Two acceptor-donor-acceptor (A-D-A) type of hydrogen bonded thiophene azomethine building blocks, TTAZ and BTAZ, were synthesized. Both compounds incorporated the electron-withdrawing unit 3-cyanothiophene, with the electron-rich moieties consisting of carbamate functionalized thieno[3,2-b]thiophene for TTAZ and carbamate functionalized 2,2'-bithiophene for BTAZ, respectively. The corresponding polymer PTTAZ and PBTAZ were synthesized via Stille cross-coupling reaction. Although the absorption spectra of the two polyazomehines exhibited distinct aggregation behaviors, both showed broad full width at half maximum (FWHM) and similar electrochemical energy levels. Organic field-effect transistors (OFETs) fabricated using PTTAZ and PBTAZ as electroactive layers demonstrated p-type charge transport characteristic, with maximum hole mobility of 4.32 x 10-3 for PTTAZ and 3.64 x 10-3 cm2 V- 1 s- 1 for PBTAZ. The microstructures of the polymer thin films were further analyzed using atomic force microscope (AFM) and two-dimensional grazing incidence wide-angle X-ray scattering (2D-GIWAXS).

We report two model compounds, TTPY and BTPY, which feature resonance-assisted hydrogen bonds (RAHBs) formed between carbamate-functionalized thieno[3,2-b]thiophene or 2,2'-bithiophene cores and flanking pyridine units. Single-crystal structure analysis reveals that moderate RAHBs run along the long axis, whereas weaker noncovalent interactions (e.g., S···O and O···H) are present along the short axis. The synergetic effect of these interactions imparts a rigid, coplanar structure to both TTPY and BTPY. Both computational and experimental studies indicate that RAHBs stabilize the planar molecular conformation through an enthalpic effect, with stabilization energies exceeding 10 kcal mol-1. The formation of these RAHBs is also entropically favorable, which ensures the stability of the planar conformation at elevated temperatures. Both single crystals adopt a one-dimensional layered stacking mode, and TTPY exhibits closer π-π stacking compared to BTPY. Consequently, TTPY-based organic field-effect transistors (OFETs) show optimal charge transport performance, achieving a maximum hole mobility of 0.035 cm2 V-1 s-1, which is slightly higher than that of BTPY-based devices (0.026 cm2 V-1 s-1). Thin film microstructural characterization confirms that TTPY possesses higher crystallinity and greater structural order, accounting for its superior device performance.

Organic field-effect transistors (OFETs) is the basic unit of complementary logic circuit, however, the development of n-type OFETs lags behind of p-type ones due to the barrier of electron injection and the interference from oxygen and water, which hinders the development of complementary logic circuit. Therefore, the design and synthesis of high-performance n-type organic semiconductors and the improvement of device performance and stability have important scientific significance. In this work, a novel naphthalene diimide (NDI)-vinylogous tetrathiafulvalene derivative (BDTNDIDTYA)(2) was designed and synthesized via a pi-expanded strategy by fusing the benzene-1,2-dithiol (BDT) and 2-(1,3-dithiol-2-ylidene) acetonitrile (DTYA) moieties onto the NDI core. The chemical structure of the compound was characterized by H-1 NMR, C-13 NMR, Fourier transform infrared spectroscopy (FT-IR) and high-resolution mass spectrometry (HRMS). The thermal, optical and electrochemical properties of (BDTNDI-DTYA)(2) were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), ultraviolet-visible (UV-Vis) absorption spectra and cyclic voltammetry (CV). The energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of (BDTNDI-DTYA)(2) calculated from CV were -5.66 and -4.01 eV, respectively. The edge absorption of (BDTNDI-DTYA)(2) in thin film showed obvious red-shift (68 nm) relative to that in CHCl3 solution, indicating strong intermolecular interactions in solid state. The bottom-gate and top-contact (BGTC) OFETs based on (BDTNDI-DTYA)2 fabricated by spin-coating method, showed n-type electron transporting characteristics. The average electron mobility of the untreated devices was 0.04 cm(2)center dot V-1 center dot s(-1) when measured in nitrogen atmosphere and was increased of up to 1.00 cm(2) center dot V-1 center dot s(-1) when the thin films of (BDTNDI-DTYA)2 were thermal annealed at 160 degree celsius. On the other hand, azulene was used as an additive to treat the thin films of (BDTNDI-DTYA)2 via sublimation, the average electron mobility of OFETs was increased to 0.98 cm(2)center dot V-1 center dot s(-1). The effect of thermal annealing treatment and azulene-treatment on the performance of (BDTNDIDTYA)(2)-based OFETs were investigated by UV-Vis absorption spectra, atomic force microscopy (AFM) and X-ray diffraction (XRD). For UV-Vis absorption spectra of thin films of (BDTNDI-DTYA)(2), after thermal annealing at 160 degree celsius and azulene-treatment, the absorption peak in long-wavelength was enhanced and widened relative to that of the untreated thin films with obvious shoulder peaks and red-shifts (35 and 39 nm, respectively). The AFM and XRD results indicated that the improvement of device performance originated from the improved (BDTNDI-DTYA)(2) thin film crystallinity and morphology. In this work, a pi-expanded NDI-vinylogous tetrathiafulvalene derivative as n-type organic semiconductor was designed and synthesized, and azulene was used for the first time to effectively regulated the structure and morphology of the active layer of OFETs, which both provide new insights for development of novel organic semiconductors and their high performance OFET devices.

