Excitonic dynamics of Chlorophyll-a molecules in chitosan hydrogel scaffold

Abstract

Biomimetic photo harvesting architecture has been proposed as an alternative for existing solar conversion systems. This fact led us to the successful realization of non-coherent electron hopping [hopping rate 4.28 ns⁻¹] through excitonically coupled Chlorophyll-a (Chl-a) molecules within chitosan hydrogel matrix via TCSPC (Time Correlated Single Photon Count) and fluorescence anisotropy measurements. Chl-a molecules remain stable within the hydrogel matrix up to 3 months, as evidenced from UV-vis spectroscopy. The mono-exponential decay parameter with 78 picoseconds time scale, high initial anisotropy data [r₀ = 0.33] and with reduced TCSPC lifetime [1.311 ns] of 23° in plane aligned Chl-a macrocycles, indicate that hopping excitonic cascade is prominent among chlorophyll molecules. From the Raman Spectra, it can be postulated that they form a highly co-ordinated closely packed structure via water molecules within chitosan hydrogel due to 6th co-ordination through central Mg of porphyrin macrocycle. All these data predict that this chlorophyll-chitosan hydrogel can be an active component in artificial light harvesting systems.