p-Type Conjugated Polymers Containing Electron-Deficient Pentacyclic Azepinedione.

Bisthienoazepinedione (BTA) has been reported for constructing high-performing p-type conjugated polymers in organic electronics, but the ring extended version of BTA is not well explored. In this work, we report a new synthesis of a key building block to the ring expanded electron-deficient pentacyclic azepinedione (BTTA). Three copolymers of BTAA with benzodithiophene substituted by different side chains are prepared. These polymers exhibit similar energy levels and optical absorption in solution and solid state, while significant differences are revealed in their film morphologies and behavior in transistor and photovoltaic devices. The best-performing polymers in transistor devices contained alkylthienyl side chains on the BDT unit (pBDT-BTTA-2 and pBDT-BTTA-3) and demonstrated maximum saturation hole mobilities of 0.027 and 0.017 cm2 V-1 s-1. Blends of these polymers with PC71BM exhibited a best photovoltaic efficiency of 6.78% for pBDT-BTTA-3-based devices. Changing to a low band gap non-fullerene acceptor (BTP-eC9) resulted in improved efficiency of up to 13.5%. Our results are among the best device performances for BTA and BTTA-based p-type polymers and highlight the versatile applications of this electron-deficient BTTA unit.

Ultra-Narrowband Near-Infrared Responsive J-Aggregates of Fused Quinoidal Tetracyanoindacenodithiophene.

Narrowband photoresponsive molecules are highly coveted in high-resolution imaging, sensing, and monochromatic photodetection, especially those extending into the near-infrared (NIR) spectral range. Here, a new class of J-aggregating materials based on quinoidal indacenodithiophenes (IDTs) that exhibit an ultra-narrowband (full width half maxima of 22 nm) NIR absorption peak centered at 770 nm is reported. The spectral width is readily tuned by the length of the solubilizing alkyl group, with longer chains resulting in significant spectral narrowing. The J-aggregate behavior is confirmed by a combination of excited state lifetime measurements and single-crystal X-ray diffraction measurements. Their utility as electron-transporting materials is demonstrated in both transistor and phototransistor devices, with the latter demonstrating good response at NIR wavelengths (780 nm) over a range of intensities.

Hypercrosslinking porous polymer layers on TiO2-graphene photocatalyst: Enhanced adsorption of water pollutants for efficient degradation.

Solar-driven photocatalysis offers an environmentally friendly and sustainable approach for the degradation of organic pollutants in water without chemical additives, but the low specific surface area and adsorption capacity of common photocatalysts restricts the surface reactions with the contaminants. Herein, we hypercrosslinked polymer layers on TiO2-graphene surface to enlarge the specific surface area from 136 to 988 m2/g, leading to a high adsorption capacity of sulfadiazine as 54.3 mg/g, which is 15.5 times that of TiO2-graphene (3.5 mg/g). The adsorption kinetics reveals the combination of physical and chemical adsorption by porous benzene-based polymer for sulfadiazine enrichment. Besides, the polymer layers with broad light absorption enable the composite to function efficiently as visible-light-driven photocatalysts. Thus, the as-designed composite exhibits excellent performance for sulfadiazine removal by integrating the adsorptive and photocatalytic processes, especially for the diluted sulfadiazine solution. More importantly, the porous polymer layer can function as a filter for weakening the interference of TiO2 surface with the natural matters from complex water matrices. Based on the identification of dominant reactive species, the possible attacking pathway and the sulfadiazine subsequent degradation are presented. Further, the enhanced adsorption and photodegradation efficiency can also be achieved for the removal of other typical pollutants such as 4-chlorophenol and methylene blue. This study highlights an adsorption-enhanced-degradation mechanism for water pollutants that can direct the design of high-performance photocatalysts under visible light.

Probing the electronic structure and photophysics of thiophene-diketopyrrolopyrrole derivatives in solution.

