Azulene-Containing Bis(squaraine) Dyes: Design, Synthesis and Aggregation Behaviors.

The relationship among chemical structure, physicochemical property and aggregation behavior of organic functional material is an important research topic. Here, we designed and synthesized three bis(squaraine) dyes BSQ1, BSQ2 and BSQ3 through the combination of two kinds of unsymmetrical azulenyl squaraine monomers. Their physicochemical properties were investigated in both molecular and aggregate states. Generally, BSQ1 displayed different assembly behaviors from BSQ2 and BSQ3. Upon fabrication into nanoparticles, BSQ1 tend to form J-aggregates while BSQ2 and BSQ3 tend to form H-aggregates in aqueous medium. When in the form of thin films, three bis(squaraine) dyes all adopted J-aggregation packing modes while only BSQ1 presented the most significant rearrangement of aggregate structures as well as the improvement in the carrier mobilities upon thermal annealing. Our research highlights the discrepancy of aggregation behaviors originating from the molecular structure and surrounding circumstances, providing guidance for the molecular design and functional applications of squaraines.

Fused Azulenyl Squaraine Derivatives Improve Phototheranostics in the Second Near-Infrared Window by Concentrating Excited State Energy on Non-Radiative Decay Pathways.

The second near-infrared (NIR-II) theranostics offer new opportunities for precise disease phototheranostic due to the enhanced tissue penetration and higher maximum permissible exposure of NIR-II light. However, traditional regimens lacking effective NIR-II absorption and uncontrollable excited-state energy decay pathways often result in insufficient theranostic outcomes. Herein a phototheranostic nano-agent (PS-1 NPs) based on azulenyl squaraine derivatives with a strong NIR-II absorption band centered at 1092 nm is reported, allowing almost all absorbed excitation energy to dissipate through non-radiative decay pathways, leading to high photothermal conversion efficiency (90.98 %) and strong photoacoustic response. Both in vitro and in vivo photoacoustic/photothermal therapy results demonstrate enhanced deep tissue cancer theranostic performance of PS-1 NPs. Even in the 5 mm deep-seated tumor model, PS-1 NPs demonstrated a satisfactory anti-tumor effect in photoacoustic imaging-guided photothermal therapy. Moreover, for the human extracted tooth root canal infection model, the synergistic outcomes of the photothermal effect of PS-1 NPs and 0.5 % NaClO solution resulted in therapeutic efficacy comparable to the clinical gold standard irrigation agent 5.25 % NaClO, opening up possibilities for the expansion of NIR-II theranostic agents in oral medicine.

Enhanced π-π Stacking between Dipole-Bearing Single Molecules Revealed by Conductance Measurement.

Dipoles are widely involved in π-π interactions and are central to many chemical and biological functions, but their influence on the strength of π-π interactions remains unclear. Here, we report a study of π-π interaction between azulene-based, polar single molecules and between naphthalene-based, nonpolar single molecules. By performing scanning tunneling microscopy break junction measurements of single-molecule conductance, we show that the π-stacked dimers formed by the azulene-based, polar aromatic structures feature higher electrical conductivity and mechanical stability than those formed by the naphthalene-based, nonpolar molecules. Mechanical control of π-π interactions in both rotational and translational motion reveals a sensitive dependence of the stacking strength on relative alignment between the dipoles. The antiparallel alignment of the dipoles was found to be the optimal stacking configuration that underpins the observed enhancement of π-π stacking between azulene-based single molecules. Density functional theory calculations further explained the observed enhancement of stacking strength and the corresponding charge transport efficiency. Our experimental and theoretical results show that the antiparallel alignment of the dipole moments significantly enhances the electronic coupling and mechanical stability of π-π stacking. In addition, in the formation of single-molecule junctions, the azulene group was experimentally and theoretically proved to form a Au-π contact with electrodes with high charge transport efficiency. This paper provides evidence and interpretation of the role of dipoles in π-π interactions at the single-molecule level and offers new insights into potential applications in supramolecular devices.

Synchronously Manipulating Absorption and Extinction Coefficient of Semiconducting Polymers via Precise Dual-Acceptor Engineering for NIR-II Excited Photothermal Theranostics.

