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It remains challenging to comprehensively understand the packing models of conjugated polymers, in which side chains play extremely critical roles. The side chains are typically flexible and non-conductive and are widely used to improve the polymer solubility in organic solutions. Herein, a buffer chain model is proposed to describe link between conjugated backbone and side chains for understanding the relationship of crystallization competition of conductive conjugated backbones and non-conductive side chains. A longer buffer chain is beneficial for alleviating such crystallization competition and further promoting the spontaneous packing of conjugated backbones, resulting in enhanced charge transport properties. Our results provide a novel concept for designing conjugated polymers towards ordered organization and enhanced electronic properties and highlight the importance of balancing the competitive interactions between different parts of conjugated polymers., (© 2024 Wiley-VCH GmbH.)

Realizing ideal charge transport in field-effect transistors (FETs) of conjugated polymers is crucial for evaluating device performance, such as carrier mobility and practical applications of conjugated polymers. However, the current FETs using conjugated polymers as the active layers generally show certain non-ideal transport characteristics and poor stability. Here, ideal charge transport of n-type polymer FETs is achieved on flexible polyimide substrates by using an organic-inorganic hybrid double-layer dielectric. Deposited conjugated polymer films show highly ordered structures and low disorder, which are supported by grazing-incidence wide-angle X-ray scattering, near-edge X-ray absorption fine structure, and molecular dynamics simulations. Furthermore, the organic-inorganic hybrid double-layer dielectric provides low interfacial defects, leading to excellent charge transport in FETs with high electron mobility (1.49 ± 0.46 cm 2  V -1  s -1 ) and ideal reliability factors (102 ± 7%). Fabricated polymer FETs show a self-encapsulation effect, resulting in high stability of the FET charge transport. The polymer FETs still work with high mobility above 1 cm 2  V -1  s -1 after storage in air for more than 300 days. Compared with state-of-the-art conjugated polymer FETs, this work simultaneously achieves ideal charge transport and environmental stability in n-type polymer FETs, facilitating rapid device optimization of high-performance polymer electronics., (© 2023 Wiley‐VCH GmbH.)

Incorporating heteroatoms can effectively modulate the molecular optoelectronic properties. However, the fundamental understanding of BN doping effects in BN-embedded polycyclic aromatic hydrocarbons (PAHs) is underexplored, lacking rational guidelines to modulate the electronic structures through BN units for advanced materials. Herein, a concise synthesis of novel B 2 N 2 -perylenes with BN doped at the bay area is achieved to systematically explore the doping effect of BN position on the photophysical properties of PAHs. The shift of BN position in B 2 N 2 -perylenes alters the π electron conjugation, aromaticity and molecular rigidness significantly, achieving substantially higher electron transition abilities than those with BN doped in the nodal plane. It is further clarified that BN position dominates the photophysical properties over BN orientation. The revealed guideline here may apply generally to novel BN-PAHs, and aid the advancement of BN-PAHs with highly-emissive performance., (© 2024 Wiley‐VCH GmbH.)

Conjugated polymers that can efficiently transport both ionic and electronic charges have broad applications in next-generation optoelectronic, bioelectronic, and energy storage devices. To date, almost all the conjugated polymers have hydrophobic backbones, which impedes efficient ion diffusion/transport in aqueous media. Here, we design and synthesize a novel hydrophilic polymer building block, 4a-azonia-naphthalene (AN), drawing inspiration from biological systems. Because of the strong electron-withdrawing ability of AN, the AN-based polymers show typical n-type charge transport behaviors. We find that cationic aromatics exhibit strong cation-π interactions, leading to smaller π-π stacking distance, interesting ion diffusion behavior, and good morphology stability. Additionally, AN enhances the hydrophilicity and ionic-electronic coupling of the polymer, which can help to improve ion diffusion/injection speed, and operational stability of organic electrochemical transistors (OECTs). The integration of cationic building blocks will undoubtedly enrich the material library for high-performance n-type conjugated polymers., (© 2023 Wiley-VCH GmbH.)

