Chirality and spatially pre-organized multi-porphyrinoids

Abstract

We report herein that chiral and enantiopure compounds such nucleosides and peptides can pre-organize multi-porphyrinic systems and influence their properties. The first example given concerns star-shaped mutli-porphyrins with chiral and enantiopure nucleosidic linkers. If the configuration is indeed a star-shaped nanomolecule, it appears that the induced conformation is nothing as expected. The four peripheral Zn(II) porphyrins collapse over the free-base central one, inducing totally different photo-physical properties. Despite a minor expected light energy harvesting behavior, the principal capability of this system is to quench the collected light energy and convert it from radiative to non-radiative de-activation. The second example concerns polypeptides with pendant porphyrins. The peptidic backbone confers to the systems, after a certain degree of oligomerization, a 310 right handed helical conformation which induces cavities within the multi-porphyrinc architecture, ready to welcome guests and render, for example, the complexation of C60 much easier. We thus have constructed novel organic photovoltaic systems using supramolecular complexes of porphyrin-peptide oligomers with fullerene clusters. The composite cluster OTE/SnO2 electrode prepared with (P(ZnP)16+ C60)m, exhibits an impressive incident photon-to-photocurrent efficiency (IPCE) with values reaching as high as 56%. The power conversion efficiency of the (P(H2P)16+ C60)m modified electrode reaches 1.6%, which is 40 times higher than the value (0.043%) of the porphyrin monomer (P(H2P)1 + C60)m modified electrode. Thus, the organization approach between porphyrins and fullerenes with polypeptide structures is promising, and may make it possible to further improve the light energy conversion properties by using a larger number of porphyrins in a polypeptide unit. © 2018 World Scientific Publishing Company.