Synthesis of π-Extended Dibenzophospholes by Intramolecular Radical Cyclization and Their Properties

Abstract

Intramolecular radical cyclization of phosphine oxides (R(1)R(2)P(O)H) induced by radical generators affords the corresponding dibenzophosphole oxides in excellent yields. By applying this method, linearly π-extended ladder-type dibenzophosphole oxides were successfully synthesized.

Organophosphorus Compounds in Organic Electronics

“…Interestingly the different isomers have almost no influence on absorption, but significantly affect the emission properties. Isomer a nti ‐ 9 b⋅O has its maximum emission at 454 nm ( Φ =0.46, solid), while the syn isomer is red‐shifted by about 20 nm (476 nm, Φ =0.63) . In an earlier study by Liu and co‐workers a similar series of ladder‐type dibenzophospholes ( 9 c : R 4 =H) was studied, confirming that phosphole oxidation induces significant red‐shifts of absorption and emission through a stabilization of the LUMO levels corroborated by electrochemical studies …”

“…Isomer anti-9b·O has its maximum emission at 454 nm (F = 0.46, solid), while the syn isomer is red-shifted by about2 0nm( 476 nm, F = 0.63). [44] In an earlier studyb yL iu and co-workers as imilar series of ladder-typed ibenzophospholes (9c:R 4 = H) was studied, confirming that phosphole oxidation induces significant red-shifts of absorption and emission through as tabilizationo f the LUMO levels corroborated by electrochemical studies. [45] Benzophospholebenzofuranes (10;F igure 3) are intramolecular donor-acceptor molecules.…”

Pluripotent Features of Doubly Thiophene‐Fused Benzodiphospholes as Organic Functional Materials

“…On the other hand, cis ‐ 1 reveals a slightly warped structure, which probably originates from the packing forces (Figure b). The C−C and C−P bond lengths of the benzodiphosphole unit are similar to those of reported benzodiphospholes;,, thus indicating that the fusion of thiophene to the benzodiphosphole has little impact on their structural parameters (Figures S1 and S2 in the Supporting Information). The trans and cis isomers reveal unusual contrasts in packing modes.…”

“…Additionally, Liu and co‐workers reported the synthesis of aromatic‐fused benzodiphospholes through a radical phosphanylation reaction . With the assistance of synthetic methodologies for dibenzophospholes, doubly benzo‐fused, and naphtho‐fused benzodiphospholes have also been prepared.…”

Silver‐Catalyzed Aerobic Oxidative Decarboxylative Coupling of Arylpropiolic Acids with H‐Phosphine Oxides: Mild and Facile Synthesis of β‐Oxophosphine Oxides

“…[10][11][12][13][14] It is known that phosphorus radicals can be produced under various conditions, such as from Et 3 B/O 2 , [10] peroxides, [11] azo compounds, [12] Mn(OAc) 3 /AcOH, [13] and Ag. [14,15] On the other and C-heteroatom bonds.…”