Quinacridone Derivatives Research Articles

Synthesis of Quinacridone Derivatives and Their Application as High Performance Levelers in Electroplating

Synthesis of Quinacridone Derivatives and Their Application as High Performance Levelers in Electroplating

Synthesis of Soluble Quinacridone Photocatalysts for the Homogeneous Oxidation of Thioethers

AbstractEvaluation of quinacridone (QA) derivatives as homogeneous metal‐free photocatalysts is here presented. QA derivatives were synthetized and systematically characterized, measuring their ground state and excited state redox potentials in dichloromethane (DCM) and 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP), in order to understand how structural modifications influenced their photocatalytic properties. In particular, the effect of dicyanomethylene and nitro EWG groups was investigated, in order to develop a photocatalyst capable of promoting oxidative processes in the presence of molecular oxygen. Among the analyzed derivatives, 2,9‐dinitro‐N,N′‐dibutylquinacridone (DNDBQA) was the one with the highest excited state reduction potential (Ered*=1.60 V in HFIP vs SCE), while N,N’‐dibutylquinacridone (DBQA) showed valuable excited state redox potentials (Ered*=1.29 V; Eox*=−1.28 V in HFIP vs SCE), making it suitable for bimodal applications in oxidative and reductive photocatalytic processes. Afterwards, the synthetized QA derivatives were examined as photocatalysts to promote the selective aerobic oxidation of thioether to sulfoxide. Promising results in thioanisole oxidation were achieved with all the QA derivatives tested as photocatalysts, in terms of yield and selectivity. Remarkably, DBQA showed the best performances, catalyzing the reaction in only 20 minutes, using 0.5 % of the photocatalyst, and showing excellent performances in the oxidation of several thioether derivatives.

Adjustment of active protons of end-electron-withdrawing groups in small molecules for different memory characteristics

Owing to the diverse design strategy and convenient structural modification, the small molecular organic materials have been widely applicated in the fabrication of memory devices with complex memory behavior. In this work, we successfully synthesized two asymmetric quinacridone derivatives, BQTCH and BQTCE, with the same electron donors and molecular backbone, but different terminal groups. The sandwich-structured memory devices based on BQTCH and BQTCE have also successfully been prepared via spin-coating. The optical properties, packing performances, thermal stabilities and surface morphologies of the small molecules and their corresponding films are characterized via UV–vis and emission spectra, AFM, TGA and XRD. The I–V curves indicate all the as-prepared devices exhibit excellent memory performances, and the sandwich-structured memory devices based on ITO/BQTCH/Al exhibit a ternary memory behavior (WORM type from OFF to ON1 but FLASH type from ON1 to ON2), while the memory devices based on ITO/BQTCE/Al exhibit a typical ternary memory behavior (WORM type). To explain this difference, DFT molecular simulation and the energy level diagrams of HOMO and LUMO orbitals of BQTCH and BQTCE are investigated to demonstrate the crucial role of terminal groups in influencing the memory behavior.

Quinacridone based 2D covalent organic frameworks as efficient photocatalysts for aerobic oxidative Povarov reaction

Quinacridone (QA) derivatives, one of cost-effective dyes with intriguing optical activity, have been extensively investigated in many fields such as organic light-emitting diodes, organic solar cells, and photocatalysis. Herein, a new QA-monomer (QA-PCHO) with a zigzag configuration was synthesized via N-arylation of benzene halide and quinacridone. The new monomer could enrich eventual structural diversity of the corresponding covalent organic frameworks (COFs). And based on the precursor, we developed two new QA-based 2D imine COFs with large pore size (> 4.7 nm) which exhibited superior photocatalytic activity toward Povarov reaction with broad substrate scopes and excellent functional group compatibility.