Charge transport of conjugated polymers in functional devices closely relates to their density of states (DOS) distributions. However, systemic DOS engineering for conjugated polymers is challenging due to the lack of modulated methods and the unclear relationship between DOS and electrical properties. Here, the DOS distribution of conjugated polymers is engineered to enhance their electrical performances. The DOS distributions of polymer films are tailored using three processing solvents with different Hansen solubility parameters. The highest n-type electrical conductivity (39 ± 3 S cm -1 ), the highest power factor (63 ± 11 µW m -1 K -2 ), and the highest Hall mobility (0.14 ± 0.02 cm 2 V -1 s -1 ) of the polymer (FBDPPV-OEG) are obtained in three films with three various DOS distributions, respectively. Through theoretical and experimental exploration, it is revealed that the carrier concentration and transport property of conjugated polymers can be efficiently controlled by DOS engineering, paving the way for rationally fabricating organic semiconductors., (© 2023 Wiley-VCH GmbH.)

Molecular ordering of conjugated polymers both in solution-state aggregates and in solid-state microstructures is a determining factor of the charge transport properties in optoelectronic devices. However, the effect of backbone conformation in conjugated polymers on assembly structures is still unclear. Herein, to understand such backbone conformation effect, three novel chlorinated benzodifurandionge-based oligo(p-phenylene vinylene) (BDOPV) polymers are systematically developed. These BDOPV-based polymers exhibit significantly twisted backbone conformation (near 90° interunit torsion angle) between conjugated units, which can prevent polymer chains from forming ordered assembly structures by increasing conformational energy penalty in closely packed chains. A higher rotational barrier of the torsion angle would further prevent polymer chains from assembling, finally resulting in nonaggregated chains in solution and highly disordered solid-state packing structures. This work will deepen the understanding of the relationship between polymer backbone conformation and assembly structures, contributing to the exploration of the structure-property relationship of polymers., (© 2022 Wiley-VCH GmbH.)

Despite the remarkable synthetic accomplishments in creating diverse polycyclic aromatic hydrocarbons with B-N bonds (BN-PAHs), their optoelectronic applications have been less exploited. Herein, we report the achievement of high-mobility organic semiconductors based on existing BN-PAHs through a "periphery engineering" strategy. Tetraphenyl- and diphenyl-substituted BN-anthracenes (TPBNA and DPBNA, respectively) are designed and synthesized. DPBNA exhibits the highest hole mobility of 1.3 cm 2  V -1  s -1 in organic field-effect transistors, significantly outperforming TPBNA and all the reported BN-PAHs. Remarkably, this is the first BN-PAH with mobility over 1 cm 2  V -1  s -1 , which is a benchmark value for practical applications as compared with amorphous silicon. Furthermore, high-performance phototransistors based on DPBNA are also demonstrated, implying the high potential of BN-PAHs for optoelectronic applications when the "periphery engineering" strategy is implemented., (© 2022 Wiley-VCH GmbH.)

Strong interchain interactions of conjugated polymers usually result in poor miscibility with molecular dopants, limiting the doping efficiency because of uncontrolled phase separation. We have developed a strategy to achieve efficient charge-transport and high doping miscibility in n-doped conjugated polymers. We solve the miscibility issue through disorder side-chains containing dopants better. Systemic structural characterization reveals a farther side-chain branching point will lead to higher disorders, which provides appropriate sites to accommodate extrinsic molecular dopants without harming original chain packings and charge-transport channels. Therefore, better sustainability of solid-state microstructure is obtained, yielding a stable conductivity even when overloading massive dopants. This work highlights the importance of realizing high host-dopant miscibility in molecular doping of conjugated polymers., (© 2022 Wiley-VCH GmbH.)

Introducing BN units into polycyclic aromatic hydrocarbons expands the chemical space of conjugated materials with novel properties. However, it is challenging to achieve accurate synthesis of BN-PAHs with specific BN positions and orientations. Here, three new parent B 2 N 2 -perylenes with different BN orientations are synthesized with BN-naphthalene as the building block, providing systematic insight into the effects of BN incorporation with different orientations on the structure, (anti)aromaticity, crystal packing and photophysical properties. The intermolecular dipole-dipole interaction shortens the π-π stacking distance. The crystal structure, (anti)aromaticity, and photophysical properties vary with the change of BN orientation. The revealed BN doping effects may provide a guideline for the synthesis of BN-PAHs with specific stacking structures, and the synthetic strategy employed here can be extended toward the synthesis of larger BN-embedded PAHs with adjustable BN patterns., (© 2021 Wiley-VCH GmbH.)

