Strong Electron-withdrawing Unit Research Articles

N-Type semiconducting polymers based on an bithiophene imide-bridged isoindigo for organic field-effect transistors

n-Type polymer semiconductors are essential for enabling high-performance organic electronic devices; however, their development still remains a challenge. Herein, we reported a new electron-deficient building block, i.e. bithiophene imide (BTI)-bridged isoindigo (IID), BTIID, through a Knoevenagel condensation reaction between the bisaldehyde BTI and the alkylated indolinones. Three donor-acceptor (D-A) copolymers were then successfully synthesized via standard Stille coupling reaction based on this novel building block, which exhibit highly planar backbones and low-lying lowest unoccupied molecular orbitals (LUMO) energy levels. When integrated into organic field-effect transistors (OFETs), these polymers demonstrated unipolar n-type transport characteristics with a highest electron mobility of 5.79 × 10−4 cm2 V−1 s−1. Our research results indicate that the design of strong electron-withdrawing units via integrating two different electron-acceptor units into one single structure represents a promising strategy for developing n-type polymer semiconductors with low-lying LUMO energy levels.

A computational insight into enhancement of photovoltaic properties of non-fullerene acceptors by end-group modulations in the structural framework of INPIC molecule

Improving the open circuit voltage is a major challenge for enhancing the overall efficiency of organic solar cells. Current work has concentrated on improving open-circuit voltage by designing new molecular frameworks from an INPIC molecule having a conjugated fused core. We modulated the structure by changing the terminal groups of the reference molecule (INPIC) with seven strong electron-withdrawing units. We investigated various optoelectronic attributes, charge transfer, and photovoltaic and geometrical parameters by compiling the B3LYP/6-31G(d,p) functional of the DFT approach. The optical absorption for modulated molecules ranges from 748.51 nm to 845.96 nm while showing higher oscillation strength than INPIC. At the same time, their impressive charge transport is attributed to their smaller excitation and exciton binding energy, higher electron/hole mobility, narrower band gap, and a more than 99 % intramolecular charge transfer. The larger dipole moments help in the dense interaction of acceptors with employed donor J61 which, in turn, improves charge transfer at the donor-acceptor interface. One of the triumphs that are difficult to get in organic molecules is success in achieving a higher open circuit voltage (VOC). Our conceptualized molecular frameworks of acceptors are featured with a notable VOC improvement in the range of 1.84–2.05 eV. Thus, the results of the current investigation pave the root for architecting the acceptor molecules with impressive optoelectrical properties that may be capable of providing high photovoltaic output. Thus these acceptors can be utilized for the development of advanced organic solar cells in future.

Sulfone/Carbonyl-Based Donor-Acceptor Fluorescent Dyes: Synthesis, Structures, Photophysical Properties and Cell Imaging.

Electron-accepting units play vital roles in constructing donor-acceptor (D-A) conjugated organic optoelectronic materials; the electronic structures and functions of the acceptors need to be carefully unveiled to controllably tailor the optoelectronic properties. We have synthesized two D-A conjugated organic fluorophores, TPA-SO and TPA-CO, with similar molecular skeletons based on sulfone- or carbonyl-containing polycyclic aromatic acceptors. Both TPA-SO and TPA-CO display obvious solvent polarity-dependent photophysical properties and large Stokes shift of over 100 nm for strong intramolecular charge transfer processes. Experimental evidence indicates that the sulfone group in TPA-SO merely serves as a strong electron-withdrawing unit. TPA-SO shows yellowish-green emission with a peak at 542 nm and an absolute photoluminescence quantum yield (PLQY) of 98 % in solution, whereas the carbonyl group in TPA-CO can act as both an electron-withdrawing unit and spin transition convertor, so TPA-CO displays red emission with a low absolute PLQY of 0.32 % in solution. Impressively, upon going from solution to aggregate state, TPA-SO nanoparticles keep a high PLQY of 9.5 % and moderate biocompatibility, thus they are good nano-agents for cellular fluorescence imaging. The results reveal that the inherent acceptor characteristic acts as a crucial effect in the photophysical properties and applications of the organic fluorophores.

