculations revealed that the electrostatic attraction was dominant with binding energy of 32.8 kcal mol-1 .

Axially Arylene-bridged "Dumbbell" B(III)-Subporphyrin Dimers and a Tetrameric Subporphyrin Nanocage.

Axially B-arylene-bridged "dumbbell" BIII -subporphyrin (abbreviated as subporphyrin in this paper) dimers 3, 4, and 5 were prepared by reactions of B-methoxy subporphyrins with bromoaryl Grignard reagents and subsequent reductive coupling of the resulting B-bromoaryl subporphyrins with Ni(cod)2 . This reductive coupling method was also used for synthesis of tetrameric subporphyrin nanocage 8 from meso-meso linked subporphyrin dimer 7. Nanocage 8 displayed a red-shifted Q-like band and reduced fluorescence quantum yield as compared with 6 and 7.

Simultaneous Implementation of N-Heterocycle-Fused Bridge and Modified Pyrrole Unit on Ni(II) Porphyrin Dimers.

The oxidation of NiII-porphyrin dimer 10 with PbO2 or MnO2 resulted in the simultaneous implementation of an N-heterocycle-fused bridge and a modified pyrrole to give three unprecedented porphyrin dimers 11, 12, and 13. The reduction of 12 smoothly afforded 14. The structures of these dimers were all unambiguously confirmed by X-ray crystallographic analysis. These dimers show significantly red-shifted absorption bands and perturbed electrochemical properties with a decreasing HOMO-LUMO gap in the order of 14 > 13 > 11 > 12.

Singly and Doubly Neo-Confused Smaragdyrins.

Smaragdyrin had been an important but elusive expanded porphyrin until our recent first synthesis (Xie et al., J. Am. Chem. Soc. 2018, 140, 16553). In this paper, we report the synthesis of singly and doubly neo-confused [22]smaragdyrin BF2-complexes 13 and 15 both as stable smaragdyrin mutants by nucleophilic substitution reactions of 1,9-dibromo-5-mesityldipyrrin 1 with singly and doubly N-confused tripyrranes, 10 and 11, respectively. Demetalation of 13 and 15 with methanesulfonic acid furnished singly and doubly neo-confused [22]smaragdyrin free bases 16 and 18, respectively, both as air-sensitive porphyrinoids. These neo-confused [22]smaragdyrin free bases display characteristic properties such as decreased diatropic ring current, regioselective diprotonation at the inner α-carbon of the neo-confused pyrrole to give 16H22+ and 18H22+, and smooth oxygenation at the inner α-position of the neo-confused pyrroles, giving neo-confused [22]oxosmaragdyrin 17 and doubly neo-confused [24]dioxosmaragdyrin Cu(II) complex 19Cu via metalation of 18 with CuCl2 in the presence of NaOAc. Finally, demetalation of 19Cu with methanesulfonic acid gave the corresponding doubly neo-confused [24]dioxosmaragdyrin 19.

Carbazole-containing porphyrinoid and its oligomers.

A novel carbazole-containing porphyrinoid 4H and its oligomers 6H and 7H were synthesized for the first time via the Suzuki-Miyaura cross-coupling reaction. The structures of 4H, 4Pd, 6H, and 6Zn were finally confirmed by X-ray analysis. The exciton coupling strength (628 cm-1) in 4Zn, 6Zn, and 7Zn was found to be larger than that of the directly-linked porphyrin arrays (570 cm-1), extending their absorption spectra to the NIR region as well as enhancing the extinction coefficients.

meso-Triaryl-Substituted Smaragdyrins: Facile Aromaticity Switching.

All-aza smaragdyrin, a historic but elusive pentapyrrolic macrocycle, was successfully synthesized and characterized for the first time. [22]Smaragdyrin BF2-complex 3 was smoothly synthesized by 2-fold SNAr reaction of 1,9-dibromo-5-mesityldipyrrin with 5,10-dimesityltripyrrane. Treatment of 3 with methanesulfonic acid gave [20]smaragdyrin 5 as a stable antiaromatic compound. Reduction of 5 with NaBH4 under inert conditions gave [22]smaragdyrin 6 as an aromatic congener, which was easily oxidized back to 5 in the air. Complex 3 was interconvertible with its 20π-congener 4 via oxidation with MnO2 and reduction with NaBH4. Treatment of 3 or 4 with CuCl2 in the presence of NaOAc gave hetero bimetal complex 8.