The singlet triplet (ST) gap of linear polyacenes decays exponentially with the system size as a result of extended conjugation and reducing highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps. These low ST gaps can ideally be leveraged toward energy applications but are hindered by the decreasing stability of the systems. Thus, there is the need to understand the ST gap of nonlinear polyacenes, which are markedly more stable than their linear counterparts. Here, we show that the ST gaps of the nonlinear polyacenes do not decrease with the system size and have no correlation with the HOMO-LUMO gaps or increased conjugation. The reason behind this is identified as the high multireference character of the triplet high-spin state. These unprecedented results are in stark contrast to the observations in linear polyacenes and are due to the combined effects of topology and geometrical factors.
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