An A2–π–A1–π–A2-type small molecule donor for high-performance organic solar cells

A new A2–π–A1–π–A2-type small-molecule donor using a strong electron-withdrawing unit as the central unit was synthesized and its photovoltaic performance was investigated.

Fusing Benzo[c][1,2,5]oxadiazole Unit with Thiophene for Constructing Wide-bandgap High-performance IDT-based Polymer Solar Cell Donor Material.

Benzo[c][1,2,5]oxadiazole (BO) moiety is a strong electron-withdrawing unit compared to benzo[c][1,2,5]thiadiazole (BT). It is usually introduced as an acceptor to construct narrow band-gap donor-acceptor (D-A) materials. Herein, the π-extended conjugated moiety dithieno[3',2':3,4″;2,3″:5,6]benzo[1,2-c][1,2,5]oxadiazole (BOT) was adopted as the acceptor moiety to design D-A polymers. Considering the more extended π-conjugated molecular system of BOT compared to the BO unit, a narrower optical band-gap is expected for BOT-based IDT polymer (PIDT-BOT). Unexpectedly, the UV-vis absorption spectra of PIDT-BOT films display a great hypochromatic shift of about 60 nm compared to a BO-based analog (PIDT-BO). The optical band-gaps of the materials are broadened from 1.63 eV (PIDT-BO) to 2.00 eV (PIDT-BOT) accordingly. Although the range of external quantum efficiency (EQE) of PIDT-BOT-based polymer solar cell (PSC) devices is not as wide as for PIDT-BO-based devices, the EQE response intensities of the PIDT-BOT based device are evidently high. As a result, PSC devices based on PIDT-BOT reveal the best power conversion efficiency at 6.08%.

2,1,3-Benzothiadiazole-5,6-dicarboxylicimide-Based Polymer Semiconductors for Organic Thin-Film Transistors and Polymer Solar Cells.

A series of polymer semiconductors incorporating 2,1,3-benzothiadiazole-5,6-dicarboxylicimide (BTZI) as strong electron-withdrawing unit and an alkoxy-functionalized head-to-head linkage containing bithiophene or bithiazole as highly electron-rich co-unit are designed and synthesized. Because of the strong intramolecular charge transfer characteristics, all three polymers BTZI-TRTOR (P1), BTZI-BTOR (P2), and BTZI-BTzOR (P3) exhibit narrow bandgaps of 1.13, 1.05, and 0.92 eV, respectively, resulting in a very broad absorption ranging from 350 to 1400 nm. The highly electron-deficient 2,1,3-benzothiadiazole-5,6-dicarboxylicimide and alkoxy-functionalized bithiophene (or thiazole) lead to polymers with low-lying lowest unoccupied molecular orbitals (-3.96 to -4.28 eV) and high-lying highest occupied molecular orbitals (-5.01 to -5.20 eV). Hence, P1 and P3 show substantial and balanced ambipolar transport with electron mobilities/hole mobilities of up to 0.86/0.51 and 0.95/0.50 cm2 V-1 s-1, respectively, and polymer P2 containing the strongest donor unit exhibited unipolar p-type performance with an average hole mobility of 0.40 cm2 V-1 s-1 in top-gate/bottom-contact thin-film transistors with gold as the source and drain electrodes. When incorporated into bulk heterojunction polymer solar cells, the narrow bandgap (1.13 eV) polymer P1 shows an encouraging power conversion efficiency of 4.15% with a relatively large open-circuit voltage of 0.69 V, which corresponds to a remarkably small energy loss of 0.44 eV. The power conversion efficiency of P1 is among the highest reported to date with such a small energy loss in polymer:fullerene solar cells.

