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Effect of Cp‐Ligand Methylation on Rhodium(III)‐Catalyzed Annulations of Aromatic Carboxylic Acids with Alkynes: Synthesis of Isocoumarins and PAHs for Organic Light‐Emitting Devices
Author(s) -
Molotkov Alexander P.,
Arsenov Mikhail A.,
Kapustin Daniil A.,
Muratov Dmitry V.,
Shepel' Nikolay E.,
Fedorov Yury V.,
Smol'yakov Alexander F.,
Knyazeva Elena I.,
Lypenko Dmitry A.,
Dmitriev Artem V.,
Aleksandrov Alexey E.,
Maltsev Eugeny I.,
Loginov Dmitry A.
Publication year - 2020
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.202000048
Subject(s) - isocoumarins , chemistry , carboxylic acid , rhodium , catalysis , chemoselectivity , ligand (biochemistry) , cyclopentadienyl complex , dibenzofuran , fluorene , medicinal chemistry , organic chemistry , biochemistry , polymer , receptor
An efficient protocol was developed for the synthesis of π‐extended isocoumarins and polycyclic aromatic hydrocarbons based on the oxidative coupling of aromatic carboxylic acids with internal alkynes catalyzed by (cyclopentadienyl)rhodium complexes. The coupling chemoselectivity strongly depends on whether Cp or the methylated Cp* ligands are used. The pentamethyl derivative [Cp*RhCl 2 ] 2 predominantly gives isocoumarins, while the non‐methylated complex [CpRhI 2 ] n produces naphthalene derivatives. The polyaromatic carboxylic acids (such as 1‐naphthoic acid, 1‐pyrenecarboxylic acid, fluorene‐1‐carboxylic acid, and dibenzofuran‐4‐carboxylic acid) are suitable for this approach. A mixture of Cp*H/RhCl 3 can be used as a catalyst instead of [Cp*RhCl 2 ] 2 . The structures of 3,4‐diphenylindeno[1,2‐ h ]isochromen‐1(11 H )‐one and 7,10‐dimethyl‐8,9‐diphenylbenzo[ pqr ]tetraphene were determined by X‐ray diffraction. In addition, the optical properties of the prepared compounds were studied. 7,8‐Diphenyl‐10H‐phenaleno[1,9‐ gh ]isochromen‐10‐one was employed as an emissive layer for OLED manufacturing. The OLED emits yellow‐green light with a maximum intensity 1740 cd ⋅ m −2 at 15 V.