The synthesis of modified chlorophyll carbon nanotube photoactive dyad systems

M.Sc.Donor-acceptor (D-A) systems consist of a donor covalently or non-covalently linked to an acceptor. The simplest D–A system consists of a donor linked to an acceptor and is called a dyad system. Photoactive dyad systems are molecular devices designed to perform through the separation of charge separation states and the conversion of solar energy to chemical energy in analogy to photosynthesis.1 These dyad systems consist of a donor which is usually a chromophore and an acceptor. The design of these systems is guided to mimic photo-induced electron transfer (PET) and charge separation (CS), which are fundamental processes of photosynthesis. In nature, photosynthetic units are often built from dyads consisting of pigments like chlorophyll (donors), non–covalently linked to quinones, (acceptors). The donor harvests light energy and transfers the energy to the nearby pigment molecules until it eventually reaches a special region of the chlorophyll macrocycle called the reaction centre where this light energy is then converted to electrochemical energy. Photoactive dyad systems act as artificial photosynthetic models as they reproduce photo–induced electron transfer and charge separation of natural photosynthesis. In this project, dyad systems were made by covalently linking zinc pheophorbide, a modified chlorophyll derivative to double–walled carbon nanotubes (DWCNTs). Zinc pheophorbide acts as the donor and DWCNTs as the acceptors. Chlorophyll was modified by cutting the phytol chain and inserting zinc as the central metal to yield zinc pheophorbide. This derivative is stable against irradiation, has a good range of acceptor wavelength and is also a good light harvester. DWCNTs are one dimensional nanowires with two concentric tubes. They readily accept electrons because they have an extended π electron system. These electrons are then transported efficiently under ballistic conditions. DWCNTs were synthesised by catalytic chemical vapour deposition (CCVD) of methane over Mg0.99Co0.075Mo0.025O catalyst. In dyad system 1, amidated zinc pheophorbide molecules were covalently attached to oxidised DWCNTs in the presence of N–ethyl–N’–(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) \ and N–hydroxysuccinnimide (NHS) as a catalysts. Dyad system 2 was synthesized by attaching zinc pheophorbide molecules to amidated DWCNTs using the same catalysts