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.

Fused Aromatic and Antiaromatic Smaragdyrin Dimers.

Singly-linked aromatic [22]smaragdyrin BF2 complex dimer was synthesized by the reductive coupling of 16-brominated [22]smaragdyrin BF2 complex, which was oxidized to a stable diradical with PbO2. As the first example of fused smaragdyrin dimer, a fused [22]smaragdyrin BF2 complex dimer was synthesized by the oxidation of a CuCl-BF2 complex dimer with FeCl3 and subsequent reduction with NaBH4. After removal of the BF2 group, the singly-linked and fused aromatic dimers were oxidized to the corresponding antiaromatic [20]smaragdyrin free base dimers. The first oxidation and reduction potentials of these dimers are split depending upon the intramolecular electronic interactions, which are larger for the fused dimers. Despite the large electronic interactions, the aromatic and antiaromatic characters are well preserved in the fused dimers.

5,18-Dimesitylorangarin: a Stable Antiaromatic [20]Pentaphyrin(1.0.1.0.0) Displaying Remarkable Oxidative Self-Coupling Reactions.

5,18-Dimesitylorangarin and its BF2 complex were synthesized by double SNAr reaction of 3,5-dibromo-BODIPY with a-(pyro-2-ly)dipyrrin as the first examples of meso-aryl-substituted orangarin. These orangarins, delineated as [20]pentaphyrin(1.0.1.0.0), are strongly antiaromatic but rather stable. The free base orangarin was coupled by oxidation with MnO2 to give a 11,11'-linked dimer, a cyclooctatetraene(COT)-centered trimer, and a spiro-trimer. Fused COT-centered 3H-orangarin dimer was oxidized to the corresponding 2H-orangarin dimer, which was further coupled to give a triply COT centered 2H-orangarin tetramer. 3H-Orangarin oligomers are all antiaromatic as evinced by extremely low-field-shifted 1H NMR signals of the inner NH and ill-defined absorption spectra with broad tails. In contrast, COT-centered 2H-orangarin dimer and tetramer show moderately low-field-shifted NH signals and intense NIR absorbance over 900 nm, suggesting the effective p-conjugation through the COT bridge and almost non-antiaromatic character. These orangarin oligomers exhibit many reversible redox potentials owing to the intramolecular electronic interactions. Regardless of the different aromatic characters, all the orangarin monomers and oligomers exhibit very rapid excited-state decays.

[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 ß-ß coupled face-to-face CuII complex dimer and an outer ß-ß 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.

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.

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.

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.

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 .

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.

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.

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.

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.

Synthesis and characterization of π-extended "earring" subporphyrins.

A π-extended "earring" subporphyrin 3 was synthesized from ß,ß'-diiodosubporphyrin and diboryltripyrrane via a Suzuki-Miyaura coupling and following oxidation. Its Pd complex 3Pd was also synthesized and both of the compounds were fully characterized by 1H NMR, MS and X-ray single crystal diffraction. The 1H NMR spectra and single crystal structures revealed that aromatic ring current did not extend to the "ear" in both of the two compounds. Their UV-vis/NIR spectra were recorded and the absorption of both compounds is extended to the NIR region and that the absorption of 3Pd is further red-shifted and more intense.

Strategic Construction of Directly Linked Porphyrin-BODIPY Hybrids.

A powerful and concise synthesis of directly linked porphyrin-BODIPY hybrids has been demonstrated, which consists of condensation of directly linked meso-pyrroyl NiII -porphyrin with arylaldehyde, oxidation with p-chloranil, and complexation with BF3 ⋅Et2 O. Synthesized hybrids include porphyrin dimer 6Ni, trimers 8Ni, 9Ni, tetramer 12Ni, pentamer 16Ni, hexamer 13Ni, and nonamers 17Ni and 18Ni. The structures of 6Ni, 9Ni and 12Ni were unambiguously confirmed by X-ray diffraction analysis. Some NiII porphyrins were effectively converted to the corresponding ZnII porphryins. In these hybrids, the pigments are three-dimensionally arranged with a face-to-face dimeric porphyrin unit in a well-defined manner, featuring their potential as light-harvesting antenna and functional hosts.

