The photophysics of dialkylamino- and/or pyridine-containing functional chromophores, 1,4-distyryl-2,5-bis(ethynylaryl) benzenes (cruciforms) was investigated; their fluorescence quantum yields and emissive lifetimes were determined. Depending upon their substituents, the frontier molecular orbitals (FMOs) of these cruciforms are either congruent, i.e., HOMO and LUMO occupy the same real space, or disjoint, i.e., the HOMO is located on one branch of the cruciform while the LUMO is located on the second one. Donor-acceptor substitution leads to a disjoint FMO pattern, while the parent 1,4-distyryl-2,5-bis(phenylethynyl)benzene shows congruent FMOs. The photophysics of the cruciforms was investigated upon addition of either an excess of trifluoroacetic acid or an excess of selected metal (Mg2+, Ca2+, Mn2+, Zn2+) trifluoromethanesulfonate salts. Addition of either metal ions or protons led to analogous but not identical changes in the spectroscopic properties of the investigated cruciforms. The collected data suggest that the metals bind preferentially at the aniline nitrogen and not at the electron-rich arene. The spatially separated FMOs permit the independent manipulation of the HOMO and the LUMO of such cruciforms. If the branches contain metal-complexing moieties, metal binding leads to either a hypsochromic or a bathochromic shift in emission via interaction of the metal cations with either the HOMO or the LUMO.