Final Activity Report Summary - SESYPCNLO (SElective SYnthesis of Non-centrosymmetric PhtaloCyanines for NonLinear Optics)
During this fellowship I was involved in the design, synthesis and characterisation of novel phthalocyanine systems with the aim of preparing compounds with improved nonlinear optical properties.
In order to prepare these new phthalocyanine-based molecular structures different synthetic strategies were applied with various degrees of success, such as high pressure methods and transition-metal catalysed reactions. Unfortunately, the high pressure strategy proved to be non feasible due to the serious reagents solubility problems that were encountered, hence all the efforts were concentrated on the transition-metal catalysed reactions, such as the Sonogashira, Heck, Suzuki, Stille, Buchwald, cobalt-catalysed cyclotrimerisation reactions etc, with excellent results. The cobalt-catalysed cyclotrimerisation was applied to ethynyl-containing Pc systems providing a quite elegant and facile method for the synthesis of sterically-crowded, benzene-centred multi-phthalocyanine systems which would otherwise be difficult to obtain via other synthetic strategies. The study of the nonlinear optical properties of these molecules was under progress by the time of the project completion.
A new family of Pc-C60 fullerene dyads where the two active units, namely the Pc and the C60 fullerene, were connected by an ethynyl linker were prepared, giving unexpected and surprising results for some dyads, such as the first example of a supramolecular-driven regioselective and stereoselective synthesis of a C60 fullerene bisadduct. Photophysical and electrochemical studies of these dyads were under progress beyond the project timeframe.
New liquid crystals based on phthalocyanine architectures were prepared, showing an unusual mesomorphic behaviour since each disk of the hexagonal columnar mesophase was formed by two phthalocyanine units. Further studies were in progress on mesogenic Pc-based systems in order to gain a better understanding on the phthalocyanine structural features that were required to influence the resulting columnar organisation. Most of the results obtained along the fellowship were either published, sent for publication or in preparation for submission in top-quality international journals.
In order to prepare these new phthalocyanine-based molecular structures different synthetic strategies were applied with various degrees of success, such as high pressure methods and transition-metal catalysed reactions. Unfortunately, the high pressure strategy proved to be non feasible due to the serious reagents solubility problems that were encountered, hence all the efforts were concentrated on the transition-metal catalysed reactions, such as the Sonogashira, Heck, Suzuki, Stille, Buchwald, cobalt-catalysed cyclotrimerisation reactions etc, with excellent results. The cobalt-catalysed cyclotrimerisation was applied to ethynyl-containing Pc systems providing a quite elegant and facile method for the synthesis of sterically-crowded, benzene-centred multi-phthalocyanine systems which would otherwise be difficult to obtain via other synthetic strategies. The study of the nonlinear optical properties of these molecules was under progress by the time of the project completion.
A new family of Pc-C60 fullerene dyads where the two active units, namely the Pc and the C60 fullerene, were connected by an ethynyl linker were prepared, giving unexpected and surprising results for some dyads, such as the first example of a supramolecular-driven regioselective and stereoselective synthesis of a C60 fullerene bisadduct. Photophysical and electrochemical studies of these dyads were under progress beyond the project timeframe.
New liquid crystals based on phthalocyanine architectures were prepared, showing an unusual mesomorphic behaviour since each disk of the hexagonal columnar mesophase was formed by two phthalocyanine units. Further studies were in progress on mesogenic Pc-based systems in order to gain a better understanding on the phthalocyanine structural features that were required to influence the resulting columnar organisation. Most of the results obtained along the fellowship were either published, sent for publication or in preparation for submission in top-quality international journals.