New heteroaromatic azomethine building blocks with multiple hydrogen bonds have been synthesized for degradable π-conjugated polymers. The hydrogen bonds ensured the planarity of the building blocks, therefore enhanced π-conjugation. Two π-conjugated polymers of PPD and PTDD based on the building blocks were also synthesized. The organic field effect transistors (OFETs) based on PPD displayed a balanced ambipolar charge carrier transport, and the maximum hole/electron mobility were 0.08/0.14 cm2 V-1 s-1. While the OFETs based on PTDD exhibited a n-type dominant ambipolar charge transport, with the maximum hole/electron mobility of 6.0 × 10-4/3.8 × 10-3 cm2 V-1 s-1. The microstructures of the polymer thin films were studied by two-dimensional grazing incidence wide-angle X-ray scattering (2D-GIWAXS). The π-conjugated polyazomethines were stable in ambient and can be degraded in acidic solutions. The main degradation products of the polymers were also identified.

In comparison with the combination of p- and n-type organic semiconductors, the way to construct logic complementary circuits by ambipolar organic semiconductors has obvious advantages. However, so far, the ambipolar ones with high performance are still scarce. In this work, a series of benzo six-membered nitrogen/oxygen/sulfur heterocycles core-substituted naphthalene diimides-vinylogous tetrathiafulvalene (NDI-VTTF) derivatives 1 similar to 5 were designed by energy level regulation strategy. Subsequently, bottom-gate and top-contact organic field-effect transistors (OFETs) based on compounds 1 similar to 5 were fabricated and systematically studied. The results showed that all the OFET devices exhibit ambipolar semiconducting behaviors, among them the OFET devices based on compounds 1 , 3 similar to 5 displayed electron-dominated ambipolar charge transport characteristics, while the devices based on compound 2 showed balanced ambipolar charge transport features. Due to the improvement of thin-film crystallinity and morphology by thermal annealing treatment, the performance of OFETs based on compounds 1 similar to 5 was improved with the increase of thermal annealing temperature. When thermal annealed at 180 degrees C, OFETs based on compound 2 showed the balanced electron and hole mobilities of up to 0.037 and 0.050 cm(2)center dot V-1 center dot s(-1), respectively.

Azulene has aroused widespread interest for constructing optoelectronic materials. However, controlling the dipole orientation of 2,6-azulene units in the conjugated polymer backbone is a significant challenge so far. Herein, by C-H activation strategy, three 2,6-azulene-TPD-based conjugated copolymers with different dipole arrangements were synthesized, where TPD = thieno[3,4-c]pyrrole-4,6-dione. The dipole arrangements of 2,6-azulene units were random for P(AzTPD-1), head-tohead/tail-to-tail for P(AzTPD-2), and head-to-tail for P(AzTPD3). These polymers exhibited unipolar n-type semiconductor characteristics in organic field effect transistors. Moreover, regioregular polymer P(AzTPD-3) displayed the best device performance with an electron mobility of up to 0.33 cm2 V-1 s-1, which makes P(AzTPD-3) a high-performance n-type polymeric semiconductor. These results demonstrate that incorporation of 2,6-azulene units into the polymeric backbone together with the regulation of the dipole orientation of 2,6-azulene units is an effective strategy for obtaining high-performance organic optoelectronic materials.