Integrating the ultralong excitation wavelength, high extinction coefficient, and prominent photothermal conversion ability into a single photothermal agent is an appealing yet significantly challenging task. Herein, a precise dual-acceptor engineering strategy is exploited for this attempt based on donor-acceptor (D-A) type semiconductor polymers by subtly regulating the molar proportions of the two employed electron acceptor moieties featuring different electronic affinity and π-conjugation degrees, and making full use of the active intramolecular motion-induced photothermal effect. The optimal polymer SP4 synchronously shows desirable second near-infrared (NIR-II) absorption, an extremely high extinction coefficient, and satisfactory photothermal conversion behavior. Consequently, the unprecedented performance of SP4 NPs on 1064 nm laser-excited photoacoustic imaging (PAI)-guided photothermal therapy (PTT) is demonstrated by the precise tumor diagnosis and complete tumor elimination.

Dipole-Modulated Charge Transport through PNP-Type Single-Molecule Junctions.

The PNP structure realized by energy band engineering is widely used in various electronic and optoelectronic devices. In this work, we succeed in constructing a PNP-type single-molecule junction and explore the intrinsic characteristics of the PNP structure at the single-molecule level. A back-to-back azulene molecule is designed with opposite ∼1.7 D dipole moments to create PNP-type single-molecule junctions. In combination with theoretical and experimental studies, it is found that the intrinsic dipole can effectively adjust single-molecule charge transport and the corresponding potential barriers. This energy band control and charge transport regulation at the single-molecule level improve deep understanding of molecular charge transport mechanisms and provide important insights into the development of high-performance functional molecular nanocircuits toward practical applications.

Azulene-Based π-Functional Materials: Design, Synthesis, and Applications.

ConspectusAzulene, an isomer of naphthalene, is a molecule of historical interest for its unusual photophysical properties, including a beautiful blue color derived from the narrow HOMO-LUMO energy gap and anti-Kasha fluorescence from S2 to S0. More recently, it has attracted increasing attention for its novel electronic structure, including an electron-rich five-membered ring and an electron-deficient seven-membered ring with a dipole moment of 1.08 D resulting from resonance delocalization, its different reactivities at odd and even positions, and its stimuli-responsive behavior. As a key building block, azulene has been used in various fields because of its unique physicochemical properties. Recent studies have demonstrated the great potential of azulene for constructing advanced organic materials. However, exploring azulene-based materials has long been hindered by challenges in molecular design and synthesis. Most of the reported azulene-based materials have the azulene unit incorporated through the five-membered ring or seven-membered ring. Creating azulene-based novel building blocks for optoelectronics and using 2,6-connected azulene units to construct conjugated polymers that can adequately utilize the "donor-acceptor" structure of azulene remained underexplored before our contributions. Besides, for most azulene-fused polycyclic aromatic hydrocarbons (PAHs) and heteroaromatics, the azulene substructures were created during later synthesis stages, and the use of azulene derivatives as starting materials to design and synthesize PAHs and heteroaromatics intelligently is still limited.In this Account, we summarize our efforts on the design, synthesis, and applications of azulene-based π-functional materials. Our studies start with the creation of novel π-conjugated structures based on azulene. The design strategy, synthesis, and optoelectronic performance of the first class of azulene-based aromatic diimides, 2,2'-biazulene-1,1',3,3'-tetracarboxylic diimide (BAzDI) and its π-extended and π-bridged derivatives, are presented. Notably, antiparallel stacking between adjacent azulene units derived from azulene's dipole was observed in single crystals of BAzDI and its derivatives. Besides, we developed an azulene-fused isoindigo analogue, azulenoisoindigo, which combines the merits of both isoindigo and azulene, including reversible redox behavior and reversible proton responsiveness. Then we discuss our contributions to the design and synthesis of 2,6-azulene-based conjugated polymers. By incorporation of 2,6-connected azulene units into the polymeric backbone, two conjugated polymers with high organic field-effect transistor (OFET) performance were developed. Two 2,6-azulene-based polymers with proton responsiveness and high electrical conductivity upon protonation were also provided. We also discuss our recent studies on azulene-based heteroaromatics. Two azulene-fused BN-heteroaromatics were designed and synthesized, and they exhibited a selective response to fluoride ion and unexpected deboronization upon the addition of trifluoroacetic acid. An unexpected synthesis of azulene-pyridine-fused heteroaromatics (Az-Py) by reductive cyclization of 1-nitroazulenes and the OFET performance of Az-Py-1 are included. Afterward, we discuss several examples of azulene-capped organic conjugated molecules. The molecules capped with the five-membered ring of azulene favor hole transport, whereas the ones capped with the seven-membered ring favor electron transport.