The role of solution aggregates on the charge transport process of conjugated polymers in electronic devices has gained increasing attention; however, the correlation of the charge carrier mobilities between the solution aggregates and the solid-state films remains elusive. Herein, three polymers, FBDOPV-2T, FBDOPV-2F2T, and FBDOPV-4F2T, are designed and synthesized with distinct aggregation behavior in solution. By combining contact-free ultrafast terahertz (THz) spectroscopy and field-effect transistor measurements, we track the charge carrier mobility of the aggregates of these polymers from the solution to the thin-film state. Remarkably, the mobility of these three polymers is found to follow nearly the same trend (FBDOPV-2T>FBDOPV-2F2T≫FBDOPV-4F2T) in both solutions and thin-film states. The quantitative mobility correlation indicates that the charge transport properties of solution aggregates play a critical role in determining the thin-film charge transport properties and final device performance. Our results highlight the importance of investigating and controlling solution aggregation structures towards efficient organic electronic devices., (© 2021 Wiley-VCH GmbH.)

Doping of polymeric semiconductors limits the miscibility between polymers and dopants. Although significant efforts have been devoted to enhancing miscibility through chemical modification, the electrical conductivities of n-doped polymeric semiconductors are usually below 10 S cm -1 . We report a different approach to overcome the miscibility issue by modulating the solution-state aggregates of conjugated polymers. We found that the solution-state aggregates of conjugated polymers not only changed with solvent and temperature but also changed with solution aging time. Modulating the solution-state polymer aggregates can directly influence their solid-state microstructures and miscibility with dopants. As a result, both high doping efficiency and high charge-carrier mobility were simultaneously obtained. The n-doped electrical conductivity of P(PzDPP-CT2) can be tuned up to 32.1 S cm -1 . This method can also be used to improve the doping efficiency of other polymer systems (e.g. N2200) with different aggregation tendencies and behaviors., (© 2021 Wiley-VCH GmbH.)

Molecular doping plays an important role in the modification of carrier density of organic semiconductors thus enhancing their optoelectronic performance. However, efficient n-doping remains challenging, especially owing to the lack of strongly reducing and air-stable n-dopants. Herein, an N-heterocyclic carbene (NHC) precursor, DMImC, is developed as a thermally activated n-dopant with the excellent stability in air. Its thermolysis in situ regenerates free NHC and subsequently dopes typical organic semiconductors. In sequentially doped FBDPPV films, DMImC does not disturb the π-π packing of the polymer and achieves good miscibility with the polymer. As a result, a high electrical conductivity of up to 8.4 S cm -1 is obtained. Additionally, the thermally activated doping and the excellent air stability permit DMImC to be noninteractively co-processed with polymers in air. Our results reveal that DMImC can be served as an efficient n-dopant suitable for various organic semiconductors., (© 2020 Wiley-VCH GmbH.)

Conjugated polymers usually form crystallized and amorphous regions in the solid state simultaneously, making it difficult to accurately determine their precise microstructures. The lack of multiscale microstructures of conjugated polymers limits the fundamental understanding of the structure-property relationships in polymer-based optoelectronic devices. Here, crystals of two typical conjugated polymers based on four-fluorinated benzodifurandione-based oligo(p-phenylene vinylene) (F 4 BDOPV) and naphthalenediimide (NDI) motifs, respectively, are obtained by a controlled self-assembly process. The strong diffractivity of the polymer crystals brings an opportunity to determine the crystal structures by combining X-ray techniques and molecular simulations. The precise polymer packing structures are useful as initial models to evaluate the charge transport properties in the ordered and disordered phases. Compared to the spin-coated thin films, the highly oriented polymer chains in crystals endow higher mobilities with a lower hopping energy barrier. Microwire crystal transistors of F 4 BDOPV- and NDI-based polymers exhibit high electron mobilities of up to 5.58 and 2.56 cm 2  V -1  s -1 , respectively, which are among the highest values in polymer crystals. This work presents a simple method to obtain polymer crystals and their precise microstructures, promoting a deep understanding of molecular packing and charge transport for conjugated polymers., (© 2021 Wiley-VCH GmbH.)

High-spin conjugated radicals have great potential in magnetic materials and organic spintronics. However, to obtain high-spin conjugated radicals is still quite challenging due to their poor stability. We report the successful synthesis and isolation of a stable triplet conjugated diradical, 10,12-diaryldiindeno[1,2-b:2',1'-e]pyrazine (m-DIP). With the m-xylylene analogue skeleton containing electron-deficient sp 2 -nitrogen atoms, m-DIP displays significant aromatic character within its pyrazine ring and its spin density mainly delocalizes on the meta-pyrazine unit, making it a triplet ground state conjugated diradical. Our work provides an effective "spin density tuning" strategy for stable high-spin conjugated radicals., (© 2020 Wiley-VCH GmbH.)