Quinacridone-based small molecule acceptor as a third component in ternary organic solar cells

• A novel electron-accepting quinacridone derivative was used as a core of the acceptor. • The new acceptor CN-QA-RH presented a broad absorption in the solar spectrum and high crystallinity. • The ternary OSCs based on PBDB-T:PC 71 BM:CN-QA-RH demonstrated the PCE of 19.13% under LED (6500 K) illumination at 1000 lx. Ternary blend strategy has exhibited great prospect in organic solar cells (OSCs) due to the potential to boost the power conversion efficiency (PCE) by mainly enhancing the light absorption and morphology of the active layer. In particular, introduction of non-fullerene acceptor as the third component can overcome the intrinsic shortages of fullerene in the binary fullerene OSCs. Herein, an acceptor–donor-acceptor’-donor–acceptor(A-D-A’-D-A) type molecule, CN-QA-RH, containing a rigid acceptor unit quinacridone (QA) derivative as a central core, is designed and synthesized. The compound exhibits a wide absorption in the solar spectrum and good crystallinity. Both absorption and morphology of the active layer were improved by incorporating CN-QA-RH as the third component into PBDB-T:PC 71 BM. As a result, the best PCE of the ternary OSCs based on PBDB-T:PC 71 BM:CN-QA-RH was 8.96% while the binary OSCs based on PBDB-T:CN-QA-RH and PBDB-T:PC 71 BM exhibited PCEs of 2.66% and 7.84%, respectively. Moreover, the optimized ternary OSCs yielded a PCE of 19.13% under LED illumination at 1000 lx. Therefore, QA derivatives can be applied as non-fullerene acceptors with wide absorption and high crystallinity and demonstrated a great potential as the third component to construct highly efficient ternary OSCs for indoor light.

High-performance electrochromic supercapacitor based on quinacridone dye with good specific capacitance, fast switching time and robust stability

• QA dyes were designed and firstly prepared into electrochromic polymers. • The polymers with three donor units show different electrochemical behaviors. • pC10QA-2EDOT film exhibits remarkable electrochromic properties. • The device based on pC10QA-2EDOT exhibits robust cyclic stability. • The electrochromic supercapacitor can make a LED light for more than 85 s. Quinacridone (QA) dye with large π-conjugation system exhibit excellent optical, thermal and chemical properties. A series of QA derivatives (C10QA-2T, C10QA-2EDOT, C10QA-2DT) were designed and synthesized with different donor units (including thiophene, EDOT and bithiophene) in this work. Three monomers show different HOMO energy levels and onset oxidation potentials. Their corresponding polymer films were obtained by electrochemical polymerization. Compared to pC10QA-2T and pC10QA-2DT, pC10QA-2EDOT exhibits better integrated electrochromic properties in terms of multicolor showing (yellow, gray and blue), higher optical contrast (more than 40% in the visible region), larger coloration efficiency (498 cm 2 /C at 455 nm), faster switching time (less than 1 s) and better cyclic stability. It is intriguing that the electrochromic device based on pC10QA-2EDOT exhibits robust stability over 50,000 cycles with almost no decay of its original optical contrast. In addition, pC10QA-2EDOT film possesses large volume specific capacitance of up to 322 F/cm 3 , which should be ascribed to that the loose and porous structures owing to large dihedral angles caused by the steric hindrance of oxygen on the EDOT may facilitate the ion diffusion during the doping/dedoping process. Hence, the electrochromic supercapacitor can supply power to a green LED for 85 s. This work pioneers QA dye in the electrochromic field and further develops a new electrochromic energy storage device with visual color display, which may have potential prospects in portable and wearable electronic devices.

Developing Flexible Quinacridone-Derivatives-Based Photothermal Evaporaters for Solar Steam and Thermoelectric Power Generation.