Azulene-Embedded [n]Helicenes (n=5, 6 and 7).

Azulene is a non-benzenoid aromatic building block with unique chemical structure and physicochemical properties. By using the "bottom-up" synthetic strategy, we synthesized three azulene-embedded [n]helicenes ([n]AzHs, n=5, 6 and 7), in which one terminal azulene subunit was fused with n-2 benzene rings. P- and M-enantiomers were observed in the packing diagrams of [5]-, and [6]AzHs. However, P- and M-[7]AzHs could be isolated by recrystallization of the racemic mixture. These [n]AzHs were endowed with new properties through the azulene moiety such as low-lying first electric state (S1 ), small optical energy gap and anti-Kasha emission. [6]-, and [7]AzHs exhibit strong chiroptical responses with high absorption dissymmetry factor (gabs ) maxima of about 0.02, which is among the highest |gabs | values of helicenes in the visible range. These azulene-embedded [n]helicenes contribute to the non-benzenoid helicene library and allow the structure-property relationships to be better understood.

Azulene-Pyridine-Fused Heteroaromatics.

Azulene, a nonbenzenoid bicyclic aromatic hydrocarbon with unique electronic structure, is a promising building block for constructing nonbenzenoid π-conjugated systems. However, azulene-fused (hetero)aromatics remain rare as a result of limited synthetic methods. We report herein the unexpected synthesis of azulene- and pyridine-fused heteroaromatics Az-Py-1, a seven fused ring system with 30π electrons, by reductive cyclization of a 1-nitroazulene. The structure of Az-Py-1 was unambiguously confirmed by single-crystal X-ray analysis, and analogues Az-Py-2-Az-Py-6 were also synthesized, demonstrating that this is an effective method for constructing azulene- and pyridine-fused heteroaromatics. Theoretical calculations and photophysical and electrochemical studies of Az-Py-1-Az-Py-6 suggest their potential as semiconductors, and the single-crystal ribbons of Az-Py-1 show high hole mobilities up to 0.29 cm2 V-1 s-1.

Azulene-Based BN-Heteroaromatics.

Azulene, a nonalternant bicyclic aromatic hydrocarbon, has unique chemical and physical properties and is considered to be a promising building block for constructing novel polycyclic aromatic hydrocarbons (PAHs) and heteroaromatics. We present here the first two azulene-based BN-heteroaromatics Az-BN-1 and Az-BN-2. The chemical structures and optical and electrochemical properties of both compounds have been investigated, as well as their sensing behavior in response to fluoride ion. Az-BN-1 and Az-BN-2 show different photophysical properties from other reported BN-embedded PAHs, such as lower band gaps and unusual fluorescence. In addition, Az-BN-1 and Az-BN-2 exhibit unexpected deboronization upon addition of trifluoroacetic acid, which distinguishes them from other reported BN-heteroaromatics and can be ascribed to the unique property of the azulene unit.

Monolayer Two-dimensional Molecular Crystals for an Ultrasensitive OFET-based Chemical Sensor.

The sensitivity of conventional thin-film OFET-based sensors is limited by the diffusion of analytes through bulk films and remains the central challenge in sensing technology. Now, for the first time, an ultrasensitive (sub-ppb level) sensor is reported that exploits n-type monolayer molecular crystals (MMCs) with porous two-dimensional structures. Thanks to monolayer crystal structure of NDI3HU-DTYM2 (NDI) and controlled formation of porous structure, a world-record detection limit of NH3 (0.1 ppb) was achieved. Moreover, the MMC-OFETs also enabled direct detection of solid analytes of biological amine derivatives, such as dopamine at an extremely low concentration of 500 ppb. The remarkably improved sensing performances of MMC-OFETs opens up the possibility of engineering OFETs for ultrasensitive (bio)chemical sensing.

From Homochiral Assembly to Heterochiral Assembly: A Leap in Charge Transport Properties of Binaphthol-Based Axially Chiral Materials.

