Molecular design of star-shaped benzotrithiophene materials for organic electronics

Progresses in the design and application of conjugated small molecules, oligomers and polymers have empowered rapid development of organic electronic technology as an alternative to conventional devices. Among the numerous organic electronic materials, benzotrithiophene (BTT)-based oligomers and polymers have recently come in the limelight demonstrating great potential in organic electronics as high performance photovoltaic devices, field-effect transistors, electrochromic materials, high-area capacitors and charge carrier discotic liquid crystals. In this digest, we propose an overview of the organic electronic materials based on BTT isomers, highlighting the structure-performance relationship. The results obtained so far clearly indicate that the BTT isomers are among the most promising building blocks for the development π-extended materials for optoelectronic applications in the near future.     

Progresses in organic field-effect transistors and molecular electronics

In the past years, organic semiconductors have been extensively investigated as electronic materials for organic field-effect transistors (OFETs). In this review, we briefly summarize the current status of organic field-effect transistors including materials design, device physics, molecular electronics and the applications of carbon nanotubes in molecular electronics. Future prospects and investigations required to improve the OFET performance are also involved. __________ Translated from Huaxue Tongbao (Chemistry), 2006, 69(6) (in Chinese)     

Synthesis and characterization of fluorene and carbazole dithienosilole derivatives for potential applications in organic light-emitting diodes

Several fluorene or carbazole-based dithienosiloles (DTSs) have been synthesized and their thermal, photophysical, and electrochemical properties have been systematically investigated. These compounds show high thermal stability with glass transition temperature above 110 °C as well as decomposition temperatures at ∼400 °C. Intense green emission is observed in the spectral region of 500-510 nm for all compounds (Φ_PL=0.31-0.80), that is, attributed to both the 5,5′-substituents of the DTS ring and DTS-based π-π^∗ transition. Based on the emission spectra at 77 K, the triplet energy for these compounds was calculated to be within 2.1-2.2 eV, indicating that they may be used as host materials for red emitters in organic light-emitting diodes (OLEDs). All compounds exhibit reversible oxidation and possess low-lying LUMO energies, owing to the conjugated fluorene/carbazole substituents on the DTS. This along with the high thermal/electrochemical stabilities and high fluorescent quantum efficiencies makes the new DTSs compounds promising candidates for use in OLEDs as emitters, host and electron-transporting materials.     

Azulene-based organic functional molecules for optoelectronics

Design and synthesis of new organic functional materials with improved performance or novel properties are of great importance in the field of optoelectronics. Azulene, as a non-alternant aromatic hydrocarbon, has attracted rising attention in the last few years. Different from most common aromatic hydrocarbons, azulene has unique characteristics, including large dipole moment, small gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). However, the design and synthesis of azulene-based functional materials are still facing several challenges. This review focuses on the recent development of organic functional materials employing azulene unit. The synthesis of various functionalized azulene derivatives is summarized and their applications in optoelectronics are discussed, with particular attention to the fields including nonlinear optics (NLO), organic field-effect transistors (OFETs), solar cells, and molecular devices.     

Color tuning of iridium complexes for organic light-emitting diodes: The electronegative effect and π-conjugation effect

Novel red phosphorescent emitter bis(4-phenylquinazolinato-N,C^2′) iridium(acetylacetonate) [(pqz)₂Ir(acac)], bis(1-(1′-naphthyl)-5-methylisoquinolinato-N,C^2′)iridium(acetylacetonate) [(1-mniq)₂Ir(acac)] and bis(1-(2′-naphthyl)-5-methylisoquinolinato-N,C^2′)iridium(acetylacetonate) [(2-mniq)₂Ir(acac)] have been synthesized and fully characterized. The electronegative effect of (pqz)₂Ir(acac) ligand shows almost the same influence as the extended π-conjugation effect of (2-mniq)₂Ir(acac). Density functional theory (DFT) was applied to calculate the Kohn-Sham orbitals of HOMOs and LUMOs in the iridium complexes to illustrate the N(1) electronegative atom effect. Finally, lowest triplet state (T₁) energies calculated by time-dependent DFT (TDDFT) were compared with the experimental electroluminescent data. The calculated data for the iridium complexes agreed fairly well with experimental data. Electroluminescent devices with a configuration of ITO/NPB/CBP:dopant/BCP/AlQ₃/LiF/Al were fabricated. The device using (pqz)₂Ir(acac) as a dopant showed deep-red emission with 1931 CIE (Commission International de L’Eclairage) chromaticity coordinates x = 0.70, y = 0.30.     

