In this programme we aim to execute a feasibility study where unique assemblies of chromophoric, charge injection units are arranged to deliver energy (electrons) to a generic/versatile acceptor. The assemblies can, in many ways, be viewed as synthetic analogues of the chlorophyl active site light harvesting array. The fundamental design principle is extremely simple but nevertheless represents a significant conceptual and synthetic advance. There are several key differences between the work proposed and more conventional approaches which make it both adventurous and most appropriate for support as a feasibility study.

• We aim to prepare, using reproducible, potentially scalable chemistry, multichromophore assemblies with defined geometry but little or no ground state interaction. The adventurous ultimate aim, which is acknowledged as high risk, is to engineer photoelectrochemical crossover from conventional single electron processes to massively more useful multielectron domains.

• The key to success of the approach is use of a suitable template for the crucial synthetic operations. This template can itself perform a function in the energy generation process  as a multielectron redox centre and/or be easily removed to reveal a covalent molecular assembly with cooperative binding sites ready for encapsulating inorganic semiconductor nanoparticles or surface binding.

Phthalocyanines are chosen initially, and the project plan for the first year will involve synthesis of unsymmetrical phthalocyanines suitable for covalent assembly only a central core

M. J. Cook, A. N. Cammidge, I. Chambrier, E. H. G. Langner, M. Rahman and J. Swarts Characterisation, liquid crystallinity and spin-coated films of some metallated 1,4,8,11,15,18,22,25-octaalkyl tetrabenzo[b,g,l,q][5,10,15]triazaporphyrin derivatives" J. Porphyrins and Phthalocyanines, 15, 890-897, 2011.

Z. Zhao, A. N. Cammidge, D. L. Hughes and M. J. Cook "Modular face-to-face assembly of multichromophore arrays that absorb across the complete UV-visible spectrum and into the near-IR" Org. Lett. 12, 5138-5141, 2010.

A. N. Cammidge, I. Chambrier, M. J. Cook, D. L. Hughes, M. Rahman  and L. Sosa-Vargas "Phthalocyanine analogues: unexpectedly facile access to non-peripherally substituted octa-alkyl tetrabenzotriazaporphyrins, tetrabenzodiazaporphyrins,  tetrabenzomonoazaporphyrins and tetrabenzoporphyrins" Chem Eur. J. 17, 3136-3146, 2011.

Z. Zhao, A. N. Cammidge and M. J. Cook "Towards black chromophores: mu-oxo linked phthalocyanine-porphyrin dyads and phthalocyanine-subphthalocyanine dyad and triad arrays" Chem. Commun. 7530-7532, 2009.