Solar-driven interfacial vaporization by localizing solar-thermal energy conversion to the air-water interface has attracted tremendous attention. In the process of converting solar energy into heat energy, photothermal materials play an essential role. Herein, a flexible solar-thermal material di-cyan substituted 5,12-dibutylquinacridone (DCN-4CQA)@Paper was developed by coating photothermal quinacridone derivatives on the cellulose paper. The DCN-4CQA@Paper combines desired chemical and physical properties, broadband light-absorbing, and shape-conforming abilities that render efficient photothermic vaporization. Notably, synergetic coupling of solar-steam and solar-electricity technologies by integrating DCN-4CQA@Paper and the thermoelectric devices is realized without trade-offs, highlighting the practical consideration toward more impactful solar heat exploitation. Such solar distillation and low-grade heat-to-electricity generation functions can provide potential opportunities for fresh water and electricity supply in off-grid or remote areas.

Acridone and quinacridone derivatives with carbazole or phenoxazine substituents: synthesis, electrochemistry, photophysics and application as TADF electroluminophores

Six acridone (quinacridone) derivatives containing either carbazole or phenoxazine substituents were synthesized aiming to elucidate the effect of the donor and acceptor linking pattern on their photophysical and electrochemical properties.

First-principles study on optoelectronic properties of new quinacridone dye derivatives in dye sensitized photovoltaic cells

In this work, we design new organic dyes for dye sensitized photovoltaic cells (DSPVs). We use density functional theory (DFT) and time dependent-density functional theory (TD-DFT) calculations to study the novel dyes based quinacridone derivatives (A1-A8). In particular, we examine the molecular orbitals distributions, absorption proprieties, light collection efficiency, injection driving force, electronic vertical excitation energy and oscillator forces. We reveal that all designed molecules have a low band gap and excellent optical properties. In addition, we investigate the photovoltaic performance of new dyes. Therefore, the engineered dyes present a potential effective electron injection into the semiconductor conduction band. The achieved outcomes motivate the scientific committees to investigate such molecules experimentally, that might improve the efficiency of dye sensitized photovoltaic cells (DSPVs).

Green electrogenerated chemiluminescence using a quinacridone derivative as a guest molecule

We have developed a solution-based green electrogenerated chemiluminescence (ECL) cell using a quinacridone derivative, 5,12-dibutyl-1,3,8,10-tetramethylquinacridone (TMDBQA), as a fluorescent guest. 2-tert-Butyl-9,10-di(naphth-2-yl)anthracene (TBADN) and 4,4′-bis[4-(diphenylamino)styryl]biphenyl (BDAVBi) were used as host and assist dopant molecules, respectively, and dissolved in an organic solvent with the guest. When a direct current voltage of 5.5 V was applied, the microfluidic ECL cell, which has a 5-μm-thick microchannel sandwiched between two transparent electrodes, exhibited bright green emission from TMDBQA with a maximum luminance of 40.9 cd/m2 and a maximum current efficiency of 2.25 cd/A. However, if both TBADN and BDAVBi were absent from the solution, ECL emission was not observed. Thus, a possible mechanism for the efficient ECL emission of TMDBQA is proposed, involving a two-step energy transfer from TBADN through BDAVBi. We believe that the concept of host–guest solutions will be useful in developing novel light-emitting devices.

Quinacridone skeleton as a promising efficient leveler for smooth and conformal copper electrodeposition

Superconformal copper electrodeposition of nano-micro printed circuit board (PCB) is of prime importance in microelectronics manufacturing. It is very challenging and still remains deficient exploration to fully realize efficient conformal electrodeposition in the emerging organic additives. Herein, a family of quinacridone (QA) derivatives bearing quaternary ammonium groups were synthesized via two steps with high yields. These compounds were functionalized as promising levelers for superconformal Cu deposition for the first time. Alkyl chains and aryl groups tuning strategies were performed to precisely synthesize and optimize these QA levelers. The optimal leveling agent (DCQA-C8-QAS) and electrodeposition formula were obtained through electrochemical measurements, theoretical calculations and through-hole (TH) electrodeposition experiments. The superior leveling behavior of DCQA-C8-QAS was mainly attributed to the strong interaction and adhesion ability towards copper surface, which were verified by X-ray photoelectron spectra (XPS), atomic force microscope (AFM) and contact angle detection (CA).

