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

Abstract

Rosenthal's-reagent-mediated intramolecular cyclometallation of α,α-dialkynyldipyrrin nickel(II) complex and subsequent acid treatment afforded a 1,3butadiene-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 CÀ H•••π interaction. DFT calculations revealed that the electrostatic attraction was dominant with binding energy of 32.8 kcal mol À 1 .

Bent Dithienoporphyrin(2.1.2.1): Synthesis, Structure, Optical and Electronic Properties, and Metal Complexation

“…The bond distances for [2,3]­F 5 TP and [3,4]­F 5 TP indicated that they are nonaromatic properties (Figure ). , The optimized structures of [2,3]­F 5 TP ( syn - and anti -isomers) and [3,4]­F 5 TP , obtained by DFT calculations, also supported the observation of nonaromaticity (Figure S19, SI). , …”

Pyrene-Bridged Expanded Carbaporphyrin Nanobelts

“…This progress not withstanding, nanorings and nanobelts containing functional groups that would allow for postsynthetic modification, including metal cation complexation, remain rare. − One attractive approach to such systems involves the use of porphyrins, classic planar and aromatic macrocycles whose rich functional chemistry is well documented . Anderson and co-workers and Osuka, Song et al have reported, respectively, template directed syntheses of wheel-like porphyrin oligomers − and the metal-mediated preparation of belt-like porphyrins, respectively. − However, systems that combine PAHs and the free pyrrolic functionality characteristic of porphyrins in a single discrete molecular belt-like arrangement are essentially unknown. , Herein, we report two isomeric nanosized pyrene-containing carboporphyrin hybrids, NB1 and NB2 (Scheme ), and show that these belt-like systems can be converted to their corresponding zinc complexes.…”

Direct Synthesis of ABCD‐Porphyrin Platinum(II) Complexes via Dehydrative Aromatization

“… [7c] Later, his group applied the metal‐templated cyclization to construction of ABCD porphyrins using Mg(II), Zn(II), and Ni(II) from ABCD‐functionalized bilanes (Figure 1D). [5b,7c] This strategy has also been applied to other porphyrinoids such as diazaporphyrin, [8a,b] norcorrole, [8c,d] and porphyrin(2.1.2.1) [8f] derivatives. In all compounds, the affinity of metal(II) ion for square‐planar geometry plays a crucial role.…”