Azulene has attracted significant attention for constructing novel optoelectronic materials. Tuning the dipole orientation of azulene unit in azulene-based conjugated polymers has recently aroused widespread concern and remains a great challenge due to the lack of synthetic method. Herein, we report three 2,6-azulene and 3,4-propylenedioxythiophene (ProDOT) based conjugated copolymers P(AzProDOT-1), P(AzProDOT-2) and P(AzProDOT-3) with different dipole arrangements of azulene moieties. The regioregularity of these 2,6-azulene-ProDOT-based conjugated polymers was tuned by monomer design and direct arylation polymerization strategy, which enables a thorough study of the impact of the regioregularity on the properties of these polymers and their charge transport performance. The dipole orientation of 2,6-azulene units were regiorandom for P(AzProDOT-1), regularity with medium regioregularity for P(AzProDOT-2) and regularity with high regioregularity for P(AzProDOT-3), respectively. The number-average molecular weight values of P(AzProDOT-1), P(AzProDOT-2) and P(AzProDOT-3) estimated by gel permeation chromatography (GPC) were 11.1, 11.4 and 9.3 kDa, respectively, and the chemical structures of these three polymers were also characterized by high-temperature 1H NMR spectra. Ultraviolet-visible (UV-vis) absorption spectra and cyclic voltammetry were conducted to evaluate the optoelectronic properties of these polymers. The blue-shift of the maximum absorption peak for P(AzProDOT-2) indicates its twisted polymer backbone and short effective p-conjugation length, while the red-shift of the maximum absorption peak for P(AzProDOT-3) demonstrates the more planar conjugated skeleton and the longer effective p-conjugation length, although its molecular weight was a little lower. Besides, there was a prominent shoulder peak in the thin film of P(AzProDOT-3) in UV-vis absorption spectrum, indicating the stronger interchain interactions in solid state. All these observations were in agreement with the density functional theory (DFT) calculation results. Due to the electron-donating property of ProDOT, these three polymers displayed strong and sensitive proton responsiveness. The ultraviolet-visible-near infrared (UV-vis-NIR) spectra of these three polymers showed obvious red-shifts (>150 nm) upon protonation, and the films of these polymers also possess strong proton responsiveness properties. Charge-carrier mobilities of these three polymers were measured by the space-charge-limited current (SCLC). The hole mobilities of thin films of P(AzProDOT-1), P(AzProDOT-2) and P(AzProDOT-3) were 1.32x10(-5), 9.14x10(-5) and 1.41x10(-4) cm(2).V-1.s(-1), respectively, and their electron mobilities were 1.62x10(-6), 7.91x10(-6) and 1.66x10-5 cm(2).V-1.s(-1), respectively. The atomic force microscopy (AFM) study demonstrated that the thin film of P(AzProDOT-3) possessed the smoothest surface and the smallest root mean square (RMS) roughness,

Comprehensive Summary Organic semiconductors have drawn extensive attention due to their optoelectronic properties and wide applications in organic optoelectronics. In comparison with the popular 1,4,5,8‐naphthalene diimides (1,4,5,8‐NDIs), the angular‐shaped 1,2,5,6‐NDIs have exhibited tunable photophysical properties, self‐assembly behaviors and charge transporting properties. Due to these unique features, 1,2,5,6‐NDIs show great potential for construction of high performance π‐functional materials. In this review, we highlight the recent advances and future prospects of 1,2,5,6‐NDI‐based π‐systems in the field of organic optoelectronics, including molecular design, synthesis, structure‐property relationships as well as the applications in high performance organic field‐effect transistors, organic photovoltaics, perovskite solar cells, and so on. What is the most favorite and original chemistry developed in your research group? Chemistry of π‐functional materials by using naphthalene and azulene as the basic structural units. How do you get into this specific field? Could you please share some experiences with our readers? This comes from my previous research experience, independent thinking and academic exchange & discussion. When I was a PhD student, my research topic focused on p‐type organic semiconductors. Since I independently carried out scientific research, my research interest turned to developing more challenging n‐type organic semiconductors by using core‐expanded 1,4,5,8‐naphthalene diimides (NDIs). Later on, 1,2,5,6‐NDIs as high‐performance organic semiconductors, the topic of this review paper, entered our study perspective based on the concept of isomerism. Also, based on the concept of isomerism and academic discussion, azulene, the isomer of naphthalene with unique chemical structure and physicochemical properties, became the dominant building block for constructing novel π‐functional materials in my group. How do you supervise your students? Select a research topic with scientific significance and certain challenges, let students consult and intensively read relevant literatures and obtain research inspiration, basic knowledge, experimental skills, writing skills, etc . Encourage students to think independently, try more, and pay more attention to communication and cooperation. Fully train students to write research papers independently. The last but not the least, advocate the academic spirit of being innovative, pursuing excellence as well as rigorous scholarship. What is the most important personality for scientific research? Curiosity and perseverance. What are your hobbies? Reading and walking. If you have anything else to tell our readers, please feel free to do so. No one can imprison your mind and hold your hand to prevent you from doing research work, follow your heart to do what you like and different from others.

