%0 Journal Article %1 Labella_2023 %A Labella, Jorge %A Shoyama, Kazutaka %A Guzman, David %A Schembri, Tim %A Stolte, Matthias %A Torres, Tomas %A Würthner, Frank %D 2023 %I American Chemical Society (ACS) %J ACS Materials Letters %K myown %P 543--548 %R 10.1021/acsmaterialslett.2c01132 %T Naphthalimide-Fused Subphthalocyanines: Electron-Deficient Materials Prepared by Cascade Annulation %U https://doi.org/10.1021%2Facsmaterialslett.2c01132 %X Imide-fused porphyrinoids are becoming key components in the area of molecular materials. Herein we report the synthesis of naphthalimide (NMI)-annulated subphthalocyanines (SubPcs) designed as an NIR-absorbing n-type organic semiconductor. Two different synthetic pathways could be applied for the preparation of NMI-fused SubPcs. The first consists of a 3 + 2 annulation between SubPc boronic ester and dibromo-NMI. This annulation, which involves the first CH activation reaction of a SubPc derivative reported so far, is totally regioselective to the β-position. Density functional theory (DFT) indicated that such position is favored both kinetically and thermodynamically. On the other hand, the second method relies on a cyclotrimerization of NMI-fused phthalonitrile. Electrochemical measurements and DFT calculations revealed that these NMI-fused SubPcs have low-lying LUMO energy levels suitable for electron charge transport. The N-alkyl substituted derivative (NMI-SubPc 2) was successfully applied as an nonfullerene acceptor (NFA) in combination with donor polymer PM6 in bulk-heterojunction (BHJ) organic solar cells (OSCs) with a highest power conversion efficiency (PCE) of 7.0%. This value is comparable to the record PCE of SubPc derivatives in BHJ-OSCs. Our results open a new vista in the preparation of π-extended contracted porphyrinoids and substantiate the potential of this new class of strong-absorbing electron-acceptor materials for applications in optoelectronic devices.

@article{Labella_2023, abstract = {Imide-fused porphyrinoids are becoming key components in the area of molecular materials. Herein we report the synthesis of naphthalimide (NMI)-annulated subphthalocyanines (SubPcs) designed as an NIR-absorbing n-type organic semiconductor. Two different synthetic pathways could be applied for the preparation of NMI-fused SubPcs. The first consists of a [3 + 2] annulation between SubPc boronic ester and dibromo-NMI. This annulation, which involves the first CH activation reaction of a SubPc derivative reported so far, is totally regioselective to the β-position. Density functional theory (DFT) indicated that such position is favored both kinetically and thermodynamically. On the other hand, the second method relies on a cyclotrimerization of NMI-fused phthalonitrile. Electrochemical measurements and DFT calculations revealed that these NMI-fused SubPcs have low-lying LUMO energy levels suitable for electron charge transport. The N-alkyl substituted derivative (NMI-SubPc 2) was successfully applied as an nonfullerene acceptor (NFA) in combination with donor polymer PM6 in bulk-heterojunction (BHJ) organic solar cells (OSCs) with a highest power conversion efficiency (PCE) of 7.0%. This value is comparable to the record PCE of SubPc derivatives in BHJ-OSCs. Our results open a new vista in the preparation of π-extended contracted porphyrinoids and substantiate the potential of this new class of strong-absorbing electron-acceptor materials for applications in optoelectronic devices.}, added-at = {2023-01-24T09:22:57.000+0100}, author = {Labella, Jorge and Shoyama, Kazutaka and Guzman, David and Schembri, Tim and Stolte, Matthias and Torres, Tomas and Würthner, Frank}, biburl = {https://www.bibsonomy.org/bibtex/298139c472b8a07c51154a68015e394d6/wuerthner_group}, doi = {10.1021/acsmaterialslett.2c01132}, interhash = {02a94333cc8165b91ecab59e111f7f53}, intrahash = {98139c472b8a07c51154a68015e394d6}, journal = {ACS Materials Letters}, keywords = {myown}, month = jan, pages = {543--548}, publisher = {American Chemical Society ({ACS})}, timestamp = {2023-05-23T13:14:49.000+0200}, title = {Naphthalimide-Fused Subphthalocyanines: Electron-Deficient Materials Prepared by Cascade Annulation}, url = {https://doi.org/10.1021%2Facsmaterialslett.2c01132}, year = 2023 }