Construction of Layer-Blocked Covalent Organic Framework Heterogenous Films via Surface-Initiated Polycondensations with Strongly Enhanced Photocatalytic Properties.

Imine-linked covalent organic frameworks (COFs) usually show high crystallinity and porosity, while vinyl-linked COFs have excellent semiconducting properties and stability. Therefore, achieving the advantages of imine- and vinyl-linkages in a single COF material is highly interesting but remains challenging. Herein, we demonstrate the fabrication of a layer-blocked COF (LB-COF) heterogeneous film that is composed of imine- and vinyl-linkages through two successive surface-initiated polycondensations. In brief, the bottom layer of imine-linked COF film was constructed on an amino-functionalized substrate via Schiff-base polycondensation, in which the unreacted aldehyde edges could be utilized for initiating aldol polycondensation to prepare the second layer of vinyl-linked COF film. The resultant LB-COF film displays excellent ordering due to the crystalline templating effect from the bottom imine-linked COF layer; meanwhile, the upper vinyl-linked COF layer could strongly enhance its stability and photocatalytic properties. The LB COF also presents superior performance in photocatalytic uranium extraction (320 mg g-1), which is higher than the imine-linked (35 mg g-1) and the vinyl-linked (295 mg g-1) counterpart. This study provides a novel surface-initiated strategy to synthesize layer-blocked COF heterogeneous films that combine the advantages of each building block.

2D Conjugated Polymer Thin Films for Organic Electronics: Opportunities and Challenges.

2D conjugated polymers (2DCPs) possess extended in-plane π-conjugated lattice and out-of-plane π-π stacking, which results in enhanced electronic performance and potentially unique band structures. These properties, along with predesignability, well-defined channels, easy postmodification, and order structure attract extensive attention from material science to organic electronics. In this review, the recent advance in the interfacial synthesis and conductivity tuning strategies of 2DCP thin films, as well as their application in organic electronics is summarized. Furthermore, it is shown that, by combining topology structure design and targeted conductivity adjustment, researchers have fabricated 2DCP thin films with predesigned active groups, highly ordered structures, and enhanced conductivity. These films exhibit great potential for various thin-film organic electronics, such as organic transistors, memristors, electrochromism, chemiresistors, and photodetectors. Finally, the future research directions and perspectives of 2DCPs are discussed in terms of the interfacial synthetic design and structure engineering for the fabrication of fully conjugated 2DCP thin films, as well as the functional manipulation of conductivity to advance their applications in future organic electronics.

Construction of Thiadiazole-Bridged sp2-Carbon-Conjugated Covalent Organic Frameworks with Diminished Excitation Binding Energy Toward Superior Photocatalysis.

Sp2-carbon-conjugated covalent organic frameworks (sp2c-COFs) have emerged as promising platforms for phototo-chemical energy conversion due to their tailorable optoelectronic properties, in-plane π-conjugations, and robust structures. However, the development of sp2c-COFs in photocatalysis is still highly hindered by their limited linkage chemistry. Herein, we report a novel thiadiazole-bridged sp2c-COF (sp2c-COF-ST) synthesized by thiadiazole-mediated aldol-type polycondensation. The resultant sp2c-COF-ST demonstrates high chemical stability under strong acids and bases (12 M HCl or 12 M NaOH). The electro-deficient thiadiazole together with fully conjugated and planar skeleton endows sp2c-COF-ST with superior photoelectrochemical performance and charge-carrier separation and migration ability. As a result, when employed as a photocathode, sp2c-COF-ST exhibits a significant photocurrent up to ∼14.5 µA cm-2 at 0.3 V vs reversible hydrogen electrode (RHE) under visible-light irradiation (>420 nm), which is much higher than those analogous COFs with partial imine linkages (mix-COF-SNT ∼ 9.5 µA cm-2) and full imine linkages (imi-COF-SNNT ∼ 4.9 µA cm-2), emphasizing the importance of the structure-property relationships. Further temperature-dependent photoluminescence spectra and density functional theory calculations demonstrate that the sp2c-COF-ST has smaller exciton binding energy as well as effective mass in comparison to mix-COF-SNT and imi-COF-SNNT, which suggests that the sp2c-conjugated skeleton enhances the exciton dissociation and carrier migration under light irradiation. This work highlights the design and preparation of thiadiazole-bridged sp2c-COFs with promising photocatalytic performance.

