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Stable Subporphyrin meso‐Aminyl Radicals without Resonance Stabilization by a Neighboring Heteroatom
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(26):7543-7547
Most aminyl radicals studied so far are resonance‐stabilized by neighboring heteroatoms, and those without such stabilization are usually short‐lived. We report herein that subporphyrin meso ‐2,4,6‐trichlorophenylaminyl radicals and a bis(5‐subporphyrinyl)aminyl radical are fairly stable under ambient conditions without such stabilization. The subporphyrin meso ‐2,4,6‐trichlorophenylaminyl radical crystal structure displays a characteristically short Cmeso −N bond and a perpendicular arrangement of the meso ‐arylamino group. The stabilities of these radicals have been ascribed to extensive spin delocalization over the subporphyrin π‐electronic network as well as steric protection around the aminyl radical center. 相似文献
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《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(9):2532-2536
A pyrrole‐cleaving modification to transform boron(III) meso ‐triphenylsubporphyrin into boron(III) meso ‐triphenylsubchlorophin has been developed. Boron(III) subchlorophins thus synthesized show absorption and fluorescence spectra that are roughly similar to those of boron(III) subchlorins, but B ‐methoxy boron(III) subchlorophin showed considerably intensified fluorescence and a small Stokes shift. Peripheral modification reactions of B ‐phenyl boron(III) subchlorophin such as regioselective nitration with Cu(NO3)2⋅3 H2O, ipso ‐substitution reactions of boron(III) α‐nitrosubchlorophin with CsF and CsCl, and Pd‐catalyzed cross‐coupling reactions of boron(III) α‐chlorosubchlorophin with arylacetylenes, have been also explored to tune the optical properties of subchlorophins. 相似文献
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《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2018,130(1):344-348
Pyrrole‐modified subporphyrins bearing a non‐pyrrolic cyclic unit, subporpholactone, subporpholactam, and imidazolosubporphyrin were newly synthesized. They show subporphyrin‐like absorption and fluorescence spectra that are red‐shifted in the order of subporpholactam<subporpholactone<imidazolosubporphyrin. Metalation of the imidazolosubporphyrin with (pentamethylcyclopentadienyl)iridium(III) dichloride dimer gave a complex, in which the iridium(III) atom was attached at the peripheral nitrogen atom of the imidazole moiety and the ortho‐position of the meso‐phenyl group. Reaction of this complex with diphenylacetylene gave different products depending on the used additive; a phenyl‐rearranged product in the presence of NaBArF4 (ArF=3,5‐bis(trifluoromethyl)phenyl) and two isomeric carbene complexes in the presence of KPF6. 相似文献
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《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(40):12485-12489
A meso–meso β‐β β‐β triply linked subporphyrin dimer 6 was synthesized by stepwise reductive elimination of β‐to‐β doubly PtII‐bridged subporphyrin dimer 9 . Dimer 6 was characterized by spectroscopic and electrochemical measurements, theoretical calculations, and picosecond time‐resolved transient absorption spectroscopy. X‐ray diffraction analysis reveals that 6 has a bowl‐shaped structure with a positive Gaussian curvature. Despite the curved structure, 6 exhibits a remarkably red‐shifted absorption band at 942 nm and a small electrochemical HOMO–LUMO gap (1.35 eV), indicating an effectively conjugated π‐electronic network. 相似文献
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Giulia Lavarda Dr. Daiki Shimizu Prof. Dr. Tomás Torres Prof. Dr. Atsuhiro Osuka 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(8):3151-3154
Peripherally metalated porphyrinoids are promising functional π-systems displaying characteristic optical, electronic, and catalytic properties. In this work, 5-(2-pyridyl)- and 5,10,15-tri(2-pyridyl)-BIII-subporphyrins were prepared and used to produce cyclometalated subporphyrins by reactions with [Cp*IrCl2]2, which proceeded through an efficient C−H activation to give the corresponding mono- and tri-IrIII complexes, respectively. While the mono-IrIII complex was obtained as a diastereomeric mixture, a C3-symmetric tri-IrIII complex with the three Cp*-units all at the concave side was predominantly obtained in a high yield of 90 %, which displays weak NIR phosphorescence even at room temperature in degassed CH2Cl2, differently from the mono-IrIII complexes. 相似文献
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