Diketopyrrolopyrrole-based functional supramolecular polymers: next-generation materials for optoelectronic applications

The very concept of dye and pigment chemistry that was long known to the industrial world underwent a radical revision after the discovery and commercialization of dyes such as mauveine, indigo, and so on. Apart from their conventional role as coloring agents, organic dyes, and pigments have been identified as indispensable sources for high-end technological applications including optical and electronic devices. Simultaneous with the advancement in the supramolecular chemistry of π-conjugated systems and the divergent evolution of organic semiconductor materials, several dyes, and pigments have emerged as potential candidates for contemporary optoelectronic devices. Of all the major pigments, diketopyrrolopyrrole (DPP) better known as the ‘Ferrari Pigment’ and its derivatives have emerged as a major class of organic functional dyes that find varied applications in fields such as industrial pigments, organic solar cells, organic field–effect transistors, and in bioimaging. Since its discovery in 1974 by Farnum and Mehta, DPP-derived dyes gained rapid attention because of its attractive color, synthetic feasibility, ease of functionalization, and tunable optical and electronic properties. The advancement in supramolecular polymerization of DPP-based small molecules and oligomers with directed morphological and electronic features have led to the development of high performing optoelectronic devices. In this review, we highlight the recent developments in the optoelectronic applications of DPP derivatives specifically engineered to form supramolecular polymers.     

Structural engineering of dipolar organic dyes with an electron-deficient diphenylquinoxaline moiety for efficient dye-sensitized solar cells

A series of new organic dyes containing an electron-deficient diphenylquinoxaline moiety was synthesized and employed as the photosensitizers in dye-sensitized solar cells (DSSCs). The multiple phenyl rings in the peripheral positions of the dye structure provide a hydrophobic barrier to slow down the charge recombination. The photophysical and electrochemical properties of these dyes were investigated in detail. The cell performance and the associated photophysical and electrochemical properties can be easily tuned by the modification of the aromatic fragments within the π spacer. Dye CR204-based DSSC reached the best energy conversion efficiency of 6.49% with an open-circuit voltage of 666 mV, a short-circuit photocurrent density of 14.9 mA cm⁻², and a fill factor of 0.66. The IPCE of CR204-based DSSC covers the light-harvesting to NIR region.     

Evolution of emission manners of organic light-emitting diodes: From emission of singlet exciton to emission of doublet exciton

The emission manners of organic light-emitting diodes(OLEDs) have experienced almost three-decade evolution.In this review,we briefly summarized the emission manners of OLEDs including:(ⅰ) emission from singlet exciton;(ⅱ) emission from triplet exciton;(ⅲ) emission from singlet exciton converted from triplet exciton.Then we introduced a new type of OLEDs with the emission from doublet exciton,wherein organic neutral radicals are used as emitters.Due to the spin-allowed transition of doublet excitons,using neutral radicals as emitters is believed to be a new way to break the 25%upper limit of internal quantum efficiency of OLEDs.The progress of emissive stable neutral radicals is also shortly reviewed.     

Self-assembled gelators for organic electronics

Nature excels at engineering materials by using the principles of chemical synthesis and molecular self-assembly with the help of noncovalent forces. Learning from these phenomena, scientists have been able to create a variety of self-assembled artificial materials of different size, shapes, and properties for wide ranging applications. An area of great interest in this regard is solvent-assisted gel formation with functional organic molecules, thus leading to one-dimensional fibers. Such fibers have improved electronic properties and are potential soft materials for organic electronic devices, particularly in bulk heterojunction solar cells. Described herein is how molecular self-assembly, which was originally proposed as a simple laboratory curiosity, has helped the evolution of a variety of soft functional materials useful for advanced electronic devices such as organic field-effect transistors and organic solar cells. Highlights on some of the recent developments are discussed.     

Application of direct (hetero)arylation in constructing conjugated small molecules and polymers for organic optoelectronic devices

Direct (hetero)arylation, as a sustainable, atom-economic and environmentally benign synthetic protocol compared to conventional coupling techniques, has been extensively applied to the sustainable preparation of π-conjugated materials for organic optoelectronic devices. In this review, we will highlight recent advances made in direct arylation for conjugated small molecules and polymers toward high performance organic optoelectronic devices. Some important insights in direct arylation for synthesizing organic optoelectronic materials are given, together with the challenges and outlook in this significant and hot research field.     

New applications of poly(arylene ether)s in organic light-emitting diodes

Compared with conventional π-conjugated polymers,poly(arylene ether)s(PAEs) may take advantages of excellent thermal properties,well-defined effective conjugated length and no catalyst contamination.Recently,their applications have been extended from engineering plastics to optoelectronic materials.In this review,various kinds of functional PAEs used as fluorescent polymers,host polymers and phosphorescent polymers in organic light-emitting diodes(OLEDs) are outlined,and their molecular design,synthesis and device performance are overviewed.     