ß-to-ß 2,5-Pyrrolylene-Linked Cyclic Porphyrin Oligomers.

ß-to-ß 2,5-Pyrrolylene linked cyclic porphyrin oligomers have been synthesized by Suzuki-Miyaura coupling of 2,5-diborylpyrrole and 3,7-dibromoporphyrin. The cyclic porphyrin oligomers exhibit roughly coplanar structures, strong excitonic coupling, small electrochemical HOMO-LUMO gaps, and ultrafast excitation energy transfer between the neighboring porphyrins via the pyrrolylene bridge.

π-Extended "Earring" Porphyrins with Multiple Cavities and Near-Infrared Absorption.

ß,ß-tripyrrin-bridged earring porphyrins were synthesized through Suzuki-Miyaura cross coupling reactions. These porphyrinoids have multiple cavities and can accommodate two or three metal ions per molecule. The structures of the porphyrins have been elucidated by x-ray diffraction analysis, and feature curved π planes. The electronic spectra of the porphyrins exhibit near-infrared (NIR) absorptions and metal insertion leads to red-shifted and intensified absorption features. Electrochemical analysis and transient absorption measurements indicated that the porphyrins exhibit effective electronic communication between their central and peripheral moieties.

Azobenzene-Bridged Porphyrin Nanorings: Syntheses, Structures, and Photophysical Properties.

Azobenzene-bridged ß-to-ß and meso-to-meso porphyrin nanorings were successfully synthesized by a palladium-catalyzed Suzuki-Miyaura coupling reaction in a logical synthesis. The dimeric structure was confirmed by XRD analysis. The azo linkages in di- and tetramers are in the all-trans conformation, whereas in the trimers one azo linkage can be interconverted between cis and trans under external stimulation. When trimeric isomers are heated to 333 K or higher, the azo linkages will be in the all-trans configurations: the pure all-trans trimer can be kept in the dark for several months. Fluorescence anisotropy and pump-power-dependent decay results revealed excitation energy transfer for azobenzene-bridged zinc-porphyrin nanorings. The distances between porphyrin units of these azobenzene-bridged porphyrin arrays are almost the same, but the exciton energy hopping (EEH) times for each wheel are markedly different. The dimer and meso-to-meso tetramer possess relatively short excitation energy transfer (EET) times (1.28 and 2.48 ps, respectively) due to their good planarity and rigidity. In contrast, the EET time for the trimeric zinc(II)-porphyrin array (6.9 ps) is relatively long due to its nonradiative decay pathway (i.e., cis/trans isomerization of azobenzene). Both di- and tetramers exhibit relatively high fluorescence quantum yields, whereas the trimers show weak emission because of structural differences.

[Rapid determination of ATP, ADP, AMP and phosphate in drug by 31P NMR spectroscopy].

The content of ATP, ADP, AMP, sodium phosphate and sodium pyrophosphate were determined by 31P NMR, the linear range of ATP, ADP and AMP were found to be 0.004-0.080 mol x L(-1), sodium phosphate and sodium pyrophosphate were 0.005-0.100 mol x L(-1). The RSD were 0.40%-1.30%, the recovery were 96.9% - 105.2%. The method has been applied to the determination of ATP injection. The impurities of ATP injection were ADP and sodium phosphate. The content of ATP is in line with the requirement of the pharmacopoeia. The results indicated that the method is of good reproducibility, high accuracy, rapid and simple operation, without pretreatment and interference of other elements, 31P NMR is a new and reliable method of analyzing ATP, ADP, AMP and phosphate.

Synthesis of direct ß-to-ß linked porphyrin arrays with large electronic interactions: branched and cyclic oligomers.

Direct ß-to-ß linked branched and cyclic porphyrin trimers and pentamers have been synthesized by the Suzuki-Miyaura coupling of ß-borylporphyrins and ß-bromoporphyrins. The cyclic porphyrin trimer, the smallest directly linked cyclic porphyrin wheel to date, and its twined pentamer, exhibit small electrochemical HOMO-LUMO gaps, broad nonsplit Soret bands, and red-shifted Q-bands, thus indicating large electronic interactions between the constituent porphyrin units.