Simultaneous Implementation of <i>N</i>-Heterocycle-Fused Bridge and Modified Pyrrole Unit on Ni(II) Porphyrin Dimers

Li, Yuanyuan; Zhou, Mingbo; Xu, Ling; Zhou, Bixiang; Rao, Yutao; Nie, Haigen; Gu, Tingting; Zhou, Jie; Xu, Ling; Yin, Bangshao; Zhu, Weihua; Osuka, Atsuhiro; Song, Jianxin

doi:10.1021/acs.orglett.0c02084

Cited by 15 publications

(13 citation statements)

References 41 publications

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“…Interesting cases from structural as well as mechanistic points of view are the N -heterocycle-fused PMP dimer nickel(II) complexes 73Ni 2 through 75Ni 2 (Scheme ). A palladium-catalyzed Suzuki–Miyaura coupling reaction of meso -triaryl, meso -bromo nickel(II) porphyrin 70Ni with β-borylated meso -triaryl nickel(II) porphyrin 71Ni afforded a meso -to-β-linked porphyrin dimer. This could be nitrated and then reduced to form the meso -amino porphyrin dimer 72Ni 2 , the key precursor.…”

Section: Metalloporphyrinoids Containing Nonpyrrolic Building Blocksmentioning

confidence: 99%

“…The formation of the 3-keto-4-imidopyrrole-based dimer 73Ni 2 is the result of an oxidative coupling/framework oxidation, without alteration of the porphyrin frameworks. However, the formation of the pyrrole-modified 6-membered dihydropyri-midine 74Ni 2 and imidazolinone 75Ni 2 involved the insertion of the (former) amine nitrogen into the fused pyrrole or the formal replacement of a β-carbon atom by the amine nitrogen atom, respectively . While the former reaction is unprecedented among the reactions converting porphyrins to their pyrrole-modified analogues, the latter reaction resembles the formation of porpholactams , by means of the collapse of a larger ring (see Section ).…”

Section: Metalloporphyrinoids Containing Nonpyrrolic Building Blocksmentioning

confidence: 99%

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Metal Complexes of Porphyrinoids Containing Nonpyrrolic Heterocycles

Thuita

Brückner

2022

Chem. Rev.

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The replacement of one or more pyrrolic building block(s) of a porphyrin by a nonpyrrolic heterocycle leads to the formation of so-called pyrrole-modified porphyrins (PMPs), porphyrinoids of broad structural variability. The wide range of coordination environments (type, number, charge, and architecture of the donor atoms) that the pyrrole-modified frameworks provide to the central metal ions, the frequent presence of donor atoms at their periphery, and their often observed nonplanarity or conformational flexibility distinguish the complexes of the PMPs clearly from those of the traditional square-planar, dianionic, N 4 -coordinating (hydro)porphyrins. Their different coordination properties suggest their utilization in areas beyond which regular metalloporphyrins are suitable. Following a general introduction to the synthetic methodologies available to generate pyrrole-modified porphyrins, their general structure, history, coordination chemistry, and optical properties, this Review highlights the chemical, electronic (optical), and structural differences of specific classes of metalloporphyrinoids containing nonpyrrolic heterocycles. The focus is on macrocycles with similar "tetrapyrrolic" architectures as porphyrins, thusly excluding the majority of expanded porphyrins. We highlight the relevance and application of these metal complexes in biological and technical fields as chemosensors, catalysts, photochemotherapeutics, or imaging agents. This Review provides an introduction to the field of metallo-PMPs as well as a comprehensive snapshot of the current state of the art of their synthesis, structures, and properties. It also aims to provide encouragement for the further study of these intriguing and structurally versatile metalloporphyrinoids.

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Section: Metalloporphyrinoids Containing Nonpyrrolic Building Blocksmentioning

confidence: 99%

Section: Metalloporphyrinoids Containing Nonpyrrolic Building Blocksmentioning

confidence: 99%

Metal Complexes of Porphyrinoids Containing Nonpyrrolic Heterocycles

Thuita

Brückner

2022

Chem. Rev.

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“…Oxidation of the β– meso -linked porphyrin dimer 363.1 resulted in the formation of three differently fused porphyrin dimers 363.2 , 363.3 , and 363.4 (Scheme ). Specifically, the use of PbO 2 in DCM at rt gave 363.2 and 363.3 in yields of 68 and 19%, respectively, whereas oxidation with MnO 2 produced 363.4 was obtained in 1% yield along with 363.2 (58%) and 363.3 (9%). The UV–vis–NIR absorption spectra showed perturbed optical properties with a large red-shift in the lowest-energy Q-like band (937 nm) for 363.3 .…”

Section: Macrocyclic Systemsmentioning

confidence: 99%

“… a Reagents and conditions: (a) PbO 2 (100 equiv), DCM, rt, 12 h; (b) MnO 2 (100 equiv), DCM, rt, 16 h. …”

Section: Macrocyclic Systemsmentioning

confidence: 99%

Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

et al. 2021

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“…Here, it is worthy to note that porphyrins fused with seven‐membered ring have still remained scarce, though some polycyclic systems bearing heptagon(s) were prepared, whose properties and structure are intriguing [7] . A limited number of porphyrin examples were synthesized via multi‐step reactions by Osuka, [8a,b] Scott, [8c] and our group [8d] (Scheme 1, 1 e – h ). Thus, the development of a convenient and general route to preparation of seven‐membered ring is highly desirable.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2022

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Rhodium-catalyzed reaction of meso-pyrrol-2yl Ni II porphyrins with internal alkynes proceeded smoothly to give singly, doubly, and quadruply sevenmembered-ring fused Ni II 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 Zn II and Ni II porphyrins possessing an unsubstituted meso-position were dimerized to meso-meso linked dimers by aerobic oxidation with Zn-(OAc) 2 •2 H 2 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.

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

Cited by 15 publications

References 41 publications

Metal Complexes of Porphyrinoids Containing Nonpyrrolic Heterocycles

Metal Complexes of Porphyrinoids Containing Nonpyrrolic Heterocycles

Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

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

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