Charge transfer induced unexpected red-shift absorption of Zn and Cu porous coordination polymers based on electron-withdrawing ligand

In the research of wide-range light-absorbing coordination polymers, to enhance intermolecular or intramolecular charge transfer (CT) and decrease the electron transition excitation energy, a dedicatedly designed novel pyridine diketopyrrolopyrrole (DPP) ligand with strong electron-withdrawing unit were introduced into the Zn, Cu and 1,4-benzenedicarboxylic acid (BDC) based coordination frameworks and porous coordination polymers DPP-Zn(BDC) and DPP-Cu(BDC) were obtained, respectively. By comparing study with physically-mixed samples DPP + Zn(BDC) and DPP + Cu(BDC), a fresh light-absorbing peak around 720 nm is observed and makes the samples exhibit a wide-range absorption in the range of 200–1400 nm and gives another experimental evidence for the research of charge transfer effect in naphthalenediimide-based metal-organic framework Zn2(NDC)2(DPNI) (J. Phys. Chem. Lett. 2013, 4, 453–458). The tremendous red-shift of absorbing onset wavelength could be ascribed to the enhanced intermolecular or intramolecular CT due to electron-withdrawing DPP ligands. At the mean time slow-photon effect is also discussed. The materials have been also characterized through powder XRD, FT-IR, SEM, XPS, solution-state spectra techniques and etc. This study underscores the importance of analyzing the extended structure for interpreting photophysical data based on the potential factors: CT, slow photon, or J-coupling. Moreover the research work might inspire the construction of light-responsive coordination polymers or metal-organic frameworks (MOFs) for charge or electron transfer.

Regulating Molecular Aggregations of Polymers via Ternary Copolymerization Strategy for Efficient Solar Cells.

For many high-performance photovoltaic materials in polymer solar cells (PSCs), the active layers usually need to be spin-coated at high temperature due to the strong intermolecular aggregation of donor polymers, which is unfavorable in device repeatability and large-scale PSC printing. In this work, we adopted a ternary copolymerization strategy to regulate polymer solubility and molecular aggregation. A series of D-A1-D-A2 random polymers based on different acceptors, strong electron-withdrawing unit ester substituted thieno[3,4-b]thiophene (TT-E), and highly planar dithiazole linked TT-E (DTzTT) were constructed to realize the regulation of molecular aggregation and simplification of device fabrication. The results showed that as the relative proportion of TT-E segment in the backbone increased, the absorption evidently red-shifted with a gradually decreased aggregation in solution, eventually leading to the active layers that can be fabricated at low temperature. Furthermore, due to the excellent phase separation and low recombination, the optimized solar cells based on the terpolymer P1 containing 30% of TT-E segment exhibit high power conversion efficiency (PCE) of 9.09% with a significantly enhanced fill factor up to 72.86%. Encouragingly, the photovoltaic performance is insensitive to the fabrication temperature of the active layer, and it still could maintain high PCE of 8.82%, even at room temperature. This work not only develops the highly efficient photovoltaic materials for low temperature processed PSCs through ternary copolymerization strategy but also preliminarily constructs the relationship between aggregation and photovoltaic performance.

Rational design of π-bridges for ambipolar DPP-RH-based small molecules in organic photovoltaic cells

We report the synthesis of a series of A1–π–A2–π–A1-type small molecules, DPP2T-RH, DPPFT-RH, and DPPT-RH, in which thiophene and furan were introduced to bridge the two strong electron-withdrawing units of DPP and rhodanine (RH). Interestingly, these DPP-RH-based small molecules exhibited ambipolar characteristics, showing photovoltaic performance both as donors and acceptors in combination with PC71BM and P3HT, respectively. The best power conversion efficiencies were obtained from DPPFT-RH (1.77%) and DPP2T-RH (1.28%) as donor and acceptor, respectively. Their physical properties, film packing ability, and photovoltaic performances were fine-tuned by rational design of the π-bridges.

ChemInform Abstract: Low Bandgap Semiconducting Polymers for Polymeric Photovoltaics

AbstractReview: 141 refs.