A class of nonbenzenoid analogues of poly-(p-phenylenevinylene)-s (PPVs), 2,6-azulene-vinyl-based conjugated polymers (CPs) r -PAzV, hhtt -PAzV, and ht -PAzV, have been reported with different dipole arrangements of azulene units, where the five-membered ring and seven-membered ring of azulene core are defined as "head (H)" and "tail (T)", respectively. The PAzV polymers exhibit diverse backbone structures, proton responsiveness, an unusual relationship between crystallinity and regioregularity relative to conventional CPs, and balanced ambipolar charge transport. In regiorandom r -PAzV, the proportions of the H-T, H-H, and T-T linkages are about 40, 20, and 40%, respectively. The studies on solubility, thermal/optical properties, and microstructures of these PAzV polymers reveal that the presence of H-H and T-T arranged moieties in r -PAzV and hhtt -PAzV strengthens interchain interactions. Grazing-incidence wide-angle X-ray scattering measurements demonstrate enhanced long-range order with up to four orders of side-chain stacking reflections in as-spun films of r -PAzV and hhtt -PAzV. Williamson-Hall and Scherrer's analyses indicate that the lamellar crystallites in films of ht -PAzV have a much smaller size and lower crystallite quality relative to r -PAzV and hhtt -PAzV. Therefore, organic thin-film transistors based on r -PAzV and hhtt -PAzV display 2-4 orders higher charge carrier mobilities than those of ht -PAzV-based devices. The poor device performance of ht -PAzV might be attributed to the gradient electrostatic potential distribution and localized distribution of the Frontier molecular orbitals of the main chain. Our work enriches the family of PPV-like polymers, achieves the regulation of dipole arrangements of 2,6-azulene units together with clear structural analysis, and discloses that the dipole arrangements of azulene units along the polymer backbone have a great influence on the assembly of polymer chains.

A novel air-stable n-type benzothiaphene endcapped azaarene (BTPQ ) and its sulfonated derivative (BSPQ) were prepared via two pathways and characterized by NMR, UV-vis, fluorescence and cyclic voltammetry spectroscopy. Symmetrically introducing four nitrogen atoms into acenes, the semiconductor properties could be changed from p-type to n-type detected through the space charge limited current (SCLC) method. After sulfonation of BTPQ , BSPQ is with deeper frontier orbital energy levels and enhanced the electron mobility.(c) 2022 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

A novel class of π-extended 11-ring-fused linear thienoacenes (BBDTB-H, BBDTB-TIPS, and BBDTB-Br) with four thieno[3,2- b ;4,5- b ′]dithiophenes and three benzene rings were synthesized and fully characterized.

Azulene-based homopolymers are of great interest from the point view of chemistry and material science. Herein, by means of Friedel-Crafts acylation to introduce solubilizing chains on the 1-position of azulene, we designed and synthesized two examples of 2,6-azulene-based homopolymers RP(Az-AC16) and P(Az-AC16). The arrangement of 2,6-azulene units is irregular for RP(Az-AC16), while P(Az-AC16) has head-to-head/tail-to-tail arranged 2,6-azulene units. Proton-responsive studies demonstrate that RP(Az-AC16) and P(Az-AC16) show reversible proton responsiveness in both solution and thin film. To utilize the dynamically reversible proton-responsive property of these polymers in thin films, RP(Az-AC16) and P(Az-AC16) were incorporated into a Nafion matrix as proton exchange membranes, wherein the Nafion/P(Az-AC16) composite membrane exhibits significant increases in proton conductivity relative to the Nafion membrane at different temperatures of each relative humidity (RH), which further results in a 64% improvement in hydrogen fuel cell output power under 30% RH at 80 °C. Our studies have realized the first solution synthesis of 2,6-azulene-based homopolymers and the first application of azulene-based π-systems in hydrogen fuel cells.

