Electron-deficient Building Block Research Articles

(Invited) Redox Switchable Organic Conjugated Materials for Flexible Electrochromic Devices

Organic π−conjugated compounds have experienced over the last decades a tremendous interest as versatile and highly performing active components in a large variety of devices and applications. Two peculiar characteristics of organic materials are key for their technological exploitation. Firstly, most organic conjugated materials can be manufactured by low cost, solution based deposition techniques. Moreover, the intrinsic flexibility of both their electrochemical and optical properties holds promises for custom designed active materials. On this respect, the formulation of general structure-property relationships is a key requirement. This talk will address the main characteristics connected with reversible redox behaviour in conjugated materials: charge transport capabilities and tuning of optical properties. The discussion will focus on the structural design required for the preparation of preferentially n or p dopable semiconducting polythiophenes derivates highlighting the role of heteroaromatic compounds as intrinsically electron excessive or electron deficient building blocks. The role of solid state interactions in both single and multi component thin layers will then describe, focusing on recent examples of organic-based electrochromic devices developed in the frame of the EELICON FP7 project.

A supramolecular bottlebrush polymer assembled on the basis of cucurbit[8]uril-encapsulation-enhanced donor–acceptor interaction

A supramolecular bottlebrush polymer has been constructed in water through the self-assembly of a rigid electron-deficient building block and an electron-rich monomer which bears two tetraethylene glycol chains, driven by CB[8]-encapsulation-enhanced donor–acceptor interaction. The as-formed supramolecular bottlebrush polymer has been characterized by 1H NMR titration experiment, UV–vis spectroscopy, DLS and 2D 1H NMR DOSY.

Bithiazole: An Intriguing Electron‐Deficient Building for Plastic Electronic Applications

The heterocyclic thiazole unit has been extensively used as electron-deficient building block in π-conjugated materials over the last decade. Its incorporation into organic semiconducting materials is particularly interesting due to its structural resemblance to the more commonly used thiophene building block, thus allowing the optoelectronic properties of a material to be tuned without significantly perturbing its molecular structure. Here, we discuss the structural differences between thiazole- and thiophene-based organic semiconductors, and the effects on the physical properties of the materials. An overview of thiazole-based polymers is provided, which have emerged over the past decade for organic electronic applications and it is discussed how the incorporation of thiazole has affected the device performance of organic solar cells and organic field-effect transistors. Finally, in conclusion, an outlook is presented on how thiazole-based polymers can be incorporated into all-electron deficient polymers in order to obtain high-performance acceptor polymers for use in bulk-heterojunction solar cells and as organic field-effect transistors. Computational methods are used to discuss some newly designed acceptor building blocks that have the potential to be polymerized with a fused bithiazole moiety, hence propelling the advancement of air-stable n-type organic semiconductors.

Conjugated polymers containing B←N unit as electron acceptors for all-polymer solar cells

Polymer electron acceptors are the key materials in all-polymer solar cells (all-PSCs). In this review, we focused on introducing the principle of boron-nitrogen coordination bond (B←N), and summarizing our recent research on polymer electron acceptors containing B←N unit for efficient all-PSC devices. Two approaches have been reported to design polymer electron acceptors using B←N unit. One is to replace a C–C unit by a B ← N unit in conjugated polymers to transform a polymer electron donor to a polymer electron acceptor. The other approach is to construct novel electron-deficient building block based on B←N unit for polymer electron acceptors. The polymer electron acceptors containing B←N unit showed tunable lowest unoccupied molecular orbital (LUMO) energy levels and exhibited excellent all-PSC device performance with power conversion efficiency of exceeding 6%. These results indicate that organic boron chemistry is a new toolbox to develop functional polymer materials for optoelectronic device applications.

5,5′‐Diazaisoindigo: an Electron‐Deficient Building Block for Donor–Acceptor Conjugated Polymers

A novel electron-deficient building block, 5,5'-diazaisoindigo (5DNIID), was synthesized through a facile method in good yield. As a derivative of isoindigo, 5DNIID shows an ultra-low LUMO level of -3.92 eV after incorporation of two electron-deficient nitrogen atoms into the para-position of the amine groups in the isoindigo π skeleton. Modified polymerization conditions were applied to efficiently afford the donor-acceptor (D-A) conjugated polymer 5DNIID-2T, which exhibited a p-type charge transport property.

N,N'-Bis(2-cyclohexylethyl)naphtho[2,3-b:6,7-b']dithiophene Diimides: Effects of Substituents.