Study on new quinacridone derivatives with enhanced third-order nonlinear optical properties

Seven new quinacridone derivatives were designed and synthesized. The relationship between molecular structure and nonlinear optical properties was studied by cyclic voltammetry, DFT calculation and Z-scan. By introducing strong electron donating groups at the two sides of the quinacridone, and then introducing a strong electron withdrawing group dicyanoethylene group, the band gap of the molecule can be effectively reduced, and the intramolecular charge transfer can be promoted. The results shown that the HOMO/LUMO band gaps of the target compounds are all reduced, and QA-F has the best third-order nonlinear optical performance, and its γ (γ = 5.32 × 10−33 esu) is 4.38 times that of QA-1 (γ = 1.21 × 10−33 esu).

Enhanced photoelectric and photocatalysis performances of quinacridone derivatives by forming D-π-A-A structure

Five D-π-A-A type of heterocyclic polycyclic aromatic hydrocarbons (hetero-PAHs) organic molecules with quinacridone (QA) derivatives as the core bridge connected with different donor groups of triarylamine (T), indoline derivative (W), and carbazole (K) and the auxiliary acceptor groups benzobisthiadiazole (B) and furan (F) have been designed. The potential application of designed sensitizers in solar cells and photocatalysis have been investigated. Microscopic major processes involve dye regeneration, electrons recombination, intramolecular charge transfer (ICT) properties and key parameters of molecular photoelectric performance. Besides, the coupling strength, energy gaps, dipole moments, molecular fluorescent lifetime and the bonding type between dye and TiO2 were estimated to reveal the nature of photocatalysis. Results indicated that introducing W or B unit should improve the photoelectric performance among all design strategies (especially, simultaneously introducing two moieties) due to the excellent electron-donating ability of W and the pull electrons' ability of B auxiliary acceptor. Designing WQAB@TiO2 and WQAF@TiO2 to have better photocatalytic properties owing to the stronger interaction and surface charge transfer, particularly for WQAB. Current molecular strategies using controlling moieties provide a choice for potential applications in solar cells and photocatalytic fields.

New quinacridone derivatives: Synthesis, photophysical and third-order nonlinear optical properties

A series of quinacridone third-order nonlinear optical chromophores containing phenyl, 4-methoxyphenyl and N,N-bis(4-methoxyphenyl)aniline groups were designed and synthesized. The optical properties, electrical properties, theoretical calculations and Z-Scan of the compounds were measured and analyzed to investigate the relationship between structure and third-order NLO properties. The experimental results showed that the introduction of electron-donating groups at the N-position of quinacridone decreases the energy gap (Egap) between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the molecule, and promotes intramolecular charge transfer (ICT). Quinacridone derivatives containing N, N-bis (4-methoxyphenyl) aniline have good third-order nonlinear optical properties, with the nonlinear absorption coefficient (β) value of 1.4319 × 10−13 and the second-order superpolarizability (γ) of 2.6849 × 10−33 esu.

A Quinacridone-Diphenylquinoxaline-Based Copolymer for Organic Field-Effect Transistors.

In this work, we characterized poly(quinacridone-diphenylquinoxaline) (PQCTQx). PQCTQx was synthesized by a Suzuki coupling reaction and the synthesized PQCTQx was used as a polymeric semiconducting material in organic field-effect transistors (OFETs) to research the potential of using quinacridone derivatives. The measured field-effect mobility of the pristine PQCTQx film was 6.1 × 10−3 cm2/(V·s). A PQCTQx film heat-treated at 150 °C exhibited good field-effect performances with a hole mobility of 1.2 × 10−2 cm2/(V·s). The improved OFET behaviors resulting from the mild thermal treatment was attributed to improved packing of the molecules in the film, as determined using X-ray diffraction, and to decreased channel resistance.

A quinacridone derivative with intensive emission in both solution and the solid state via a facile preparation for cell imaging applications

tert-Butyloxycarbonyl (TBOC) substituted quinacridone (QA) derivative TBOC-QA was synthesized via a one-step simple chemical reaction and showed intense emission in both solution and the solid state.

