Pearce, Kyle G and Crossley, Ian R (2020) Diphosphametacyclophanes: structural and electronic influences of substituent variation within a family of bis(diketophosphanyl) macrocycles. Journal of Organic Chemistry, 85 (22). pp. 14697-14707. ISSN 0022-3263

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Abstract

The condensation of MeP(SiMe3)2 with a series of
5-substituted isophthaloyl chlorides (5-R′C6H3-2,6-{C(O)Cl}2) affords the diphosphametacyclophanes m-{-C(O)-C6H3-5-R′-(C-(O)PMe)}2 (R′ = I, Me, tBu, Ph, and p-NCC6H4); the analogues m-{-C(O)-C5H3N-(C(O)PMe)}2 and m-{-C(O)-C6H4-(C(O)-PPh)}2 are similarly obtained in preference to higher oligomers, in contrast to precedent reports. The cyclophanes all adopt butterfly-like conformations in the solid state with the P-organyl substituents adopting mutually exo arrangements. Structural and computatiosnal data suggest the nature of the 5-R substituent is key in directing the inter-ring angle and the extent of LUMO stabilization about the diketophophanyl scaffold. The latter is substantiated by UV/vis pectroscopy and cyclic voltammetry, which demonstrate these cyclophanes to be appreciably comparable to the diketophosphanyl systems commonly explored in the context of organic electronic materials; intriguingly, the distinct dikeophosphanyl moieties within the macrocycles appear effectively “insulated” by the macrocycle geometry, rather than acting as a through-conjugate.

Item Type:	Article
Keywords:	Organophosphorus, Phosphorus, Phosphine, Macrocycle, Electrochemistry, Diketophosphanyl
Schools and Departments:	School of Life Sciences > Chemistry
SWORD Depositor:	Mx Elements Account
Depositing User:	Mx Elements Account
Date Deposited:	30 Oct 2020 08:15
Last Modified:	17 Mar 2022 10:30
URI:	http://sro.sussex.ac.uk/id/eprint/94671

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