Naphtho[2,3-b:6,7-b′]dithiophene-4,5,9,10-tetracarboxylic diimide (NDTI) is a promising electron-deficient building block for n-type organic conductors, and the performance of NDTI-based field-effect transistors (FETs) is largely dependent on the substituents that alter the supramolecular organization in the solid state and, in turn, the intermolecular orbital overlap. For this reason, the rational selection of substituent on imide nitrogen atoms and/or thiophene α-positions is the key to developing superior n-type organic semiconductors. We here report new NDTI derivatives having N-(2-cyclohexylethyl) groups. Despite their one-dimensional packing structures in the solid state regardless of the presence or absence of chlorine groups at the thiophene α-positions, their FETs show promising performance with electron mobilities higher than 0.1 cm2·V−1·s−1 under ambient conditions. We also discuss how the cyclohexylethyl groups affect the packing structure in comparison with analogous n-octyl derivatives having the same number of carbon atoms.

Achieving high performance non-fullerene organic solar cells through tuning the numbers of electron deficient building blocks of molecular acceptors

Two analogous dimer and tetramer compounds, SF-PDI2 and SF-PDI4, were designed, theoretically calculated, synthesized, and developed as electron acceptors for organic solar cells. The effects of the number of the electron deficient building blocks on the optical absorption, energy levels, charge transport, morphology, crystallinity, and photovoltaic performance of the molecules were investigated. In combination with two different donors, PTB7-Th and PffBT4T-2OD, the results showed that increasing the numbers of PDI building blocks is beneficial to photovoltaic performance and leads to efficiency over 5%.

Structure–Property Relationships Directing Transport and Charge Separation in Isoindigo Polymers

Since being introduced to the open literature in 2010, the isoindigo heterocycle has been extensively studied as a novel electron-deficient building block for organic electronic materials in conjugated polymers, discrete length oligomers, and molecular systems, particularly targeting high charge mobility values and ambipolar transport in organic field effect transistors, along with high power conversion efficiencies in organic photovoltaic devices. This article introduces results obtained on copolymers of isoindigo with thiophene and alkylated terthiophenes to highlight fundamental characteristics in isoindigo-based polymers and the resulting organic field-effect transistors and photovoltaic devices. By comparing and contrasting the optoelectronic properties, thin film morphology, organic field-effect transistor (OFET) mobilities, and organic photovoltaic (OPV) performance to previously reported polymers, structure–processing–property relationships were uncovered. In particular, isoindigo-containing polym...

First-Principles Study of Thermoelectric Properties of Covalent Organic Frameworks

Covalent organic frameworks (COFs) are new emerging functional porous materials. Strong covalent bonds result in molecular building blocks that can be arranged in layered two-dimensional (2D) or three-dimensional (3D) periodic networks. However, to the best of our knowledge, there have been no reports on experimental and theoretical studies of thermoelectrical properties of COFs to date. Therefore, density functional theory (DFT) and the Boltzmann transport equation have been applied in this work to calculate the semiclassical transport coefficients for phthalocyanine (Pc)-based NiPc, NiPc-benzothiadiazole (BTDA), and Pc COFs. Owing to the well-ordered stacking of the phthalocyanine units and linkers in these compounds, charge-carrier transport is facilitated in the stacking direction. In all studied compounds, the highly directional character of π-orbitals provides band-structure engineering and produces a type of low-dimensional hole transport along the stacking direction. All studied compounds are indirect semiconductors. The low-dimensional transport of holes and the localized states in both valence and conduction bands prevent the electron–hole compensation effect in the Seebeck coefficients, correlating with the large Seebeck coefficients of the studied compounds. Insertion of the electron-deficient building block benzothiadiazole in the NiPc-BTDA COF leads to positive Seebeck coefficients along the a-, b-, and c-directions. The relaxation time was estimated in our investigations from DFT band-structure calculations and the experimentally defined mobility, leading to determination of the electrical conductivity and electronic contribution to the thermal conductivity, as well as figure of merit (ZT) estimation. Ni atom provided greater electrical conductivity along the c-direction in comparison with metal-free Pc COF, and NiPc COF showed the highest thermoelectric performance among the studied COFs.

An Electron‐Deficient Building Block Based on the B←N Unit: An Electron Acceptor for All‐Polymer Solar Cells

A double B←N bridged bipyridyl (BNBP) is a novel electron-deficient building block for polymer electron acceptors in all-polymer solar cells. The B←N bridging units endow BNBP with fixed planar configuration and low-lying LUMO/HOMO energy levels. As a result, the polymer based on BNBP units (P-BNBP-T) exhibits high electron mobility, low-lying LUMO/HOMO energy levels, and strong absorbance in the visible region, which is desirable for polymer electron acceptors. Preliminary all-polymer solar cell (all-PSC) devices with P-BNBP-T as the electron acceptor and PTB7 as the electron donor exhibit a power conversion efficiency (PCE) of 3.38%, which is among the highest values of all-PSCs with PTB7 as the electron donor.

