Organoboron Complexes in Edge‐Sharing Macrocycles: The Triphyrin(2.1.1)–Tetraphyrin(1.1.1.1) Hybrid

Abstract

The formation of a precisely designed environment predefined for stabilizing electron‐deficient atoms, such as boron(III), is an important approach for optimizing the properties of a chromophore. A triphyrin(2.1.1) motif built on the extended π‐system of a tetraphyrin(1.1.1.1) skeleton creates a new coordination environment, with a CNN set of donors confined in a limited space predefined for binding small cations. The entrapment of boron(III) in the triphyrin(2.1.1) sector, with formation of a direct B−C bond, significantly changes the optical response and the global aromatic character of the compound, leading to an extension of the π‐delocalisation.

Toward Practical Quantum Embedding Simulation of Realistic Chemical Systems on Near-term Quantum Computers

“…2(a) and (b), we find that using larger basis set brings the potential energy curve produced by DMET-ESVQE much closer to the MRCI+Q+F12@CBS reference curve and the exact dissociation limit. Next, we study the energy profile for the addition reaction between C 6 H 8 and H 2 in gas phase, which is a simplified model for the addition of hydrogen to conjugated hydrocarbons, an essential step for many organic synthesis routes [60][61][62]. A schematic diagram of the addition reaction is depicted in Fig.…”

Triangularly shaped cyclic defects for the selective boron doping of π-extended systems

“…Consequently, the application of boron(III) halides in the simple bora-Friedel-Crafts reaction catalyzed with the corresponding aluminum halide is limited to the modification of small aromatic systems. 17 Such a process can be, of course, utilized in the formation of C-B bonds as a subsequent reaction after Si-B exchange, 18 C-Li bond substitution, 19,20 or B-N bond formation 21,22 that defines the second key aspect of structural modifications being in the focus of the modulation of the p-extended structures. A specific interaction between boron and nitrogen is very intensively explored in nanographene structures.…”

Multi‐Cation Coordination in Porphyrinoids

“…[17] Much more evident extension of delocalization was achieved by Pawlicki and co-workers for 30-a molecule merging at etraphyrin(1.1.1.1) (porphyrin)a nd triphyrin(2.1.1) motifs. [19] Formation of the final product required an intramolecular McMurry coupling of 29 (Scheme 7). As elective hydrogenation of C2 linker in 30 gave compound 32 where potential delocalization was blocked.…”

“…Therefore, the designatedm olecule can be described by two alternative resonance forms (Scheme7): an 18p tetraphyrin(1.1.1.1) or a2 6 p hexaphyrin(2.0.1.1.1.0)w ith as ignificantly increased contribution of the extended path for more planar structure. [19]…”