In this contribution we describe a combined experimental and theoretical study of the relation between the molecular structure and the electronic properties of conjugated donor-acceptor type chromophores for light-harvesting applications. A series of model systems was synthesized where a central anthracene (electron donor) is connected to dicyanovinyl units (electron acceptor) through a π-conjugated spacer. The study of the redox and optical properties of these chromophores and of reference compounds without dicyanovinyl units allows us correlate the electronic properties to the presence of the electron withdrawing groups and the molecular conformation. Comparison with calculated electronic structure shows that the construction of chromophores that consist of electron donating and accepting units does not always follow the simple rules that are generally used in the design of such molecules. The results show a subtle relation between the charge transfer character and the geometry of the molecules. In some cases this leads to significant contribution of charge transfer excitation to the absorption spectra of some chromophores while such contributions are completely absent in others.