148216-74-4Relevant academic research and scientific papers
Effect of Porphyrin Ring Distortion on the Spectral and Electrochemical Properties of Short-chain Basket-handle Porphyrins
Ravikanth, Mangalampalli,Reddy, Damodar,Misra, Ashutosh,Chandrashekar, Tavarekere K.
, p. 1137 - 1142 (2007/10/02)
The effect of porphyrin ring distortion on the spectral and electrochemical properties of short-chain basket-handle porphyrins has been investigated.The covalent attachment of opposite phenyl rings of meso-5,10,15,20-tetraphenylporphyrin (H2tpp) by short bridging groups of varying nature and length induces distortion in the porphyrine ring.Optical absorption studies indicate large bathochromic shifts (502-1139 cm-1) for both Q and Soret bands and the magnitude of these shifts are linearly correlated with the degree of distortion.The potential values for the porphyrin ring oxidation and reduction were shifted to less-positive (180-260 mV) and to more-negative (280-390 mV) values respectively relative to planar H2tpp.The magnitude of the shifts in the optical absorption bands and redox potentials are independent of the nature of the bridging chain.The origin of these shifts are traced to structural effects caused due to the introduction of a short bridging group rather than to the electronic effect of the bridging group.Introduction of Cu2+ into the porphyrin core does not affect the degree of distortion and ESR studies indicate no significant change in the electronic structure of Cu2+ ion relative to .
