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Pyrrole βC�B�N Fused Porphyrins: Molecular Structures and Opto-Electrochemical Studies

Nandi, RP and Chandra, B and Ghosh, S and Sarma, SP and Geremia, S and Hickey, N and Thilagar, P (2023) Pyrrole βC�B�N Fused Porphyrins: Molecular Structures and Opto-Electrochemical Studies. In: Chemistry - A European Journal .

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Official URL: https://doi.org/10.1002/chem.202304219


Herein, we report the design, synthesis, structure, and electrochemical study of doubly βC�B�N fused Ni(II) porphyrins (1-trans, 1-cis, 2-trans, and 2-cis). These compounds have been synthesized from A2B2 type dipyridyl Ni(II) porphyrins (Ar=Ph for 1 a; Ar=C6F5 for 2 a) via Lewis base-directed electrophilic aromatic borylation reactions. The solution state structures of these compounds have been established using 1H NMR, 11B NMR, 1H-1H COSY, 1H-13C HSQC, and 19F-13C HSQC NMR techniques. Single crystal X-ray analysis have revealed that 1-trans, 1-cis, and 2-trans adopt ruffled conformations, with alternate meso-carbons on the opposite sides of the mean porphyrin plane. The Soret bands in the absorption spectra of the B�N fused molecules are ~40 nm redshifted compared to unfused Ni(II) porphyrin precursors. The B�N fusion have diminished the redox potential of fused porphyrins. Although 1-trans and 1-cis, show four oxidation processes, 2-trans and 2-cis show only three oxidation processes. DFT studies have revealed that the tetrahedral geometry of the boron has induced a twist in the �-conjugation, which destabilizes the HOMO and stabilizes the LUMO in 1-trans, 1-cis, 2-trans, and 2-cis. © 2023 Wiley-VCH GmbH.

Item Type: Journal Article
Publication: Chemistry - A European Journal
Publisher: John Wiley and Sons Inc
Additional Information: The copyright for this article belongs to John Wiley and Sons Inc .
Keywords: Aromatic compounds; Boron; Design for testability; Energy dispersive X ray analysis; Nickel compounds; Redox reactions; Single crystals; X ray diffraction analysis, B�N fusion; Design studies; Design synthesis; Electrochemical potential; Electrochemical studies; Lewis base; Ni(II) porphyrin; Oxidation process; Synthesised; �C�H activation, Porphyrins
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 04 Mar 2024 07:21
Last Modified: 04 Mar 2024 07:21
URI: https://eprints.iisc.ac.in/id/eprint/84233

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