Quinacridone-quinoxaline-based copolymer for organic field-effect transistors and its high-voltage logic circuit operations

Abstract Poly(quinacridone-quinoxaline) (PQCQx) was synthesized to investigate the potential of quinacridone derivatives as organic semiconductors in organic field-effect transistors (OFETs) and circuits. The device showed a field-effect mobility value of 1.4 × 10−3 cm2/(Vs) at optimal conditions. The morphologies of the deposited films were characterized by performing X-ray diffraction and atomic force microscopy. And, to confirm the feasibility of using PQCQx OFETs in a high-voltage logic circuit operation, a compact model library to describe the electrical behaviors of PQCQx OFETs was developed. By implementing the developed compact model library into a circuit simulator, we successfully evaluated the high-voltage-logic operation of a p-type organic inverter with a frequency of 45.5 kHz in an 80 V supply condition.

Benzothiadiazole-oligothiophene flanked dicyanomethylenated quinacridone for non-fullerene acceptors in polymer solar cells

A new class of benzothiadiazole-oligo(3-hexylthiophene) flanked dicyanomethylenated quinacridone derivatives DCNQA-BT-Tn (n = 1–3) has been designed and synthesized in good yield by iterative bromination and Suzuki coupling reactions, followed by Knoevenagel condensation.

Design and synthesis of a series of N-donor quinacridone derivatives with novel nonlinear optical properties

In this work, five new quinacridone (QA)-based dyes containing a N-donor moiety have been synthesized, defined as C12QA–F, C12QA–G, C12QA–H, C12QA–I and C12QA–J, for the application of third-order nonlinear optical (NLO) responses. A new design has been put forward with the first step of connecting a long alkyl chain on the planar structure of parent ring of QA, with the aim to increase the solubility of the compound and reduce its π-π intermolecular stacking and the second step of connecting N-donor groups to enhance the effect of molecule. Electrochemical measurement data indicated that the tuning of the HOMO and LUMO energy levels can be easily realized by introducing the N-donor moiety. The theoretical calculations showed a smaller dihedral angle between the QA moiety and the N-donor than the usual, implying an excellent planarity between the two groups, which is beneficial for the intramolecular charge transfer (ICT). NLO tested under similar Z-scan measurements conditions showed that, the second-order hyperpolarizability (γ) of the five synthesized compounds ranged from 2.136 × 10−33 esu to 13.856 × 10−33 esu, with the maximum of C12QA-H was more than 13 times higher than N,N-di(n-dodecane) quinacridone(C12QA) of 0.964 × 10−33 esu. The results suggested that the designed QA-based compounds had good thermal stability and superior third-order NLO properties, very promising for integrated NLO devices.

A triphenylamine substituted quinacridone derivative for solution processed organic light emitting diodes

We report on a novel quinacridone derivative design, namely, 2,9-bis(4-(bis(4-methoxyphenyl)amino)phenyl)-5,12-bis(2-ethylhexyl)-5,12-dihydroquinolino[2,3-b]acridine-7,14-dione (TPA-QA-TPA) for possible use as a solution processable emissive layer in organic light emitting diodes (OLEDs). TPA-QA-TPA contains branched alkyl chains for enhanced solubility and methoxytriphenylamine moieties (TPA) as end capping groups. The end capping groups not only extend the molecular conjugation leading to a red shifted emission, but have a propeller shaped conformation. The propeller design hinders the intermolecular π-π stacking, hindering aggregation and hence suppressing concentration quenching of the fluorophores in the solid state. The new molecular design shows good thermal stability, with a decomposition temperature of 390 °C and a melting temperature of 295 °C. The absorption and emission maxima for TPA-QA-TPA compound are 552 and 622 nm respectively. Using TPA-QA-TPA as a dopant in tris(8-hydroxyquinolinato)aluminum (Alq3), organic light emitting diodes were realized in a simple device structure.