This review serves as a brief introduction to phospholes and discusses their unique favorable properties for application in organic electronic materials. Over the past several years, π-conjugated phospholes have been slowly making their way into devices. We report here the mode of synthesis of these π-conjugated phospholes as well as discuss the performances of the devices.

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π-Conjugated phospholes and their incorporation into devices: components with a great deal of potential

This Minireview describes recent advances of organophosphorus compounds as opto-electronic materials in the field of organic electronics. The progress of (hetero-) phospholes, unsaturated phosphanes, and trivalent and pentavalent phosphanes since 2010 is covered. The described applications of organophosphorus materials range from single molecule sensors, field effect transistors, organic light emitting diodes, to polymeric materials for organic photovoltaic applications.

Organophosphorus Compounds in Organic Electronics.

Electron-donating aryl groups were attached to electron-accepting benzophosphole skeletons. Among several derivatives thus prepared, one benzophosphole oxide was particularly interesting, as it retained high fluorescence quantum yields even in polar and protic solvents. This phosphole-based compound exhibited a drastic color change of its fluorescence spectrum as a function of the solvent polarity, while the absorption spectra remained virtually unchanged. Capitalizing on these features, this phosphole-based compound was used to stain adipocytes, in which the polarity of subcellular compartments could then be discriminated on the basis of the color change of the fluorescence emission.

Environment‐Sensitive Fluorescent Probe: A Benzophosphole Oxide with an Electron‐Donating Substituent

This review presents the main class of organophosphorus compounds (triaryl phosphines, phosphazenes, phospholes, phosphetes and diphosphacyclobutanes), which have been used in electronic devices (organic light-emitting diodes (OLEDs), organic photovoltaic cells (OPV cells), dye-sensitized solar cells (DSSCs), organic field-effect transistors (OFETs), and electrochromic cells).

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Organophosphorus derivatives for electronic devices

A series of heteroleptic coinage metal(I) complexes [Cu(PP)(PS)] 1, [Ag(PP)(PS)] 2, and [Au(PP)(PS)] 3 [PP = 1,2-bis(diphenylphosphino)benzene and PS− = 2-diphenylphosphinobenzenethiolate] were synthesized X-ray crystallography demonstrated that 1–3 possessed tetrahedral structures containing two types of bidentate ligands, PP and PS− Photophysical studies and time-dependent density functional theory calculations indicated that the emission from 1–3 in the solid state at room temperature originated from thermally activated delayed fluorescence (TADF) The thiolate ligand with strong electron-donating character (PS−) reduced the contribution from metal orbitals to the highest occupied molecular orbitals of the complexes, decreasing the metal-to-ligand charge-transfer character of the excited states of 1–3 The origin of TADF in 1–3 was attributed to ligand-to-ligand charge-transfer on the basis of molecular orbital calculations Au(I) complex 3 was unstable in solution because of a rapid ligand exchange reaction, and Ag(I) complex 2 showed limited solubility in organic solvents Cu(I) complex 1, which exhibited efficient green TADF with a maximum emission wavelength of 521 nm and a quantum yield of 052 in the solid state, was used to fabricate TADF-type organic light-emitting diodes via a wet process

Application of neutral d10 coinage metal complexes with an anionic bidentate ligand in delayed fluorescence-type organic light-emitting diodes

Benzofuran-fused Phosphole: Synthesis, Electronic, and Electroluminescence Properties

new angle: The insertion of a 2,2′-biphosphole subunit into π-conjugated systems offers a new way to control the HOMO-LUMO gap. Tuning of the dihedral angle (θ) between the two phosphorous heterocycles, either by metal coordination or covalent bonding through the P substitution can lead to control of the band gap. These new π-conjugated systems can be used as emitting materials in white organic light-emitting devices (WOLEDs).

2,2′‐Biphospholes: Building Blocks for Tuning the HOMO–LUMO Gap of π‐Systems Using Covalent Bonding and Metal Coordination

The discovery and molecular engineering of novel electroluminescent emitting materials is still a challenge in optoelectronics. In this work, we report on the development of new π-conjugated oligomers incorporating a dihydrophosphete skeleton. Variation of the substitution pattern of 1,2-dihydrophosphete derivatives and chemical modification of their P atoms afford thermally stable derivatives which are suitable emitters to construct organic light-emitting diodes. The optical and the electrochemical properties of these new P-based oligomers have been investigated in detail and are supported by DFT calculations. The OLED devices exhibit good performance and current independent CIE coordinates

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1,2-dihydrophosphete: a platform for the molecular engineering of electroluminescent phosphorus materials for light-emitting devices.

Monometallic gold(I)-alkynyl-helicene complexes (1 a,b) and bimetallic gold(I)-alkynyl-helicene architectures featuring the presence (2 a,b) or absence (3 a,b) of aurophilic intramolecular interactions were prepared by using different types of phosphole ligands (mono-phosphole L1 or bis-phospholes L2,3). The influence of the Au(I) d(10) metal center(s) on the electronic, photophysical, and chiroptical properties of these unprecedented phosphole-gold(I)-alkynyl-helicene complexes was examined. Experimental and theoretical results highlight the importance of ligand-to-ligand-type charge transfers and the strong effect of the presence or absence of Au(I) -Au(I) interactions in 2 a,b.

https://hal-univ-rennes1.archives-ouvertes.fr/hal-01292929/document

Bimetallic Gold(I) Complexes with Ethynyl-Helicene and Bis-Phosphole Ligands: Understanding the Role of Aurophilic Interactions in their Chiroptical Properties

Zuoyong Wang

Papers

Benzofuran-fused Phosphole: Synthesis, Electronic, and Electroluminescence Properties

2,2′‐Biphospholes: Building Blocks for Tuning the HOMO–LUMO Gap of π‐Systems Using Covalent Bonding and Metal Coordination

1,2-dihydrophosphete: a platform for the molecular engineering of electroluminescent phosphorus materials for light-emitting devices.

Bimetallic Gold(I) Complexes with Ethynyl-Helicene and Bis-Phosphole Ligands: Understanding the Role of Aurophilic Interactions in their Chiroptical Properties