Synthesis of Imidazole-Based [30]Heptaphyrin and Stable Figure-Eight [60]Tetradecaphyrins via [5 + 2] Condensations in One Pot

Abstract

Derived from a Pd-catalyzed oxidative C–H/C–H coupling reaction, two giant imidazole-based [60]­tetradecaphyrins adopting stable figure-eight geometry together with one [30]­heptaphyrin are obtained by [5 + 2] MacDonald condensations in one pot. The directional imidazole is believed to play a vital role for the diverse cyclization and conformation stabilization.

Resolution of Expanded Porphyrinoids: A Path to Persistent Chirality and Appealing Chiroptical Properties

“…This approach was highlighted by a recent report by Gao, You et al who successfully synthesized an imidazole-embedded expanded porphyrinoid, [60]tetradecaphyrin 5 (Figure 4). [22] Enantiomers (M,M)-5 and (P,P)-5 were effectively separated using chiral HPLC (Daicel, Chiralpak IA). This represented the largest expanded porphyrinoid to be successfully separated into its enantiomers to date.…”

“…This oxidative-type NFR was found to give rise to macrocycle 21, which incorporates an unprecedented aza [5]helicene motif within the expanded carbaporphyrin scaffold. In the presence of BF 3 • Et 2 O, a subsequent NFR afforded a more complicated structure (22), with a bidirectional heptacyclic S-shaped helicene ribbon (Figure 18). [40] Racemic mixtures of the two topologically chiral helicenophyrinoids 21 and 22 could be separated into their enantiomers by HPLC using a chiral stationary phase (Chirex 1030).…”

“…(b) X-ray crystal structure of 5. The meso-mesityl (Mes) groups are omitted for clarity.Reprinted with permission from Ref [22]…”

Trends in the Electronic Structure and Chemical Bonding of a Series of Porphyrinoid–Uranyl Complexes

“…With the increasing implementation of nuclear reactors, reprocessing of the spent nuclear fuel has become a hot topic and has attracted increasing attention. − The uranyl ion ([UO 2 ] 2+ ) accounts for approximately 90% of the metal ions of the nuclear waste liquid and exists stably in the natural environment; thus, its recycling is very important toward a sustainable application of nuclear power. − Therefore, it is of great significance to investigate uranyl­(VI) complexes and their stability to understand the chemical transformation and migration of nuclear waste and coordination chemistry in spent nuclear fuel recycling. − The rich and varied coordination chemistry of actinide has made these species of interest from the perspective of ligand design, electronic structure, and theory. , On the other hand, understanding the bonding and coordination environments in actinide complexes could help in the future design of extractants for target actinide elements that could be relevant to the development of the nuclear industry or the remediation of the spent nuclear fuel …”

1,4-Phenylene-Incorporated Decaphyrin(1.0.1.0.0.1.0.1.0.0): Synthesis, Structure, and Topological Chirality

“…To achieve chiral resolution, structural rigidification by means of (non)metal coordination or scaffold modification, e.g., N-fusion, N-methylation, and installation of a central chirality unit, is indispensable. In spite of these important findings, it is worth noting that direct enantiomeric separation of expanded porphyrins in their free-base form has remained an aspirational but elusive target for the past decades. , A perusal of the literature revealed that some enantiomers racemize even at room temperature, , thus further underscoring challenges in this field.…”