Recent studies of the synthesis, functionalization, optoelectronic properties and applications of dibenzophospholes

Abstract

The dibenzophospholes, synthesized in the 1950s, have recently gained a greater importance, due to their use in organic electronics and the possibility of designing new π-conjugated, optoelectronic materials that incorporate these heterocycles.

The hetero-Friedel-Crafts-Bradsher Cyclizations with Formation of Ring Carbon-Heteroatom (P, S) Bonds, Leading to Organic Functional Materials

“…One of the most efficient key approaches for the synthesis of polycyclic systems containing ring sulfur atom and utilizing intramolecular electrophilic annulation reaction of sulfoxide groups in alkylsulfinylarenes with aromatic rings was introduced by Müllen and coworkers in 1999. The mechanism of this transformation assumed protonation of oxygen atom in the sulfoxide group (1), in the presence of trifluoromethanesulfonic acid (triflic acid, TfOH) with formation of electrophilic sulfonium cation (2). Thus, this acidic activation of sulfoxide resembles activation of carbonyl group in the presence of Brönsted or Lewis acids in S E Ar reactions.…”

“…The latter possesses lower resonance energy compared to the former, originating from differences in configuration of phosphorus (flattened sp 3 ) and sulfur (sp 2 ) atoms. Thus, phosphole has nearly six times weaker aromatic character than thiophene based on aromatic stabilization energies (ASE calc = 3.2 versus 18.57 kcal mol −1 ) [ 2 ]. These differences, however, may be an asset, utilized in modulating the material properties based on these molecules.…”

Synthesis of triphenylene-fused phosphole oxides via C–H functionalizations

“…The phosphorus-containing five-membered ring, phosphole, has attracted significant attention as a structural motif in π-conjugated functional molecules [1][2][3][4][5][6][7][8][9]. Its inherently unique electronic structure, along with opportunities to modify the phosphorus center and the periphery by substitution or ring fusion, have stimulated chemists to explore a structurally diverse range of phosphole derivatives with extended π-system.…”

Doping Sumanene with Both Chalcogens and Phosphorus(V): One‐Step Synthesis, Coordination, and Selective Response Toward AgI

“…[1] It has been documented that doping PA Hs with main-group elements provides value-added functionalities. [2] Therefore,h eteroles such as chalcogenoles [3] and pyrrole [4] have been incorporated into PA Hs.T he phosphole seems to be unique compared to the other heteroles, [5] and its derivatives have been employed to fabricate various organic electronics. [6][7][8] Thev alence state of the Pa tom has ap ivotal role on electronic state of phosphole.…”

“…[6][7][8] Thev alence state of the Pa tom has ap ivotal role on electronic state of phosphole. [5,9] ThePatom shows apyramid geometry that has be used to create bowl-shaped psystem. [10] Regarding bowl-shaped PA Hs, [11] sumanene [12] and its analogues are of growing interest.…”