Chirality, as a fundamental symmetry property, plays an important role in molecular assembly in the solid state, impacting upon the properties and performance of organic materials. Here, heterochiral assembly was observed upon a binaphthol-based axially chiral material in the thin film state, where the heterochiral assemblies of racemic mixtures exhibit superior crystallization behavior and film morphologies than their homochiral counterparts. Additionally, a dramatic increase (nearly 2 orders of magnitudes) in electronic mobility was obtained upon switching the active layers of organic thin-film transistors from homochiral assemblies to heterochiral assemblies. This work not only gives insights into the structure-aggregation property relationships of axially chiral self-assemblies but also offers new opportunities for novel organic soft materials.

Incorporation of 2,6-Connected Azulene Units into the Backbone of Conjugated Polymers: Towards High-Performance Organic Optoelectronic Materials.

Azulene is a promising candidate for constructing optoelectronic materials. An effective strategy is presented to obtain high-performance conjugated polymers by incorporating 2,6-connected azulene units into the polymeric backbone, and two conjugated copolymers P(TBAzDI-TPD) and P(TBAzDI-TFB) were designed and synthesized based on this strategy. They are the first two examples for 2,6-connected azulene-based conjugated polymers and exhibit unipolar n-type transistor performance with an electron mobility of up to 0.42 cm2 V-1 s-1 , which is among the highest values for n-type polymeric semiconductors in bottom-gate top-contact organic field-effect transistors. Preliminary all-polymer solar cell devices with P(TBAzDI-TPD) as the electron acceptor and PTB7-Th as the electron donor display a power conversion efficiency of 1.82 %.

An Abnormal 3.7†Volt O3-Type Sodium-Ion Battery Cathode.

Layered O3-type sodium oxides (NaMO2 , M=transition metal) commonly exhibit an O3-P3 phase transition, which occurs at a low redox voltage of about 3 V (vs. Na+ /Na) during sodium extraction and insertion, with the result that almost 50 % of their total capacity lies at this low voltage region, and they possess insufficient energy density as cathode materials for sodium-ion batteries (NIBs). Therefore, development of high-voltage O3-type cathodes remains challenging because it is difficult to raise the phase-transition voltage by reasonable structure modulation. A new example of O3-type sodium insertion materials is presented for use in NIBs. The designed O3-type Na0.7 Ni0.35 Sn0.65 O2 material displays a highest redox potential of 3.7 V (vs. Na+ /Na) among the reported O3-type materials based on the Ni2+ /Ni3+ couple, by virtue of its increased Ni-O bond ionicity through reduced orbital overlap between transition metals and oxygen within the MO2 slabs. This study provides an orbital-level understanding of the operating potentials of the nominal redox couples for O3-NaMO2 cathodes. The strategy described could be used to tailor electrodes for improved performance.

Controlled Growth of Ultrathin Film of Organic Semiconductors by Balancing the Competitive Processes in Dip-Coating for Organic Transistors.

Ultrathin film with thickness below 15 nm of organic semiconductors provides excellent platform for some fundamental research and practical applications in the field of organic electronics. However, it is quite challenging to develop a general principle for the growth of uniform and continuous ultrathin film over large area. Dip-coating is a useful technique to prepare diverse structures of organic semiconductors, but the assembly of organic semiconductors in dip-coating is quite complicated, and there are no reports about the core rules for the growth of ultrathin film via dip-coating until now. In this work, we develop a general strategy for the growth of ultrathin film of organic semiconductor via dip-coating, which provides a relatively facile model to analyze the growth behavior. The balance between the three direct factors (nucleation rate, assembly rate, and recession rate) is the key to determine the growth of ultrathin film. Under the direction of this rule, ultrathin films of four organic semiconductors are obtained. The field-effect transistors constructed on the ultrathin film show good field-effect property. This work provides a general principle and systematic guideline to prepare ultrathin film of organic semiconductors via dip-coating, which would be highly meaningful for organic electronics as well as for the assembly of other materials via solution processes.

Bismuth Interfacial Doping of Organic Small Molecules for High Performance n-type Thermoelectric Materials.

