Recent synthetic studies on the organic molecules tetracene and pentacene have found certain dimers and oligomers to exhibit an intense absorption in the visible region of the spectrum that is not present in the monomer or many previously studied dimers. In this article we combine experimental synthesis with electronic structure theory and spectral computation to show that this absorption arises from an otherwise dark charge-transfer excitation "borrowing intensity" from an intense UV excitation. Further, by characterizing the role of relevant monomer molecular orbitals, we arrive at a design principle that allows us to predict the presence or absence of an additional absorption based on the bonding geometry of the dimer. We find this rule correctly explains the spectra of a wide range of acene derivatives and observed over 70 years ago. These results pave the way for the solves an unexplained structure-spectrum phenomenon first e design of highly absorbent chromophores with applications ranging from photovoltaics to liquid crystals.