Self-organizing donor-acceptor assemblies of cobalt(II) porphyrin ligated with gold(III) porphyrin or fullero[60]pyrrolidine in liquid medium

This work provides the results of the spectroscopic, electrochemical, and photoelectrochemical study of the self-assembly in the systems consisting of (2,3,7,8,12,13,17,18-octaethylporphinato)cobalt(II) (CoOEP), (2,3,7,8,12,18-hexamethyl,13,17-diethyl,5-(4-pyridyl)porphinato)gold(III) chloride (ClAuP)/1'-N-methyl-2'-(pyridin-4-yl)pyrrolidino[3',4':1,2][60]fullerene (PyC60), and 1,2-dichlorobenzene/toluene as an electron donor, an acceptor, and a liquid medium, respectively. The results indicate axial coordination of electron acceptor functionalized by the pyridine units by cobalt(II) porphyrin with the donor-acceptor (ClAuP)(2)CoOEP/(PyC60) 2CoOEP triad formation. The thermodynamic stability constant is (4.91 +/- 1.10)x10(9) L-2 mol(-2) and (4.10 +/- 1.14) x10(10) L-2 mol(-2) for ClAuP and PyC60, respectively. The formation of supramolecules was confirmed by UV, visible, IR, H-1 NMR spectroscopy and cyclic voltammetry. DFT calculations (B3LYP+def2-SVP) detect octahedral geometry of the coordination center with the trans configuration of the axial ligands in the triads as well as the excited state calculations establish photoinduced electron transfer (PET). The j(ph)(avg) value 266 mu A cm(-2) for the Ti vertical bar(ClAuP)(2)CoOEP vertical bar 0.5 M Na2SO4 vertical bar Pt system being 2-2.5 times higher compared with the precursors and slightly higher compared with (PyC60)(2)CoOEP shows that gold(III) porphyrin as an electron acceptor can be successfully used. The development of donor/acceptor platform selection strategy for the obtaining of photoactive supramolecules is an urgent task for future deriving of photovoltaic devices. (C) 2021 Elsevier B.V. All rights reserved.

Automated summary

This work presents the results of spectroscopic, electrochemical, and photoelectrochemical study on self-assembly systems, revealing the structural features and stability, and confirming the formation of supramolecules. The findings suggest that gold(III) porphyrin can be effectively used as an electron acceptor in the systems.