Soluble meso-tetrakis(arylethynyl)porphyrins — synthesis and optical properties

Trans-A2B2-tetrakis(arylethynyl)porphyrins with suitable solubility in CH2Cl2, CHCl3, EtOAc, acetone and toluene have been obtained for the first time. Among two possible strategies the one comprising the synthesis of 5,15-dibromo-10,20-bis[(isopropylsilyl)ethynyl]porphyrin proved to be more efficient. The pathway towards densely substituted arylacetylenes has been optimized. The use of previously identified 3,4,5-trialkoxyaryl substituent was crucial for achieving the reasonable solubility. The optical properties of meso-substituted tetrakis(arylethynyl)porphyrins were studied showing that strong polarization imparted by direct conjugation of all four substituents with porphyrin core resulted not only in strong absorption of red light but also in a relatively long triplet lifetime. Meso-tetrakis(arylethynyl)porphyrins have a significantly longer lifetime of T1 state than bis(arylethynyl)porphyrins and in their case all the states are mixtures of transitions between the HOMO-1, HOMO and LUMO, LUMO+1 MOs. We show that the presence of two additional arylethynyl substituents at meso-positions enhance the maximum two-photon absorption cross-section of trans-A2B2-tetrakis(arylethynyl)porphyrins by more than one order of magnitude. Maximum values as high as σ2 = 500 GM at 950 nm result from realization of suitable conditions for effective resonance enhancement along with a lowering of the energy and intensification of the two-photon allowed transitions in the Soret region.