A Near-Infrared Dithieno[2,3-a:3′,2′-c]phenazine-Based Organic Co-Sensitizer for Highly Efficient and Stable Quasi-Solid-State Dye-Sensitized Solar Cells

A novel near-infrared (NIR) organic sensitizer FNE53 with a strong electron-withdrawing unit, dithieno[2,3-a:3',2'-c]phenazine, has been designed and synthesized for quasi-solid-state dye-sensitized solar cells (DSSCs). By simply fusing the two thiophene rings on quinoxaline unit in sensitizer FNE48, the intramolecular charge transfer (ICT) band bathochromically shifts from 542 nm for FNE48 to 629 nm for FNE53 in toluene solution. The absorption spectrum of sensitizer FNE53 covers the whole visible region and extends to the NIR region, which exhibits complementary absorption profile to another organic dye FNE46 based on quinoxaline. When FNE46 and FNE53 are used as cosensitizers for metal-free cocktail-type quasi-solid-state DSSCs, sensitizer FNE53 not only extends the photoresponse range but also suppresses the intermolecular interactions among the dye molecules. Therefore, the cocktail-type quasi-solid-state DSSC displays much higher IPCE value compared with that for the DSSC sensitizer based on FNE53 and a broader IPCE response in comparison to that for the DSSC sensitizers based on FNE46, respectively. After the molar ratio between the two cocktail dyes is optimized, the highest energy conversion efficiency of 8.04% is achieved in a metal-free quasi-solid-state DSSC cosensitized with FNE46 and FNE53, which exhibits good long-term stability after continuous light soaking for 1000 h.

Efficient Organic Dye‐Sensitized Solar Cells: Molecular Engineering of Donor–Acceptor–Acceptor cationic dyes

Three metal-free donor-acceptor-acceptor sensitizers with ionized pyridine and a reference dye were synthesized, and a detailed investigation of the relationship between the dye structure and the photophysical and photoelectrochemical properties and the performance of dye-sensitized solar cells (DSSCs) is described. The ionization of pyridine results in a red shift of the absorption spectrum in comparison to that of the reference dye. This is mainly attributable to the ionization of pyridine increasing the electron-withdrawing ability of the total acceptor part. Incorporation of the strong electron-withdrawing units of pyridinium and cyano acrylic acid gives rise to optimized energy levels, resulting in a large response range of wavelengths. When attached to TiO2 film, the conduction band of TiO2 is negatively shifted to a different extent depending on the dye. This is attributed to the electron recombination rate between the TiO2 film and the electrolyte being efficiently suppressed by the introduction of long alkyl chains and thiophene units. DSSCs assembled using these dyes show efficiencies as high as 8.8 %.

Synthesis and Solvatofluorochromism Behaviors on Intramolecular Charge Transfer System of Novel D-π-A Dyes

Solvatochromic donor-π-acceptor (D-π-A) charge transfer dyes have been great attention from the viewpoint of their applicability as probes for the determination of solvent polarity and colorimetric chemosensors. In this work, novel solvatochromic fluorophore dyes based on D-π-A charge transfer system were designed and synthesized containing a strong electron-donating unit as a carbazole moiety and three different strong electron-withdrawing units. The corresponding molecular design and the optical properties of the D-π-A dyes were examined in various solutions with widely different polarity. The prepared dyes were found to exhibit a positive fluorescence solvatochromism. Furthermore, the energy properties of these dyes were also computationally optimized and calculated by computational simulation approaches using Material Studio 4.3 and electrochemical measurement.

A D–A copolymer of dithienosilole and a new acceptor unit of naphtho[2,3-c]thiophene-4,9-dione for efficient polymer solar cells

A strong electron-withdrawing unit, naphtho[2,3-c]thiophene-4,9-dione, was copolymerized with dithienosilole to get a D-A copolymer, PDTSNTDO, with a narrow bandgap and lower-lying HOMO level. The PCE of the PDTSNTDO-based device reached 5.21%, with a high open circuit voltage of 0.88 V.