The photophysical and two-photon absorption (2PA) properties of two tri-podal molecules and of their quadrupolar and dipolar counterparts are reported for a series of solvents with varying polarity. The molecules possess a tri-phenylamine electron donating group and mono-cyano acceptors while olefinic and acetylenic p-linkers have been used. Branching led to an increase of the molar extinction coefficient and to a slight bathochromic shift of the absorption spectra while the fluorescence quantum yields decrease but they are maintained to relatively high values. Solvatochromic measurements in the tripodal molecules revealed an emitting state with a polar nature. The 2PA cross sections in general increase upon branching but the observed behaviour strongly depends on the type of solvent. The highest 2PA cross sections are obtained in solvents of medium polarity and values as high as 1420 GM are reported.

A series of twelve tripodal push-pull molecules with central triphenylamine donor and peripheral cyano substituted acceptors has been prepared. These molecules possess systematically altered π-linker as well as cyano acceptors. Based on the experimental properties measured by differential scanning calorimetry, electrochemistry, one and two photon absorption/emission spectra, supported by the DFT calculations, thorough structureproperty relationships were elucidated.Scheme 1 Modification of the TPA core leading to precursors 13-16Scheme 2 Structure and selected synthesis of cyano-substituted acceptor moieties 23-33Scheme 3 Combination of A-and D-parts leading to tripodal push-pull molecules 1-12

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