Dibenzophosphapentaphenes: Exploiting P Chemistry for Gap Fine-Tuning and Coordination-Driven Assembly of Planar Polycyclic Aromatic Hydrocarbons

Abstract

A synthetic route to planar P-modified polycylic aromatic hydrocarbons (PAHs) is described. The presence of a reactive σ(3),λ(3)-P moiety within the sp(2)-carbon scaffold allows the preparation of a new family of PAHs displaying tunable optical and redox properties. Their frontier molecular orbitals (MOs) are derived from the corresponding phosphole MOs and show extended conjugation with the entire π framework. The coordination ability of the P center allows the coordination-driven assembly of two molecular PAHs onto a Au(I) ion.

Blue Electrofluorescence Properties of Furan–Silole Ladder Pi-Conjugated Systems

“…Sci. 2018, 8, x FOR PEER REVIEW 7 of 10 a higher band gap [12]. This is in line with the fact that linear phospholes oxides oligomers possess a smaller HOMO-LUMO gap compared to their Si analogs.…”

“…Furthermore, compounds 4-6 featuring aryl substituents are slightly easier to reduce than compound 2. Compared to its P-congeners, compounds 2, 4-6 present a higher band gap [12]. This is in line with the fact that linear phospholes oxides oligomers possess a smaller HOMO-LUMO gap compared to their Si analogs.…”

“…Following the successful incorporation of thiophene oligomers and polymers in opto-electronic devices, [1][2][3] new derivatives featuring B [4,5], N [6,7], O [8,9], Si [10] or P [11][12][13][14][15][16][17][18][19] have been developed. In particular, siloles (silacyclopentadienes) found promising applications in the field of organic light emitting devices (OLEDs) [20][21][22][23].…”

Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons

“…Photo-cyclisation, under optimised conditions, performed on compound 7 led to am ixture of two products, 8 and 9,w hich could be easily separated. [46] In the case of the thiophene-containing phospholes 10 and 11,i rradiation led to the formation of dissymmetric derivatives 12 and 13 ( Figure 3). [47] X-ray diffraction revealed that the sp 2 -carbonb ackbone of compound 9 was planar;t hus validating the strategy of placing the phosphorus atom on the edge of the PAH.…”

“…Structures of 7-13 (a);crystallographic structure (b) and packing of compound 9 (c). [46] (CCDC 861180 contains the supplementary crystallographic data for this paper.These data can be obtained free of charge from The Cambridge Crystallographic Data Centre.) ChemPhysChem 2017ChemPhysChem , 18,2618ChemPhysChem -2630 www.chemphyschem.org As an example of device application, phosphorus-containing PAHs 9 and 17 were inserted as orange dopantso fablueemitting matrix [N,N'-diphenyl-N,N'-bis(1-naphthylphenyl)-1,1'-biphenyl-4,4'-diamine (a-NPB)] in white-emitting OLEDs (WOLEDs).…”