Solution-processable highly conductive polymers are of great interest in emerging electronic applications. For p-doped polymers, conductivities as high a nearly 10 5 S cm -1 have been reported. In the case of n-doped polymers, they often fall well short of the high values noted above, which might be achievable, if much higher charge-carrier mobilities determined could be realized in combination with high charge-carrier densities. This is in part due to inefficient doping and dopant ions disturbing the ordering of polymers, limiting efficient charge transport and ultimately the achievable conductivities. Here, n-doped polymers that achieve a high conductivity of more than 90 S cm -1 by a simple solution-based co-deposition method are reported. Two conjugated polymers with rigid planar backbones, but with disordered crystalline structures, exhibit surprising structural tolerance to, and excellent miscibility with, commonly used n-dopants. These properties allow both high concentrations and high mobility of the charge carriers to be realized simultaneously in n-doped polymers, resulting in excellent electrical conductivity and thermoelectric performance., (© 2020 Wiley-VCH GmbH.)

In the past few decades, conjugated polymers have aroused extensive interest in organic electronic applications. The electrical performance of conjugated polymers has a close relationship with their backbone conformation. The conformation of the polymer backbone strongly affects the πelectron delocalization along polymer chains, the energy band gap, interchain interactions, and further affects charge transport properties. To realize a rigid coplanar backbone that usually possesses efficient intrachain charge transport properties and enhanced π-π stackings, such conformation control becomes a useful strategy to achieve high-performance (semi)conducting polymers. This minireview summarizes the most important polymer structures through conformation control at the molecular level, and then divides these rigid coplanar conjugated polymers into three categories: 1) noncovalent interactions locked conjugated polymers; 2) double-bond linked conjugated polymers; 3) ladder conjugated polymers. The effect of the conformation control on physical nature, optoelectronic properties, and their device performance is also discussed, as well as the challenges of chemical synthesis and structural characterization., (© 2020 Wiley-VCH GmbH.)

Controlling the solution-state aggregation of conjugated polymers for producing specific microstructures remains challenging. Herein, a practical approach is developed to finely tune the solid-state microstructures through temperature-controlled solution-state aggregation and polymer crystallization. High temperature generates significant conformation fluctuation of conjugated backbones in solution, which facilitates the polymer crystallization from solvated aggregates to orderly packed structures. The polymer films deposited at high temperatures exhibit less structural disorders and higher electron mobilities (up to two orders of magnitude) in field-effect transistors, compared to those deposited at low temperatures. This work provides an effective strategy to tune the solution-state aggregation to reveal the relationship between solution-state aggregation and solid-state microstructures of conjugated polymers., (© 2020 Wiley-VCH GmbH.)

Over the past three decades, the mobility of organic field-effect transistors (OFETs) has been improved from 10 -5 up to over 10 cm 2 V -1 s -1 , which reaches or has already satisfied the requirements of demanding applications. However, pronounced nonideal behaviors in current-voltage characteristics are commonly observed, which indicates that the reported mobilities may not truly reflect the device properties. Herein, a comprehensive understanding of the origins of several observed nonidealities (downward, upward, double-slope, superlinear, and humped transfer characteristics) is summarized, and how to extract comparatively reliable mobilities from nonideal behaviors in OFETs is discussed. Combining an overview of the ideal and state-of-the-art OFETs, considerable possible approaches are also provided for future OFETs., Competing Interests: The authors declare no conflict of interest., (© 2019 The Authors. Published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.)

