Effects of a Central Atom and Peripheral Substituents on Photoinduced Electron Transfer in the Phthalocyanine–Fullerene Donor–Acceptor Solution-Processable Dyads

Abstract

For understanding the physical chemistry behind improving photoelectrochemical charge separation parameters and providing solution-processability, multiple peripheral substitution by 3,5-di-tert-butylphenoxy groups in design of donor−acceptor phthalocyanine−fullerene systems with two different central atoms was realized. Their UV−vis/IR/ 1 H NMR/fluorescence/femtosecond transient absorption spectra, self-assembly thermodynamics, electrochemistry, and DFT-calculated (the B3LYP+D3BJ/6-31G level of theory) geometric/electronic structures were obtained and analyzed. The self-assembly in (octakis(3,5-di-tertbutylphenoxy)phthalocyaninato)cobalt(II)/manganese(III) acetate -1′-N-methyl-2′-(1H-imidazol-1-yl)-phenylpyrrolidino-[3′,4′:1,2][60]fullerene−toluene system, the mechanism of which depends on a central metal atom, results in the formation of phthalocyanine−fullerene donor−acceptor dyads with relatively high bonding constants and an efficient property of photoinduced charge separation. Effects of replacement of the central metal atom and functional substitution in ground and excited state interactions were discussed. The metal phthalocyanine-substituted fullerene radical ion-pairs formation proved by comparison of transient and spectroelectrochemical results suggest the potential use of functionalized phthalocyanine−fullerene dyads as a functional material for building optoelectronic devices.

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

“…Really not too different photoelectrochemical parameters of (ImF)CoPc(3,5-di-t BuPhO) 8 and (AcO)(ImF)MnPc(3,-5-di-t BuPhO) 8 are observed at the stability constant values of (6.60 ± 1.15) 10 5 and (3.83 ± 0.79) 10 4 L mol −1 (Figure 10, Table 12) and at the ImF bonding energy about 17.6 kcal mol −1 and about 8.7 kcal mol −1Á172 , respectively. When taking into account a lot of dispersion intermolecular interactions of bulky tert-butyl groups by dispersion correction for density functional (D3BJ), the authors [116] have shown mediating of substitution influence owing to averaging of the bonding energies of both dyads (about 44.3 kcal mol −1 ).…”

“…Use of femtosecond transient absorption measurements allowed the authors [116] to characterize the kinetics of the charge separation and the recombination in the photoexcited samples of the mentioned phthalocyaninecontaining dyads and evaluate the effect of the central It is seen from the data of this section that porphyrin/ phthalocyanine complexes with a highly charged central atom as these with two charged M 2+ are available satisfy all requirements for organic solar cells. This refers to the wide UV-visible absorption of both a macrocyclic donor and a fullerene-containing acceptor, chemical/photochemical stability, ability to photoinduced charge separation, solubility, solution processability, and stabile/ reproductive photoelectrochemical characteristics.…”

“…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).…”

“…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. [ 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.…”

“…[ 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 ]…”