Two-Dimensional Conjugated Polymers: a New Choice For Organic Thin-Film Transistors.

Organic thin-film transistors (OTFTs) as a vital component among transistors have shown great potential in smart sensing, flexible displays, and bionics due to their flexibility, biocompatibility and customizable chemical structures. Even though linear conjugated polymer semiconductors are common for constructing channel materials of OTFTs, advanced materials with high charge carrier mobility, tunable band structure, robust stability, and clear structure-property relationship are indispensable for propelling the evolution of OTFTs. Two-dimensional conjugated polymers (2DCPs), featured with conjugated lattice, tailorable skeletons, and functional porous structures, match aforementioned criteria closely. In this review, we firstly introduce the synthesis of 2DCP thin films, focusing on their characteristics compatible with the channels of OTFTs. Subsequently, the physics and operating mechanisms of OTFTs and the applications of 2DCPs in OTFTs are summarized in detail. Finally, the outlook and perspective in the field of OTFTs using 2DCPs are provided as well.

Monolayer-Assisted Surface-Initiated Schiff-Base-Mediated Aldol Polycondensation for the Synthesis of Crystalline sp2 Carbon-Conjugated Covalent Organic Framework Thin Films.

sp2 carbon-conjugated covalent organic frameworks (sp2c-COFs) with superb in-plane π-conjugations, high chemical stability, and robust framework structure are expected to be ideal films/membranes for a wide range of applications including energy-related devices and optoelectronics. However, so far, sp2c-COFs have been mainly limited to microcrystalline powders, and this consequently hampered their performances in devices. Herein, we report a simple and robust methodology to fabricate large-area, free-standing, and crystalline sp2c-COF films (TFPT-TMT and TB-TMT) on various solid substrates (e.g., fluorine-doped tin oxide, aluminum sheet, polyacrylonitrile membrane) by self-assembly monolayer-assisted surface-initiated Schiff-base-mediated aldol polycondensation (namely, SI-SBMAP). The resultant sp2c-COF films show lateral sizes up to 120 cm2 and tunable thickness from tens of nanometers to a few micrometers. Owing to the robust framework and highly ordered quasi-1D channels, the sp2c-COF membrane-based osmotic power generator presents an output power density of 14.1 W m-2 under harsh conditions, outperforming most reported COF membranes as well as commercialized benchmark devices (5 W m-2). This work demonstrates a simple and robust interfacial methodology for the fabrication of sp2c-COF films/membranes for green energy applications and potential optoelectronics.

Direct Construction of Isomeric Benzobisoxazole-Vinylene-Linked Covalent Organic Frameworks with Distinct Photocatalytic Properties.

Vinylene/olefin-linked two-dimensional covalent organic frameworks (v-2D-COFs) have emerged as advanced semiconducting materials with excellent in-plane conjugation, high chemical stabilities, and precisely tunable electronic structures. Exploring new linkage chemistry for the reticular construction of v-2D-COFs remains in infancy and challenging. Herein, we present a solid-state benzobisoxazole-mediated aldol polycondensation reaction for the construction of two novel isomeric benzobisoxazole-bridged v-2D-COFs (v-2D-COF-NO1 and v-2D-COF-NO2) with trans and cis configurations of benzobisoxazole. Interestingly, the isomeric benzobisoxazole linkers endow the two v-2D-COFs with distinct optoelectronic and electrochemical properties, ranging from light absorption and emission to charge-transfer properties. When employed as the photocathode, v-2D-COF-NO1 exhibits a photocurrent of up to ∼18 µA/cm2 under AM 1.5G irradiation at -0.3 V vs reversible hydrogen electrode (RHE), which is twice the value of v-2D-COF-NO2 (∼9.1 µA/cm2). With Pt as a cocatalyst, v-2D-COF-NO1 demonstrates a photocatalytic hydrogen evolution rate of ∼1.97 mmol h-1 g-1, also in clear contrast to that of v-2D-COF-NO2 (∼0.86 mmol h-1 g-1) under identical conditions. This work demonstrates the synthesis of v-2D-COFs via benzobisoxazole-mediated aldol polycondensation with isomeric structures and distinct photocatalytic properties.