1,7-Dinitroperylene bisimides: facile synthesis and characterization as n-type organic semiconductors

1,7-Dinitroperylene bisimides (1a-1b) and 1-nitroperylene bisimides (2a-2b) were synthesized under mild condition in high yields, and were characterized by FT-IR, ¹H NMR, UV-vis, HRMS spectra, cyclic voltammetry, and thermogravimetric analyses. These compounds are stable up to 260 °C according to thermogravimetric analyses. They undergo two quasi-reversible one-electron reductions in THF at modest potentials. The nitro functionalities provide stability of n-type charge carriers by lowering the LUMO to resist ambient oxidation.     

Fluorination strategy enables greatly improved performance for organic solar cells based on polythiophene derivatives

The power conversion efficiencies(PCEs) of organic solar cells(OSCs) have reached 18% recently,which have already met the demand of practical application.However,these outstanding results were generally achieved with donor-acceptor(D-A) type copolymer donors,which can hardly fulfill the low-cost largescale production due to their complicated synthesis processes.Therefore,developing polymer donors with simple chemical structures is urgent for realizing low-cost OSCs.Polythiophene(PT) derivatives are currently regarded as promising candidates for such kind of donor materials,which has been illustrated in many works.In this work,two new alkylthio substituted PT derivatives,P301 and P302,were synthesized and tested as donors in the OSCs using Y5 as the accepto r.In comparison,the introduction of fluorine atoms on the backbone of P302 can not only downshift the energy levels,but also greatly improve the phase separation morphologies of the active layers,which is ascribed to the enhanced aggregation effect and the reduced miscibility with the non-fullerene acceptor.As a result,the P302:Y5-based OSC exhibits a significantly improved PCE of 9.65% than that of P301:Y5-based one,indicating the important role of fluorination in the construction of efficient PT derivative donors.     

Alkoxy encapsulation of carbazole-based thermally activated delayed fluorescent dendrimers for highly efficient solution-processed organic light-emitting diodes

Two n-butoxy-encapsulated dendritic thermally activated delayed fluorescent(TADF) emitters(namely O-D1 and O-D2) with the first-/second-generation carbazoledendrons are designed and synthesized via C—N coupling between carbazoledendrons and 2,4,6-tris(4-bromophenyl)-1,3,5-triazine core.It is found that,compa red with the commo nly-used tert-butyl groups,the use of n-butoxy encapsulation groups can lead to smallersinglet-triplet energy gap for the dendrimers,producing stronger TADF effect together with faster reverse intersystem crossing process.Solution-processed TADF organic light-emitting diodes(OLEDs) utilizingalkoxy-encapsulated dendrimers O-D1 and O-D2 as emitters exhibitstate-of-the-art device efficiency withthe maximum external quantum efficiency up to 16.8% and 20.6%,respectively,which are ～1.6 and～2.0 times that of the tert-butyl-encapsulated counterparts.These results suggest that alkoxy encapsulation of the carbazole-based TADF dendrimers can be a promising approach for developing highly efficient emitters for solution-processed OLEDs.     

From molecular to macroscopic engineering: shaping hydrogen-bonded organic nanomaterials

The self‐assembly and self‐organization behavior of chromophoric acetylenic scaffolds bearing 2,6‐bis(acetylamino)pyridine ( 1 , 2 ) or uracyl‐type ( 3 – 9 ) terminal groups has been investigated by photophysical and microscopic methods. Systematic absorption and luminescence studies show that 1 and 2 , thanks to a combination of solvophilic/solvophobic forces and π–π stacking interactions, undergo self‐organization in apolar solvents (i.e., cyclohexane) and form spherical nanoparticles, as evidenced by wide‐field optical microscopy, TEM, and AFM analysis. For the longer molecular module, 2 , a more uniform size distribution is found (80–200 nm) compared to 1 (20–1000 nm). Temperature scans in the range 283–353 K show that the self‐organized nanoparticles are reversibly formed and destroyed, being stable at lower temperatures. Molecular modules 1 and 2 were then thoroughly mixed with the complementary triply hydrogen‐bonding units 3 – 9 . Depending on the specific geometrical structure of 3 – 9 , different nanostructures are evidenced by microscopic investigations. Combination of modules 1 or 2 with 3 , which bears only one terminal uracyl unit, leads to the formation of vesicular structures; instead, when 1 is combined with bis‐uracyl derivative 4 or 5 , a structural evolution from nanoparticles to nanowires is observed. The length of the wires obtained by mixing 1 and 4 or 1 and 5 can be controlled by addition of 3 , which prompts transformation of the wires into shorter rods. The replacement of linear system 5 with the related angular modules 6 and 7 enables formation of helical nanostructures, unambiguously evidenced by AFM. Finally, thermally induced self‐assembly was studied in parallel with modules 8 and 9 , in which the uracyl recognition sites are protected with tert‐butyloxycarbonyl (BOC) groups. This strategy allows further control of the self‐assembly/self‐organization process by temperature, since the BOC group is completely removed on heating. Microscopy studies show that the BOC‐protected ditopic modules 8 self‐assemble and self‐organize with 1 into ordered linear nanostructures, whereas BOC‐protected tritopic system 9 gives rise to extended domains of circular nano‐objects in combination with 1 .     