Development of chemically doped high performance n-type organic thermoelectric (TE) materials is of vital importance for flexible power generating applications. For the first time, bismuth (Bi) n-type chemical doping of organic semiconductors is described, enabling high performance TE materials. The Bi interfacial doping of thiophene-diketopyrrolopyrrole-based quinoidal (TDPPQ) molecules endows the film with a balanced electrical conductivity of 3.3 S cm(-1) and a Seebeck coefficient of 585 µV K(-1) . The newly developed TE material possesses a maximum power factor of 113 µW m(-1) K(-2) , which is at the forefront for organic small molecule-based n-type TE materials. These studies reveal that fine-tuning of the heavy metal doping of organic semiconductors opens up a new strategy for exploring high performance organic TE materials.

Syntheses and properties of nine-ring-fused linear thienoacenes.

π-Extended nine-ring-fused linear thienoacenes 1a­c with internal thieno[3,2-b;4,5-b']dithiophene substructures were synthesized. Their optical and electrochemical properties were investigated. Thin-film transistor characteristics showed all compounds displayed high device reproducibility and nearly no dependence on substrate temperatures. The highest performance was observed for 1c-based devices with mobility up to 1.0 cm2/Vs and current on/off ratio of 10(7), whereas the maximum mobility was 0.5 cm2/Vs for 1b and 0.011 cm2/Vs for 1a.

Critical role of alkyl chain branching of organic semiconductors in enabling solution-processed N-channel organic thin-film transistors with mobility of up to 3.50 cm² V(-1) s(-1).

Substituted side chains are fundamental units in solution processable organic semiconductors in order to achieve a balance of close intermolecular stacking, high crystallinity, and good compatibility with different wet techniques. Based on four air-stable solution-processed naphthalene diimides fused with 2-(1,3-dithiol-2-ylidene)malononitrile groups (NDI-DTYM2) that bear branched alkyl chains with varied side-chain length and different branching position, we have carried out systematic studies on the relationship between film microstructure and charge transport in their organic thin-film transistors (OTFTs). In particular synchrotron measurements (grazing incidence X-ray diffraction and near-edge X-ray absorption fine structure) are combined with device optimization studies to probe the interplay between molecular structure, molecular packing, and OTFT mobility. It is found that the side-chain length has a moderate influence on thin-film microstructure but leads to only limited changes in OTFT performance. In contrast, the position of branching point results in subtle, yet critical changes in molecular packing and leads to dramatic differences in electron mobility ranging from ~0.001 to >3.0 cm(2) V(-1) s(-1). Incorporating a NDI-DTYM2 core with three-branched N-alkyl substituents of C(11,6) results in a dense in-plane molecular packing with an unit cell area of 127 Å(2), larger domain sizes of up to 1000 × 3000 nm(2), and an electron mobility of up to 3.50 cm(2) V(-1) s(-1), which is an unprecedented value for ambient stable n-channel solution-processed OTFTs reported to date. These results demonstrate that variation of the alkyl chain branching point is a powerful strategy for tuning of molecular packing to enable high charge transport mobilities.

Electron-rich pyrroloindacenodithiophenes: synthesis, characterization, and spectroscopic studies.

N-Alkyl substituted pyrroloindacenodithiophene (PIDT) and their phenyl substituted derivatives were synthesized. Their single-crystal structures and electrochemical and spectroscopic properties were investigated. Experimental results showed PIDT displayed strong electron-donating properties, reversible redox behaviors, and strong fluorescence and could be controlled to oxidize to radical cation and dication with distinctive optical changes. These attractive properties demonstrated the potential applications of PIDT in the field of switches, molecular machines, and information memories.

Tetracyanodibenzotetrathiafulvalene diimides: design, synthesis, and property study.

Tetracyanodibenzotetrathiafulvalene diimide (TCDBTTF-DI), an isomer of core-expanded naphthalene diimides bearing two 2-(1,3-dithiol-2-ylidene)malononitrile moieties (NDI-DTYM2), has been designed and synthesized to explore the effect of its isomeric structure on the optical and electrochemical properties of the materials. UV-vis spectra show that TCDBTTF-DI exhibits variation in its absorption peaks while maintaining a similar optical band gap to NDI-DTYM2. Electrochemical studies indicate that TCDBTTF-DI can not only accept but also lose electrons, in contrast to the solely electron-accepting behavior of NDI-DTYM2.

Tuning Dipole Orientation of 2,6-Azulene Units in Conjugated Copolymers by C-H Activation Strategy toward High-Performance Organic Semiconductor.

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-to-head/tail-to-tail for P(AzTPD-2), and head-to-tail for P(AzTPD-3). 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.