Epindolidione-Based Conjugated Polymers: Synthesis, Electronic Structures, and Charge Transport Properties

Development of new electron-deficient building blocks is essential to donor-acceptor conjugated polymers. Herein, epindolidione (EPD) as electron-deficient unit was integrated into conjugated polymers for the investigation of field-effect transistors for the first time. We systematically studied the electronic structures and charge transport properties of the EPD-based donor-acceptor polymers. They exhibit p-type transport characteristics with the highest mobility of up to 0.40 cm(2) V(-1) s(-1), thus demonstrating its great potential as a building block for polymer field-effect transistors and photovoltaics.

Novel medium band gap conjugated polymers based on naphtho[1,2-c:5,6-c]bis[1,2,3]triazole for polymer solar cells

Two new donor–acceptor type of conjugated polymers derived from naphtho[1,2-c:5,6-c]bis(2-octyl-[1,2,3]triazole) and dithieno[3,2-b:2′,3′-d]silole were prepared by Stille polymerization. The thermal, electrochemical and photophysical properties of these copolymers were studied. Both polymers have excellent thermal stability with decomposition temperature up to 430 °C. The copolymers show medium band gap of ∼1.8 eV. Inverted bulk heterojunction solar cells in which these copolymers are used as electron donors in combination with PC61BM as the electron acceptor were fabricated. Under AM 1.5 G illumination at 100 mW/cm2, device based on P1:PC61BM as the photoactive layer displays a moderate power conversion efficiency of 2.58% with an open-circuit voltage of 0.83 V, a short circuit current of 5.53 mA/cm2, and a fill factor of 56.13%. Our work indicates that naphtho[1,2-c:5,6-c]bis(2-octyl-[1,2,3]triazole) can be a promising electron-deficient building block for designing donor–acceptor type of polymeric materials.

Design of (X-DADAD)n Type Copolymers for Efficient Bulk Heterojunction Organic Solar Cells

We show that extended TBTBT structure (T = thiophene, B = benzothiadiazole) can be used as an electron-deficient building block for designing conjugated polymers with deeply lying HOMO energy levels and narrow band gaps. The first carbazole–TBTBT copolymer P2 demonstrated power conversion efficiencies exceeding 6% in bulk heterojunction solar cells in combination with advanced operational stability, unlike conventional donor polymers such as PTB7, PBDTTT-CF, etc.

New form of an old natural dye: bay-annulated indigo (BAI) as an excellent electron accepting unit for high performance organic semiconductors.

A novel electron acceptor was synthesized from one-step functionalization of the readily available indigo dye. The resulting bay-annulated indigo (BAI) was utilized for the preparation of a series of novel donor-acceptor small molecules and polymers. As revealed experimentally and by theoretical calculations, substituted BAIs have stronger electron accepting characteristics when compared to several premier electron deficient building blocks. As a result, the donor-acceptor materials incorporating BAI acceptor possess low-lying LUMO energy levels and small HOMO-LUMO gaps. In situ grazing incidence wide-angle X-ray scattering studies of the thin films of BAI donor-acceptor polymers indicated improved crystallinity upon thermal treatment. Field effect transistors based on these polymers show excellent ambipolar transporting behavior, with the hole and electron mobilities reaching 1.5 and 0.41 cm(2) V(-1) s(-1), respectively, affirming BAI as a potent electron accepting unit for high performance organic electronic materials.

Dibenzothiophene-S,S-dioxide based medium-band-gap polymers for efficient bulk heterojunction solar cells

Medium-band-gap polymers based on indacenodithiophene (IDT) and dibenzothiophene-S,S-dioxide (SO) derivatives, PIDT-SO and PIDT-DHTSO, were synthesized via a microwave assisted Stille polycondensation. The polymers have the maximum absorption ∼500nm, high absorption coefficients above 0.6×10−2nm−1, and medium band gaps of ∼2.2eV. Their hole mobilities are around 2×10−4cm2V−1s−1 as measured by field effect transistors. The photovoltaic performances of the polymers were investigated on the inverted bulk heterojunction (BHJ) devices of ITO/PFN/PIDT-DHTSO:PC71BM (1:3, w/w)/MoO3/Al, and a power conversion efficiency (PCE) of 3.81% with an open-circuit voltage (Voc) of 0.95 V, a short-circuit current (Jsc) of 8.20mAcm−2 and a fill factor (FF) of 48% were achieved. Those results indicated that dibenzothiophene-S,S-dioxide derivatives could be an excellent electron-deficient building block for medium-band-gap electron-donor polymers.