Low n-doping efficiency and inferior stability restrict the thermoelectric performance of n-type conjugated polymers, making their performance lag far behind of their p-type counterparts. Reported here are two rigid coplanar poly(p-phenylene vinylene) (PPV) derivatives, LPPV-1 and LPPV-2, which show nearly torsion-free backbones. The fused electron-deficient rigid structures endow the derivatives with less conformational disorder and low-lying lowest unoccupied molecular orbital (LUMO) levels, down to -4.49 eV. After doping, two polymers exhibited high n-doping efficiency and significantly improved air stability. LPPV-1 exhibited a high conductivity of up to 1.1 S cm -1 and a power factor as high as 1.96 μW m -1  K -2 . Importantly, the power factor of the doped LPPV-1 thick film degraded only 2 % after 7 day exposure to air. This work demonstrates a new strategy for designing conjugated polymers, with planar backbones and low LUMO levels, towards high-performance and potentially air-stable n-type polymer thermoelectrics., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Considerable efforts have been devoted to achieving stable acene derivatives for electronic applications; however, the instability is still a major issue for such derivatives. To achieve higher stability with minimum structural change, CC units in the acenes were replaced with isoelectronic BN units to produce a novel BN-embedded tetrabenzopentacene (BNTBP). BNTBP, with a planar structure, is highly stable to air, moisture, light, and heat. Compared with its carbon analogue tetrabenzopentacene (TBP), BN embedment lowered the highest occupied molecular orbital (HOMO) energy level of BNTBP, changed the orbital distribution, and decreased the HOMO orbital coefficients at the central carbon atoms, which stabilize BNTBP molecules upon exposure to oxygen and sunlight. The single-crystal microribbons of BNTBP exhibited good performance in field-effect transistors (FETs). The high stability and good mobility of BNTBP indicates that BN incorporation is an effective approach to afford stable large-sized acenes with desired properties., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The joint of the donor and acceptor moieties allows a facile and effective strategy to develop novel organic conjugated materials. However, few pieces of work report the understanding of the donor-acceptor interactions at the molecular level. Herein, we developed three small molecules containing one acceptor motif with different amounts of the donor unit. By combining theoretical calculations and energy level characterization, the lowest unoccupied molecular orbital (LUMO) levels of the three molecules were proven to be almost identical. The molecular packing modes were evaluated from crystal structure prediction. Owing to the donor-acceptor interactions, the packing mode can be tuned from a 1D slipped stacking to a 2D brick layer. The 2D molecular packing and charge transport channel endowed the materials a higher electron mobility of 3.29 cm 2  V -1  s -1 in the single-crystal field-effect transistors after such modulation., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Wafer-scale fabrication of high-performance uniform organic electronic materials is of great challenge and has rarely been realized before. Previous large-scale fabrication methods always lead to different layer thickness and thereby poor film and device uniformity. Herein, the first demonstration of 4 in. wafer-scale, uniform, and high-performance n-type polymer monolayer films is reported, enabled by controlling the multi-level self-assembly process of conjugated polymers in solution. Since the self-assembly process happened in solution, the uniform 2D polymer monolayers can be facilely deposited on various substrates, and theoretically without size limitations. Polymer monolayer transistors exhibit high electron mobilities of up to 1.88 cm 2 V -1 s -1 , which is among the highest in n-type monolayer organic transistors. This method allows to easily fabricate n-type conjugated polymers with wafer-scale, high uniformity, low contact resistance, and excellent transistor performance (better than the traditional spin-coating method). This work provides an effective strategy to prepare large-scale and uniform 2D polymer monolayers, which could enable the application of conjugated polymers for wafer-scale sophisticated electronics., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Conjugated polymers with high thermoelectric performance enable the fabrication of low-cost, large-area, low-toxicity, and highly flexible thermoelectric devices. However, compared to their p-type counterparts, n-type polymer thermoelectric materials show much lower performance, which is largely due to inefficient doping and a much lower conductivity. Herein, it is reported that the development of a donor-acceptor (D-A) polymer with enhanced n-doping efficiency through donor engineering of the polymer backbone. Both a high n-type electrical conductivity of 1.30 S cm -1 and an excellent power factor (PF) of 4.65 µW mK -2 are obtained, which are the highest reported values among D-A polymers. The results of multiple characterization techniques