Does a nitrogen matter? Synthesis and photoinduced electron transfer of perylenediimide donors covalently linked to C₅₉N and C₆₀ acceptors

Abstract

The first perylenediimide (PDI) covalently linked to an azafullerene (C59N) is described. PDI-C59N and PDI-C60 dyads where PDI acts as an electron-donor moiety have been synthesized by connection of the balls to the PDI 1-bay position. Photoexcitation of the PDI unit in both systems results in formation of the charge-separated state by photoinduced electron transfer from the singlet excited state of the PDI moiety to the C59N or to the C60 moiety. The charge-separated state has a lifetime of 400 ps in the case of PDI-C59N and 120 ps for the PDI-C60 dyad in benzonitrile at 298 K. This result has significant implications for the design of organic solar cells based on covalent donor-acceptor systems using C59N as an electron acceptor, indicating that longer-lived charge-separated states can be attained using C59N systems instead of C60 systems.

ChemInform Abstract: Azafullerene C59N in Donor—Acceptor Dyads: Synthetic Approaches and Properties

“…Ar ecent report dealt with perylenediimide (PDI)d yads of both azafullerene and [60]fullerene and compared their photophysicalp roperties. [25] Particularly,C 59 N-PDI dyad 30 was prepared from the condensation of acid 27 and ah ydroxyl derivative of PDI in 8% yield, while the C 60 -PDI dyad 31 prepared in as imilar way (Scheme 9). Ar elativelyg reater deshielding effect of C 59 No nP DI protons was observed from the comparison of the 1 HNMR spectra of 30 and 31,i ndicative of ap ossible greater electron-withdrawing ability of C 59 N. On the other hand, the reduction potentials of the fullerene in both 30 and 31 were comparable.…”

Azafullerene C59N in Donor–Acceptor Dyads: Synthetic Approaches and Properties

“…A recent report dealt with perylenediimide (PDI) dyads of both azafullerene and [60]fullerene and compared their photophysical properties . Particularly, C 59 N–PDI dyad 30 was prepared from the condensation of acid 27 and a hydroxyl derivative of PDI in 8 % yield, while the C 60 –PDI dyad 31 prepared in a similar way (Scheme ).…”

Tether‐Directed Regioselective Synthesis of an Equatorialface Bisadduct of Azafullerene Using Cyclo‐[2]‐octylmalonate

“…In these, the addend is bound at the 2‐position adjacent to the nitrogen atom following electrophilic aromatic substitution with electron‐rich arenes or Mannich‐type nucleophilic substitution reactions (Figure a) . Several C 59 N‐based donor–acceptor hybrids have been synthesized, incorporating phthalocyanines, corrole, porphyrins, perylene, polycyclic aromatic hydrocarbons, ferrocene, or gold nanoparticles, and were shown to participate in ultrafast energy‐ or electron‐transfer processes. Notably, in a more recent example, an oligophenylenevinylene wire was conjugated to C 59 N, yielding an ultralong charge‐separation lifetime of 20 ms .…”

“…In these, the addend is bound at the 2positiona djacentt ot he nitrogen atom followinge lectrophilic aromatic substitution with electron-richa reneso rM annichtype nucleophilics ubstitution reactions (Figure1a). [4] Several C 59 N-based donor-acceptorh ybrids have been synthesized,i ncorporating phthalocyanines, [5,6] corrole, [7] porphyrins, [8,9] perylene, [10] polycyclica romatic hydrocarbons, [8,11] ferrocene, [12] or gold nanoparticles, [13] and were shown to participate in ultrafast energy-or electron-transfer processes. Notably,i namore recent example, an oligophenylenevinylenew ire was conjugated to C 59 N, yielding an ultralongc harge-separation lifetime of 20 ms. [14] Furthermore, (C 59 N) 2 has also been shown to engage in supramolecular interactions with two [10]cycloparaphenylene units, en route to the realization of au nique arrangement in an all-p functional system.…”

“…[4] Several C 59 N-based donor-acceptorh ybrids have been synthesized,i ncorporating phthalocyanines, [5,6] corrole, [7] porphyrins, [8,9] perylene, [10] polycyclica romatic hydrocarbons, [8,11] ferrocene, [12] or gold nanoparticles, [13] and were shown to participate in ultrafast energy-or electron-transfer processes. Notably,i namore recent example, an oligophenylenevinylenew ire was conjugated to C 59 N, yielding an ultralongc harge-separation lifetime of 20 ms. [14] Furthermore, (C 59 N) 2 has also been shown to engage in supramolecular interactions with two [10]cycloparaphenylene units, en route to the realization of au nique arrangement in an all-p functional system. [15] Azafullerenem onoadductsw ith ab ound addend at the carbona tom adjacentt ot he N-substituent represent excellent startingm aterials for the constructiono fm ultiple addition adducts derivedfrom functionalization of the double bonds of the C 59 Nc ore. For example, chlorination of an arylated derivative C 59 NAr affordedt he tetrachlorinated heterofullerene C 59 NArCl 4 containing an isolated pyrrole moiety.…”