Formation Reaction, Spectroscopy, and Photoelectrochemistry of the Donor–Acceptor Complex (5,10,15,20-Tetraphenyl-21,23H-porphinato)cobalt(II) with Pyridyl-Substituted Fullero[60]pyrrolidine

Recent progress in organometallic porphyrin‐based molecular materials for optical sensing, light conversion, and magnetic cooling

“…[114,115,117,120] IR spectra were used to establish both the presence of pyridyl-substituted fulleropirrolodine in a dyad structure and intrasphere or extrasphere bonding of anionic group, X. [111,115] To the study of the PET and determine of parameters of the state with separated charges, methods of fluorescence, [24,109,114,122] photoelectrochemistry, [24,114,115,120,122,123] and femtosecond transient absorption were chosen. [117] It can be seen that the reactions under consideration are characterized by a variety of forms and the chemical composition of dyads and triads, differing in stoichiometric mechanisms of their formation, the state of axial anionic groups in them, and a specific medium for selforganization.…”

“…The results of photoelectrochemical study of porphyrin/phthalocyanine-fullerene dyads are presented in Figure 10 where numerical values of relevant parameters were taken from the works. [14,114,115,117,120,122,123] It was primarily reported that the photosensitivity that is manifested not only by the porphyrin-fullerene donoracceptor complexes but also by the dyad precursors is not dependent on the organic solvent from which a photoactive film was obtained on the surface of the titanium electrode covered with natural oxide. Photoelectrochemical parameters of the dyad/triad films being much higher than these for the corresponding precursors depend in a complex way on both a central atom and a macrocycle chemical structure.…”

“…Both increases of structural regularity by combination of MPXs and pyridine derivative with the fullerene moiety in one supramolecule and synthesis of solution‐processable materials were used to produce SM‐OSC active layer materials in the works. [ 109–130 ] Here, a D–π–A chain was constructed based on MPXs axially bonded with pyridyl‐containing fullero[60]/[70]pyrrolidines where the role of donor, π‐spacer, and acceptor belongs to electron‐excessed aromatic tetrapyrrole macrocycle, central transition metal with asymmetrically filled shell, and the base with fullerene moiety, respectively (Table S8). Because you first need to know the regularity of donor–acceptor pair formation, its solubility and stability, and the self‐assembly thermodynamics/kinetics, the optoelectronic properties including calculation of excited states, photoelectrochemistry, and charge/electron transfer ability were obtained on examples of porphyrin–fullerene dyads and triads with In III (see Section 3), Mo V , Mn III , Co II , and Re V (Figure 7).…”

“…The chemical structure of the reaction products and intermediates was confirmed using spectral methods and quantum‐chemical calculations. Self‐assembly stoichiometry and a step mechanism were revealed from thermodynamic kinetic measurements, [ 15,69,121,113 ] whereas the dynamic of the macrocycle electron and geometric state during donor–acceptor bonding was monitored by origin of nuclear magnetic resonance (NMR) signal shifts [ 24,111,114,115,123 ] and quantum‐chemical calculation data. [ 114,115,117,120 ] IR spectra were used to establish both the presence of pyridyl‐substituted fulleropirrolodine in a dyad structure and intrasphere or extrasphere bonding of anionic group, X.…”

“…[ 114,115,117,120 ] IR spectra were used to establish both the presence of pyridyl‐substituted fulleropirrolodine in a dyad structure and intrasphere or extrasphere bonding of anionic group, X. [ 111,115 ] To the study of the PET and determine of parameters of the state with separated charges, methods of fluorescence, [ 24,109,114,122 ] photoelectrochemistry, [ 24,114,115,120,122,123 ] and femtosecond transient absorption were chosen. [ 117 ]…”