Conjugated polymers are considered as promising candidates for the use of electron transport layers (ETLs) to enhance both the device performance and stability of the inverted planar perovskite solar cells (PSCs). Therefor; constant efforts are dedicated to the design and evaluation of more efficient polymeric ETLs. Herein, two dithienochrysene diimide (DTCDI)-based polymers P(DTCDI-DTBT) and P(DTCDI-DTDFBT) have been synthesized by copolymerizing the DTCDI unit with 4,7-di(thiophen-2-yl)-benzo[c][1,2,5]thiadiazole (DTBT) and 4,7-di(thiophen-2-yl)-difluorobenzo[c][1,2,5]thiadiazole (DTDFBT) moieties, respectively, and explored as ETLs for inverted PSCs. It was found that the fluorinated polymer P(DTCDI-DTDFBT) exhibited lowest unoccupied molecular orbital energy levels similar to P(DTCDI-DTBT) but superior electron transport ability. Due to strong interaction between F atoms and the perovskite film, the better passivation effect and smaller charge transfer resistance can be revealed from the characterization of P(DTCDI-DTDFBT)-based devices when they were used as an ETL, and the inverted PSCs using P(DTCDI-DTDFBT) as the ETL showed a power conversion efficiency of 16.3%, much higher than that of P(DTCDI-DTBT)-based devices (11.8%). Moreover, the devices relying on P(DTCDI-DTDFBT) also demonstrated a considerable improvement in the stability of the PSC devices, retaining 87% of its initial performance after being exposed at an ambient environment for 168 h. This work indicates that fluorination could be an effective way for developing efficient polymeric ETLs to enhance the performance and stability of the inverted PSCs.

A series of electron-deficient conjugated polymers (P(DTCDI-T), P(DTCDI-2T) and P(DTCDI-3T)) are reported as effective ETLs for inverted PSCs, resulting in a champion power conversion efficiency (PCE) of 17.88% for P(DTCDI-2T) ETL based devices.

Atropisomerism has been studied in many research fields; however, it is rarely studied in organic semiconductors. In this work, we report a series of room-temperature-stable atropisomeric conjugated diimides, Syn-NDI and Anti-NDI based on 1,4,5,8-naphthalenetetracarboxylic diimides (NDIs) as well as Syn-PDI and Anti-PDI based on 3,4:9,10-perylenetetracarboxylic diimides (PDIs). For these two pairs of atropisomers, the Syn and Anti conformers can be interconverted when they are in heated solution, whereas in the solid state, only the Syn conformers can converted to Anti conformers when thermally annealed. This feature can be applied to realize thermally responsive organic field-effect transistors (OFETs). Remarkably, when thermally annealed at a certain temperature, the Syn atropisomers can be fast converted to their respective Anti ones, and OFETs originally based on the Syn semiconductors show a dramatic improvement in electron mobility. For OFETs originally based on Syn-NDI, a 100-fold improvement in electron mobility is recorded when Syn-NDI was converted to Anti-NDI, while for OFETs originally based on Syn-PDI, a 5000-fold improvement in electron mobility is recorded when Syn-PDI was converted to Anti-PDI. In contrast, thermal annealing is found to have a negligible effect for OFETs based on Anti semiconductors, with the electron mobility on the same order of magnitude for all Anti semiconductor devices. This is the first time that the atropisomerism has been exploited in organic semiconductors, demonstrating great potential for stimuli-responsive devices.

