Tungsten(VI) Complex of N‐Fused Porphyrin Absorbing Near‐Infrared Light beyond 1000 nm

Yamamoto, Takumi; Abraham, Jibin Alex; Mori, Shigeki; Toganoh, Motoki; Shimizu, Soji; Ishida, Masatoshi; Furuta, Hiroyuki

doi:10.1002/asia.202000014

Cited by 9 publications

(13 citation statements)

References 57 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Internal N–C bond formations within (suitably derivatized) N-confused porphyrins led to the formation of N-fused porphyrins. Their formation and rich and often unusual coordination chemistry ( inter alia , the N-fused porphyrins form inner ruthenium complexes as well as a remarkable ruthenocene-like complex in which the N-fused porphyrin and cyclopentadiene sandwich a ruthenium(II) ion), have been well-reviewed. ,,− …”

Section: Metalloporphyrinoids Containing Nonpyrrolic Building Blockssupporting

confidence: 62%

Metal Complexes of Porphyrinoids Containing Nonpyrrolic Heterocycles

Thuita

Brückner

2022

Chem. Rev.

View full text Add to dashboard Cite

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.

show abstract

Section: Metalloporphyrinoids Containing Nonpyrrolic Building Blockssupporting

confidence: 62%

Metal Complexes of Porphyrinoids Containing Nonpyrrolic Heterocycles

Thuita

Brückner

2022

Chem. Rev.

View full text Add to dashboard Cite

show abstract

“…The resulting sp 2 C16−O2 and C15−O1 bonds were typical double bonds with lengths of 1.244(5) and 1.270(5) Å, respectively. In contrast to the sitting atop metal coordination in the previously reported NFP complexes, Ir ‐ 3 displayed in‐plane coordination of the iridium cation to the NNOC core [20,38] . The corresponding σ‐carbon donor site, which originated from the cyclooctene ligand fused to the α‐confused pyrrole ring of NFP, led to the formation of an unusual C( sp 3 )‐Ir bond with a bond length of 2.069(4) Å (Figure S10).…”

Section: Figurementioning

confidence: 85%

Iridium Complex of N‐Fused Bilatrienone: Oxidative Cleavage of N‐Fused Porphyrin Induced by Iridium‐Cyclooctadiene Complexation

Abraham

Mori

Ishida

et al. 2021

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

N‐fused porphyrin (NFP) is a unique class of photostable near‐infrared dyes with an 18π aromatic tetrapyrrole macrocyclic skeleton containing a tri‐fused pentacyclic moiety. Here, the synthesis of an iridium complex of N‐fused bilatrienone is reported as the degradation product of Ir‐cyclooctadiene (cod)‐induced oxidative cleavage of NFP under aerobic conditions. Similar to the native bilin chromophores, the ring‐opened complex featured a broken π‐conjugation circuit and exhibited a broad visible absorption band. In contrast, metalation of NFP using an iridium(I)(cod) complex under an inert atmosphere resulted in the formation of a cod‐isomerized (κ1,η3‐C8H12)‐Ir complex.

show abstract

“…323 Recently, tungsten(VI) complexes of N-fused porphyrin were reported, where a narrower HOMO−LUMO band gap was observed. 324 Heating NFP with WO 2 Cl 2 afforded W(NFP)ClO 2 319 and its 21-chlorinated product 320 in 30% and 10% yields, respectively (Scheme 128). Interestingly, the tungsten(VI) complex 319 showed near-IR absorption at 1021 nm despite its compact [18]annulenic substructure.…”

Section: Syntheses and Functionalizationmentioning

confidence: 99%

“…Recently, tungsten(VI) complexes of N-fused porphyrin were reported, where a narrower HOMO–LUMO band gap was observed . Heating NFP with WO 2 Cl 2 afforded W(NFP)ClO 2 319 and its 21-chlorinated product 320 in 30% and 10% yields, respectively (Scheme ).…”

Section: N-fused Porphyrinsmentioning

confidence: 99%

Creation from Confusion and Fusion in the Porphyrin World─The Last Three Decades of N-Confused Porphyrinoid Chemistry

Toganoh

Furuta

2022

Chem. Rev.

Self Cite

View full text Add to dashboard Cite

Confusion is a novel concept of isomerism in porphyrin chemistry, delivering a steady stream of new chemistry since the discovery of N-confused porphyrin, a porphyrin mutant, in 1994. These days, the number of confused porphyrinoids is increasing, and confusion and associated fusion are found in various fields such as supramolecular chemistry, materials chemistry, biological chemistry, and catalysts. In this review, the birth and growth of confused porphyrinoids in the last three decades are described.

show abstract

Tungsten(VI) Complex of N‐Fused Porphyrin Absorbing Near‐Infrared Light beyond 1000 nm

Cited by 9 publications

References 57 publications

Metal Complexes of Porphyrinoids Containing Nonpyrrolic Heterocycles

Metal Complexes of Porphyrinoids Containing Nonpyrrolic Heterocycles

Iridium Complex of N‐Fused Bilatrienone: Oxidative Cleavage of N‐Fused Porphyrin Induced by Iridium‐Cyclooctadiene Complexation

Creation from Confusion and Fusion in the Porphyrin World─The Last Three Decades of N-Confused Porphyrinoid Chemistry

Contact Info

Product

Resources

About