indicate that electron-withdrawing modification of the donor units enhances the electron affinity of the polymer and changes the polymer packing orientation, leading to substantially improved miscibility and n-doping efficiency. Unlike previous studies in which improving the polymer-dopant miscibility typically resulted in lower mobilities, the strategy maintains the mobility of the polymer. All these factors lead to prominent enhancement of three orders magnitude in both the electrical conductivity and the PF compared to those of the non-engineered polymer. The results demonstrate that proper donor engineering can enhance the n-doping efficiency, electrical conductivity, and thermoelectric performance of D-A copolymers., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Organic field-effect transistors (OFETs) with impressively high hole mobilities over 10 cm 2 V -1 s -1 and electron mobilities over 1 cm 2 V -1 s -1 have been reported in the past few years. However, significant non-ideal electrical characteristics, e.g., voltage-dependent mobilities, have been widely observed in both small-molecule and polymer systems. This issue makes the accurate evaluation of the electrical performance impossible and also limits the practical applications of OFETs. Here, a semiconductor-unrelated, charge-trapping-induced non-ideality in OFETs is reported, and a revised model for the non-ideal transfer characteristics is provided. The trapping process can be directly observed using scanning Kelvin probe microscopy. It is found that such trapping-induced non-ideality exists in OFETs with different types of charge carriers (p-type or n-type), different types of dielectric materials (inorganic and organic) that contain different functional groups (OH, NH 2 , COOH, etc.). As fas as it is known, this is the first report for the non-ideal transport behaviors in OFETs caused by semiconductor-independent charge trapping. This work reveals the significant role of dielectric charge trapping in the non-ideal transistor characteristics and also provides guidelines for device engineering toward ideal OFETs., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Polymer self-assembly in solution prior to film fabrication makes solution-state structures critical for their solid-state packing and optoelectronic properties. However, unraveling the solution-state supramolecular structures is challenging, not to mention establishing a clear relationship between the solution-state structure and the charge-transport properties in field-effect transistors. Here, for the first time, it is revealed that the thin-film morphology of a conjugated polymer inherits the features of its solution-state supramolecular structures. A "solution-state supramolecular structure control" strategy is proposed to increase the electron mobility of a benzodifurandione-based oligo(p-phenylene vinylene) (BDOPV)-based polymer. It is shown that the solution-state structures of the BDOPV-based conjugated polymer can be tuned such that it forms a 1D rod-like structure in good solvent and a 2D lamellar structure in poor solvent. By tuning the solution-state structure, films with high crystallinity and good interdomain connectivity are obtained. The electron mobility significantly increases from the original value of 1.8 to 3.2 cm 2 V -1 s -1 . This work demonstrates that "solution-state supramolecular structure" control is critical for understanding and optimization of the thin-film morphology and charge-transport properties of conjugated polymers., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A new electron-deficient unit with a fused 5-membered heterocyclic ring was developed by replacing a cyclopenta-1,3-diene from electron-rich donor indacenodithiophene (IDT) with a cyclohepta-4,6-diene-1,3-diimde unit. The imide bridge endows dithienylbenzenebisimide (BBI) with a fixed planar configuration and low energy levels for both the highest occupied molecular orbital (HOMO; -6.24 eV) and the lowest unoccupied molecular orbit (LUMO; -2.57 eV). Organic field-effect transistors (OFETs) based on BBI polymers exhibit electron mobility up to 0.34 cm 2  V -1  s -1 , which indicates that the BBI is a promising n-type building block for optoelectronics., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Planar backbone, locked conformation, and low lowest unoccupied molecular orbital level provide polymer F4 BDOPV-2T with ultrahigh electron mobilities of up to 14.9 cm(2) V(-1) s(-1) and good air stability. It is found that the nonlinear transfer curves can be tuned to near-ideal ones by changing fabrication conditions, indicating that film morphology largely contributes to the nonlinear transfer curves in high-mobility conjugated polymers., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A strong, electron-deficient small molecule, F4 -BDOPV, has a lowest unoccupied molecular orbital (LUMO) level down to -4.44 eV and exhibits cofacial packing in single crystals. These features provide F4 -BDOPV with good ambient stability and large charge-transfer integrals for electrons, leading to a high electron mobility of up to 12.6 cm(2) V(-1) s(-1) in air., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