The 2,6-azulene unit is one of the most promising moieties for constructing organic conjugated materials. Herein, we reported the design and synthesis of 2,6-azulene-based conjugated copolymers P(AzIDT-C6), P(AzIDT-PhC6), and P-(AzIDTT-PhC6) containing electronrich indacenodithiophene (IDT) units. Because of the electronrich features of IDT moieties, all polymers can be easily protonated in both solution and solid state. The protonation states can reach saturation with as little as 0.5% volume ratio of trifluoroacetic acid in solution accompanied by a substantial red-shift (>250 nm) in the UV-vis-NIR absorption spectra, which is the most sensitive proton responsiveness among reported azulene-based polymers. The proton responsiveness of these polymers in thin films is shown to be dynamically reversible with the color changing between deep blue (neutral state) and colorless (protonated state) due to shifting of the absorption bands between the visible and near-infrared regions. Electron paramagnetic resonance experiments reveal that the protonated polymers can be further oxidized to form radical cations with strong EPR signals. A membrane containing 3 wt % P(AzIDTT-PhC6) in Nafion shows a 72.2% higher conductivity than Nafion at 125 degrees C and 0% relative humidity, implying the potential application of these polymers in polymer electrolyte membranes. Preliminary organic field-effect transistor studies suggest that all conjugated polymers investigated display typical p-channel transport behavior with hole mobilities up to 0.46 cm(2) V-1 s(-1), demonstrating that the 2,6-azulene-based conjugated copolymers can behave as p-type semiconducting materials. Our work indicates that the incorporation of electron-rich large pi-conjugated units into 2,6-azulene-based conjugated polymers is an effective strategy to develop highly sensitive proton-responsive materials and high-performance hole-transporting semiconductors.

Two poly(2,6-azuleneethynylene)s (PAzE-1 and PAzE-2) were designed and synthesized. The 2,6-azulene units are head-to-tail-arranged in PAzE-1, while there are three types of orientations of 2,6-azulene units in PAzE-2: head-to-tail, head-to head, and tail-to-tail segments, of which the head-to-tail one accounts for about 27% (determined from 1H NMR spectra). Such a structural distinction endows the two polymers with different absorption spectra in solution and aggregation states as well as different thin-film morphologies, microstructures, and field-effect transistor (FET) performances, suggesting that the dipole orientation of azulene units in a polymer backbone may be a critical issue that deserves careful consideration during the molecular design and synthesis. PAzE-1 with an ordered dipole orientation has stronger aggregation even in a very dilute solution (10-6 M). PAzE-2 films have a higher in-plane microstructural order and lower surface roughness than PAzE-1 films; hence, the PAzE-2-based transistor devices exhibit 1-2 orders higher hole and electron mobilities. Unlike typical p-type alkyl-substituted poly(p-phenyleneethynylene)s (PPEs), PAzE-1 and PAzE-2 are ambipolar semiconductors.

A hydrogen bonded pyridine-thieno[3,2- b ]thiophene-pyridine type building block TTPY has been synthesized for π-conjugated polymers and their application in organic electronic devices.

Azulene, one of representative nonbenzenoid aromatic hydrocarbons,exhibits unique molecular structure and distinctive physical and chemicalproperties. Herein, an azulene-based isoindigo analogue, azulenoisoindigo (AzII)is designed and synthesized, which has a twisted molecular backbone andR/S-isomers in single crystals. Interestingly, AzII shows the characteristics of both isoindigo and azulene, suchas completely reversible redox behavior and reversible proton responsiveness.UV-vis-NIR, 1H NMR and electron paramagnetic resonance (EPR)measurements were carried out to get insights into the possible mechanism ofthe proton-responsive property of AzII.The results demonstrated that only one azulenyl moiety of molecule of AzII was protonated and deprotonated,and the protonated AzII can befurther oxidized to form azulenium cation radicals.

Benzobisthiazole polymer with resonance-assisted hydrogen bonds (RAHBs) has been synthesized for both organic field-effect transistor and polymer solar cell applications. The properties of the hydrogen bonded polymer are compared with the reference polymer without RAHBs. Single-crystal X-ray diffraction analyses of the building block reveal that the RAHB interactions are formed between the carbamate hydrogen and imine nitrogen of the thiazoles. The hydrogen donor and acceptor are connected by π-conjugated molecular framework and the hydrogen-bridged quasi aromatic rings lock the conformation of the building block. The building block adopted a layered sandwich packing in crystal instead of slipped herringbone stacking which was often found in the crystal of benzobisthiazole derivatives. The polymer PCBTZ-TT with RAHBs showed deeper HOMO/LUMO energy level (about 0.2 eV) than reference polymer. The PCBTZ-TT demonstrated the hole mobility of 0.96 cm2·V−1·s−1 in field-effect transistor devices and achieved power conversion efficiency of 13.6% in solar cell devices with Y6 as acceptor without any additive.