3,4‐Dimethylenecyclobutene: A Building Block for Design of Macrocycles with Excited State Aromatic Low‐Lying High‐Spin States

Abstract

Abstract3,4‐Dimethylenecyclobutene (DMCB) is an unusual isomer of benzene. Motivated by recent synthetic progress to substituted derivatives of this scaffold, we carried out a theoretical and computational analysis with a particular focus on the extent of (anti)aromatic character in the lowest excited states of different multiplicities. We found that the parent DMCB is non‐aromatic in its singlet ground state (S0), lowest triplet state (T1), and lowest singlet excited state (S1), while it is aromatic in its lowest quintet state (Q1) as this state is represented by a triplet multiplicity cyclobutadiene (CBD) ring and two uncoupled same‐spin methylene radicals. Interestingly, the Q1 state, despite having four unpaired electrons, is placed merely 4.8 eV above S0, and there is a corresponding singlet tetraradical 0.16 eV above. The DMCB is potentially a highly useful structural motif for the design of larger molecular entities with interesting optoelectronic properties. Here, we designed macrocycles composed of fused DMCB units, and according to our computations, two of these have low‐lying nonet states (i. e., octaradical states) at energies merely 2.40 and 0.37 eV above their S0 states as a result of local Hückel‐ and Baird‐aromatic character of individual 6π‐ and 4π‐electron monocycles.