New BN-embedded, thiophene-fused, polycyclic aromatic compounds with planar geometry were designed and synthesized. The molecules showed excellent stability and chemical robustness. Postfunctionalization on this skeleton was demonstrated with a series of electrophilic bromination, palladium-catalyzed cross-coupling, and Knoevenagel condensation reactions. The π skeleton remained intact during these late-stage transformations. The optical and electronic properties have been well tuned through incorporation of electron-rich and -deficient groups on the backbone. This work shows the great advantage of the postfunctionalization strategy on BN-containing polycyclic aromatic compounds for fast diversification and materials screening., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Replacement of C=C unit with its isoelectronic B-N unit in aromatics provides a new class of molecules with appealing properties, which have attracted great attention recently. In this Concept, we focus on BN-substituted polycyclic aromatics with fused structures, and review their synthesis, photophysical, and redox properties, as well as their applications in organic electronics. We also present challenging synthetic targets, large BN- substituted polycyclic aromatics, such as regioregular BN heterosuperbenzenes, which can be viewed as BN-doped nanographenes. Finally, we propose an atomically precise bottom-up synthesis of structurally well-defined BN-doped graphenes., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Two functional main-chain linear polyrotaxanes, one a covalent polymeric chain that threads through many macrocycles (P1) and the other a poly[n]rotaxane chain that is composed of many repeating rotaxane units (P2), were synthesized by employing strong crown-ether/ammonium-based (DB24C8/DBA) host-guest interactions and click chemistry. Energy transfer between the wheel and axle units in both polyrotaxanes was used to provide insight into the conformational information of their resulting polyrotaxanes. Steady-state and time-resolved spectroscopy were performed to understand the conformation differences between polymers P1 and P2 in solution. Additional investigations by using dynamic/static light scattering and atomic force microscopy illustrated that polymer P1 was unbending and had a rigid rod-like structure, whilst polymer P2 was curved and flexible. This flexible topology facilitated the self-assembly of polymer P2 into relatively large ball-shaped particles. In addition, the energy transfer between the wheel and axle units was controlled by the addition of specific anions or base. The anion-induced energy enhancement was attributed to a change in electrostatic interactions between the polymer chains. The base-driven molecular shuttle broke the DB24C8/DBA host-guest interactions. These results confirm that both intra- and intermolecular electrostatic interactions are crucial for modulating conformational topology, which determines the assembly of polyrotaxanes in solution., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Over the past few years, two-dimensional (2D) nanoporous networks have attracted great interest as templates for the precise localization and confinement of guest building blocks, such as functional molecules or clusters on the solid surfaces. Herein, a series of two-component molecular networks with a 3-fold symmetry are constructed on graphite using a truxenone derivative and trimesic acid homologues with carboxylic-acid-terminated alkyl chains. The hydrogen-bonding partner-recognition-induced 2D crystallization of alkyl chains makes the flexible alkyl chains act as rigid spacers in the networks to continuously tune the pore size with an accuracy of one carbon atom per step. The two-component networks were found to accommodate and regulate the distribution and aggregation of guest molecules, such as COR and CuPc. This procedure provides a new pathway for the design and fabrication of molecular nanostructures on solid surfaces., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The binary self-assembly of copper phthalocyanine (CuPc) and 2,3,7,8,12,13-hexahexyloxy-truxenone (TrO23) at the solid/liquid interface of highly oriented pyrolytic graphite (HOPG) was investigated by using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). Pseduohexagonal and linear patterned superstructures of CuPc are obtained by co-adsorbing with TrO23. High-resolution STM images reveal the structural details of the arrangement of TrO23 and CuPc in the binary assembly structures. The molecular ratio between CuPc and TrO23 in the adlayer can be modulated by the CuPc concentration in liquid phase. The electronic properties of CuPc and TrO23 in the co-adsorbed self-assembly are investigated by STS. The results presented here are helpful to the design and fabrication of multi-component functional molecular nanostructures., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A mechanically interlocked light-harvesting system [3]rotaxane A has been synthesized in high yield through Cu(I)-catalyzed azide-alkyne cycloaddition; the hexyl-substituted truxene units are introduced into the wheels as donors and an oligo(para-phenylenevinylene) (OPV) unit into the axis as the acceptor. The structure and the purity of [3]rotaxane A were confirmed by (1)H and (13)C NMR spectroscopy and ESI HRMS. The azide-alkyne cycloaddition is demonstrated to be an efficient stoppering method in the synthesis of the rotaxane containing dibenzo[24]crown-8 and dibenzyl ammonium units. Detailed steady-state UV/Vis absorption, photoluminescent, and time-resolved fluorescence spectroscopy were performed to investigate the photophysical properties of [3]rotaxane A and its reference compounds in solution and as thin films. Even in dilute solution, efficient energy transfer from the truxene-functionalized wheels to the OPV-based axis, through the dibenzo[24]crown-8 and dibenzyl ammonium interaction, is observed in [3]rotaxane A. The unique topology of [3]rotaxane A not only efficiently promotes the intramolecular energy-transfer process, but also prevents intermolecular aggregation in the solid state. The new antenna system opens up the possibility of controllable light-harvesting molecular machines or other optoelectronic devices on the nanometer scale.