Narrow-Band-Gap Conjugated Polymers Based on 2,7-Dioctyl-Substituted Dibenzo[a,c]phenazine Derivatives for Polymer Solar Cells

A series of new 2,7-dioctyl-substituted dibenzo[a,c]phenazine (BPz) derivatives were designed and synthesized as electron-deficient units, which were copolymerized with an electron-rich indacenodithiophene (IDT) to construct narrow-band-gap copolymers PIDT–OHBPz, PIDT–OFBPz, and PIDT–OBPQ via Stille polycondensation. The 2,7-dioctyl substituents enhanced solubility and offered a new approach for developing various BPz derivatives. All copolymers showed high hole mobilities above 0.01 cm2 V–1 s–1 as measured by field effect transistors. The best performance of polymer solar cell was achieved based on PIDT–OFBPz with inverted device structure of ITO/ZnO/PFN/polymer:PC61BM/MoO3/Al, which showed an open-circuit voltage (Voc) of 0.97 V, a short-circuit current (Jsc) of 8.96 mA/cm2, and a fill factor (FF) of 58.99%, leading to a high power conversion efficiency (PCE) of 5.13%. These results indicate that 2,7-alkyl-substituted BPz derivatives can be used as an excellent electron-deficient building block for the ...

Benzotriazole-Containing Planar Conjugated Polymers with Noncovalent Conformational Locks for Thermally Stable and Efficient Polymer Field-Effect Transistors

We report a series of benzotriazole-based semicrystalline π-conjugated polymers with noncovalent conformational locks for applications in polymer field-effect transistors. The benzotriazole moiety is a versatile electron-deficient building block that offers two chemically functionalizable sites, 2(N) and 5, 6(C) positions, allowing easy modulation of the solution processability and electronic structures of the resulting polymers. Fluorine or alkoxy substituents were introduced to the benzotriazole unit to enhance the molecular ordering through intra- and intermolecular F···S, F···H–C, C–F···πF, or S···O attractive interactions. The fluorinated polymer (PTBTz-F) showed remarkably enhanced hole mobility (μh = 1.9 cm2/(V·s), on/off ratio = 8 × 107) upon thermal annealing at 305 °C, compared to the unsubstituted one (PTBTz) (μh = 7.0 × 10–3 cm2/(V·s), on/off ratio = 3 × 106). Alkoxy unit substitution (PTBTz-OR) also improved the carrier mobility up to 0.019 cm2/(V·s) with an on/off ratio of 4 × 105. Fluorine ...

“Conformation Locked” Strong Electron-Deficient Poly(p-Phenylene Vinylene) Derivatives for Ambient-Stable n-Type Field-Effect Transistors: Synthesis, Properties, and Effects of Fluorine Substitution Position

The charge carrier mobility of p-type and ambipolar polymer field-effect transistors (FETs) has been improved substantially. Nonetheless, high-mobility n-type polymers are rare, and few can be operated under ambient conditions. This situation is mainly caused by the scarcity of strong electron-deficient building blocks. Herein, we present two novel electron-deficient building blocks, FBDOPV-1 and FBDOPV-2, with low LUMO levels down to -4.38 eV. On the basis of both building blocks, we develop two poly(p-phenylene vinylene) derivatives (PPVs), FBDPPV-1 and FBDPPV-2, for high-performance n-type polymer FETs. The introduction of the fluorine atoms effectively lowers the LUMO levels of both polymers, leading to LUMO levels as low as -4.30 eV. Fluorination endows both polymers with not only lower LUMO levels, but also more ordered thin-film packing, smaller π-π stacking distance, stronger interchain interaction and locked conformation of polymer backbones. All these factors provide FBDPPV-1 with high electron mobilities up to 1.70 cm(2) V(-1) s(-1) and good stability under ambient conditions. Furthermore, when polymers have different fluorination positions, their backbone conformations in solid state differ, eventually leading to different device performance.

A BDOPV‐Based Donor–Acceptor Polymer for High‐Performance n‐Type and Oxygen‐Doped Ambipolar Field‐Effect Transistors

An electron-deficient building block BDOPV is developed to construct a new donor-acceptor conjugated polymer BDOPV-2T for high-performance n-type and oxygen-doped ambipolar polymer field-effect transistors. A high electron mobility up to 1.74 cm(2) V(-1) s(-1) is demonstrated under ambient conditions. Furthermore, the oxygen-doping effect and possible mechanism are discussed.

Electron deficient conjugated polymers based on benzotriazole

A series of solution processable conjugated polymers containing the benzotriazole unit have been synthesized and studied. The benzotriazole unit can be considered a moderately electron deficient building block that can readily incorporate a convenient alkyl substituent for solution processability. By varying the electron accepting strength of co-monomer partners, a series of polymers with different photophysical properties were obtained. Some polymers exhibit relatively high fluorescence quantum yields while others were able to quench the fluorescence of electron donor polymers in blends consistent with their ability to act as electron acceptors. The performance of these polymers as the active material in organic light emitting diode (OLED) and organic photovoltaic (OPV) devices is reported.