Diketopyrrolopyrroles are a popular class of electron-withdrawing unit in optoelectronic materials. When combined with electron donating side-chain functional groups such as thiophenes, they form a very broad class of donor-acceptor molecules: thiophene-diketopyrrolopyrroles (TDPPs). Despite their widescale use in biosensors and photovoltaic materials, studies have yet to establish the important link between the electronic structure of the specific TDPP and the critical optical properties. To bridge this gap, ultrafast transient absorption with 22 fs time resolution has been used to explore the photophysics of three prototypical TDPP molecules: a monomer, dimer and polymer in solution. Interpretation of experimental data was assisted by a recent high-level theoretical study, and additional density functional theory calculations. These studies show that the photophysics of these molecular prototypes under visible photoexcitation are determined by just two excited electronic states, having very different electronic characters (one is optically bright, the other dark), their relative energetic ordering and the timescales for internal conversion from one to the other and/or to the ground state. The underlying difference in electronic structure alters the branching between these excited states and their associated dynamics. In turn, these factors dictate the fluorescence quantum yields, which are shown to vary by ∼1-2 orders of magnitude across the TDPP prototypes investigated here. The fast non-radiative transfer of molecules from the bright to dark states is mediated by conical intersections. Remarkably, wavepacket signals in the measured transient absorption data carry signatures of the nuclear motions that enable mixing of the electronic-nuclear wavefunction and facilitate non-adiabatic coupling between the bright and dark states.

Self-Assembly of Albumin and [FeFe]-Hydrogenase Mimics for Photocatalytic Hydrogen Evolution.

To imitate the protein microenvironment surrounding the Fe2S2 active site, we established a convenient method to prepare self-assembled ovalbumin (OVA) nanogels that noncovalently incorporated hydrophobic FeFe-H2ase mimic (FeFe-1) in situ with an excellent loading efficiency up to 53.9%. The OVA@FeFe-1 composite nanogels (CG) were applied to photocatalytic hydrogen evolution in aqueous solution and exhibited improved catalytic efficiency with a turnover number amplified over 15 times relative to free FeFe-1 catalysts. The enhanced activity was attributed to the enrichment of the FeFe-1 catalyst and changes of protein secondary structures and microenvironment.

Diiron Dithiolate Complex Induced Helical Structure of Histone and Application in Photochemical Hydrogen Generation.

Very-lysine-rich calf thymus histone proteins form disordered structure and hydrophobic interaction-driven aggregates in weakly acidic solution. We reported that the conjugation of diiron dithiolate complex to the lysine residues induced formation of helical conformation and condensed nanoassemblies with a high loading capacity up to 18.7 wt %. The incorporated diiron dithiolate complex showed photocatalytic activity for hydrogen evolution in aqueous solutions, with a turnover number (based on [FeFe] catalyst moiety) up to 359 that was more than 6 times that of the free catalyst. The increase of helical conformation in proteins was well correlated to the increasing enhancement of photocatalytic activity. We demonstrated that the [FeFe]-hydrogenase-mimic biohybrid system based on the photocatalyst-induced protein conformational conversion and reassembly is efficient for hydrogen generation regardless of the relatively large size.

Mitochondria Targeting Fluorescent Probes Based on through Bond-Energy Transfer for Mutually Imaging Signaling Molecules H2 S and H2 O2.

Reactive signaling molecules participate in varieties of biochemical reactions, and methods to detect their mutual existence and crosstalk are in urgent demand. A benzothiadiazole-based handle was designed to fluorescently respond to the co-existence of H2 S and H2 O2 under pseudo-physiological conditions on a basis of a thiyl-radical-mediated mechanism that accounts for the rapid and efficient domino-like reaction processes. Then the handle motif was attached to a rhodamine moiety by means of an ethynylene linkage, and achieved a significant H2 S-H2 O2 mutual response in the mitochondria of living cells. Theoretical calculations supported that a through bond energy transfer mechanism contributes to the drastic fluorescence response.

Iron sulfur clusters in protein nanocages for photocatalytic hydrogen generation in acidic aqueous solutions.

We took advantage of the iron binding affinity of apoferritin to immobilize iron-sulfur clusters into apoferritin up to 312 moieties per protein, with a loading rate as high as 25 wt%. The photocatalytic hydrogen generation activity in acidic aqueous solutions was achieved with TONs up to 31 (based on a single catalyst moiety) or 8.3 × 103 (based on a single protein) upon 3 h of visible light irradiation. The present study provides a versatile strategy to construct uniform protein/photocatalyst supramolecular systems with FeFe-H2ase activity.