Enhanced deep-red emission in donor-acceptor molecular architecture:The role of ancillary acceptor of cyanophenyl

Organic solid-state luminescent materials with high-efficiency deep-red emission have attracted considerable interest in recent years.Constructing donor-acceptor(D-A) type molecules has been one of most commonly used strategies to achieve deep-red emission,but it is always difficult to achieve high photoluminescence(PL) quantum yield(η_(PL)) due to forbidden charge-transfer state.Herein,we report a new D-A type molecule 4-(7-(4-(diphenylamino)phenyl)-9-oxo-9 H-fluoren-2-yl)benzonitrile(TPAFOCN),deriving from donor-acceptor-donor(D-A-D) type 2,7-bis(4-(diphenylamino)phenyl)-9 Hfluoren-9-one(DTPA-FO) with a fluorescence maximum of 627 nm in solids.This molecular design enables a transformation of acceptor from fluorenone(FO) itself to 4-(9-oxo-9 H-fluoren-2-yl)benzonitrile(FOCN).Compared with DTPA-FO,the introduction of cyanophenyl not only shifts the emission of TPA-FOCN to deep red with a fluorescence maximum of 668 nm in solids,but also maintains the high η_(PL) of 10%.Additionally,a solution-processed non-doped organic light-emitting diode(OLED)was fabricated with TPA-FOCN as emitter.TPA-FOCN device showed a maximum luminous efficiency of0.13 cd/A and a maximum external quantum efficiency(EQE) of 0.22% with CIE coordinates of(0.64,0.35).This work provides a valuable strategy for the rational design of high-efficiency deep-red emission materials using cyanophenyl as an ancillary acceptor.     

Thieno[3,4-c]pyrrole-4,6-dione based copolymers for high performance organic solar cells and organic field effect transistors

Donor-acceptor type copolymers have wide applications in organic field-effect transistors and organic photovoltaic devices. Thieno[3,4-c]pyrrole-4,6-dione (TPD), as an electron-withdrawing unit, has been widely used in D-A type copolymers recently. Till now, the highest power conversion efficiency and mobility of TPD-based copolymers are over 8% and 1.0 cm² V^-1 s^-1 respectively. In this review, the recent progress of TPD-based copolymers in organic solar cells and organic transistors is summarized.     

水溶性共轭聚合物研究与应用进展

近年来,在水溶性共轭聚合物(CPs)方面的研究备受瞩目,由于它包含了聚合物共轭主链良好的光电性质的同时还兼具了良好的水溶性,因此在光电功能信息器件中有着特殊的应用,并显著地推动了包括生物传感、电致发光器件、太阳电池和场效应晶体管等有机光电子材料及其器件的发展.本文对近几年来水溶性CPs的合成及其应用进展做出简要的总结,...     

Novel iridium complexes as high-efficiency yellow and red phosphorescent light emitters for organic light-emitting diodes

A series of novel biscyclometallated iridium complexes based on spirobifluorene ligands and acetyl acetonate (acac) ancillary ligands have been synthesized and characterized. Their electrochemical properties were investigated by cyclic voltammetry (CV). HOMO, LUMO, and energy band gaps of all the complexes were calculated by the combination of UV-vis absorption spectra and CV results. TGA and DSC results indicated their excellent thermal stability and amorphous structure. All the iridium complexes were fabricated into organic light-emitting devices with the device configuration of ITO/PEDOT:PSS (50 nm)/PVK (50 wt %):PBD (40 wt %):Ir complex (10 wt %) (45 nm)/TPBI (40 nm)/LiF (0.5 nm)/Ca (20 nm)/Ag (150 nm). Yellow to red light emission has been achieved from the iridium complexes guest materials. Complex C1 (yellow light emission) achieved an efficiency of 36.4 cd/A (10.1%) at 198 cd/m² and complex C4 (red light emission) reached external quantum efficiency of 4.6%. The slight decrease of external quantum efficiency at high current density revealed that the triplet-triplet (T₁-T₁) annihilation was effectively suppressed by the new developed complexes.