Triplet State Baird Aromaticity in Macrocycles: Scope, Limitations, and Complications.

ABSTRACT: The aromaticity of cyclic 4nπ-electron molecules in their first ππ* triplet state (T₁), labeled Baird aromaticity, has gained growing attention in the past decade. Here we explore computationally the limitations of T₁ state Baird aromaticity in macrocyclic compounds, [n]CM's, which are cyclic oligomers of four different monocycles (M = p-phenylene (PP), 2,5-linked furan (FU), 1,4-linked cyclohexa-1,3-diene (CHD), and 1,4-linked cyclopentadiene (CPD)). We strive for conclusions that are general for various DFT functionals, although for macrocycles with up to 20 π-electrons in their main conjugation paths we find that for their T₁ states single-point energies at both canonical UCCSD(T) and approximative DLPNO-UCCSD(T) levels

SUBMITTER: Ayub R 

PROVIDER: S-EPMC7884009 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature