Investigations of the optical effects in thienoacene chromophores with different central atoms were performed. These chromophores provide a basis for the comparison of the linear, two-photon, and entangled two-photon properties in organic molecules with varying degrees of dipolar or quadrupolar character. Linear absorption and emission as well as time-dependent density functional theory calculations were performed for the chromophores investigated. Measurements of the classical two-photon absorption (TPA), entangled two-photon absorption (ETPA), as well as entangled two-photon fluorescence were experimentally performed for the four chromophores. Electronic structure calculations were utilized to provide estimates of the classical two-photon absorption coefficients. The results of the measured entangled two-photon cross sections were compared with theoretical estimates for the molecules investigated. It is found that the dipole (transition or permanent) pathway can have an effect on the trends in the entangled photon absorption process in dipolar organic chromophores. This study helps predict the properties of the entangled twophoton effect in chromophores with different dipolar and quadrupolar character.