Developing biodegradable light conversion films is of great significance in the agriculture and environment fields. In this work, two types of light conversion films were successfully prepared using biodegradable polylactide (PLA) and poly (butylene adipate-co-terephthalate) (PBAT) combined with different amounts of europium(iii) complexes (0.1%,0.3%, and 0.5%) through solution casting. Europium(iii) complexes were dispersed uniformly in PLA/PBAT, the hydrophilicity of the films increased with the addition of europium(iii) complexes. The films with a light transmittance of up to 80% displayed excellent light conversion capabilities and could convert UV-vis light into red light. Meanwhile, the tensile strength and elongation at the break of the PLA/PBAT/0.5% europium(iii) complex film reached 41.05 MPa and 19.29%, respectively. This work provides new ideas for research on degradable light conversion films.

Three donor (D)–acceptor (A)-type temperature-activated delayed fluorescent (TADF) molecules of 9-(2-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9H-3,9′-bicarbazole (o-TrzDCz), 9-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9H-3,9′-bicarbazole (m-TrzDCz), and 9-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9H-3,9′-bicarbazole (p-TrzDCz) were designed in this paper, and the photophysical properties, including the intersystem crossing rate, the reorganization energies (λ), and the intersystem crossing/reverse intersystem crossing (ISC/RISC) rate, were simulated to explore the effect of substitution sites on their TADF character. The values of the twist angle between the D and A moieties in ground state and the molecular root-mean-square deviation (RMSD) of the S1 and T1 states referenced to the S0 state indicate that o-TrzDCz possess bigger steric hindrance and stabler molecular configuration. The λ values of the ISC/RISC process should be 0.06/0.04 eV for o-TrzDCz, which are much smaller than those of m-TrzDCz (0.51/0.41 eV) and p-TrzDCz (1.93/1.06 eV). At the same time, o-TrzDCz possess the biggest kRISC (7.28 × 106 s−1) and kr (3.12 × 106 s−1) values and the smallest kp (0.10 s−1) value among the three titled molecules. These data indicate that o-TrzDCz should have more excellent TADF character than m-TrzDCz and p-TrzDCz. In a word, this research presents that adjusting the molecular linking manner should be a charming way to explore novel high-efficient TADF molecules. Quantum chemical calculations were performed at PBE0/6-31G* level by Gaussian 09 and ORCA 4.1.0 software packages, and reorganization energies and Huang-Rhys were performed by the DUSHIN program and MOMAP 2019B software package based on the Gaussian 09 output files, while the phosphorescence rates were performed at B3LYP/6-31G* level by Dalton 2021.

Rapid recombination of photoinduced charge carriers and photoinstability greatly hinder the large-scale appli-cation of CdS photocatalysis. Herein, non-noble metal Ni nanoparticles (NPs) as highly efficient co-catalysts are evenly anchored onto the surface of CdS nanowires (NWs) via a facile freeze calcination method. As a result, the H2 production performance of the optimal Ni/CdS NWs under the filter (lambda >= 420 nm) is about 80 times that of the bare CdS NWs, reaching 13,267.2 mu mol h-1 g-1 and the apparent quantum efficiency (AQE) is 9.3%. Further-more, Ni/CdS NWs photocatalysts have a surprising performance in the degradation of reactive red (RR2) and tetracycline hydrochloride (TCH), and the optimal photodegradation properties are 0.125 and 0.069 min- 1, respectively. According to the experimental characterization and theoretical calculation analysis, the deposition of Ni NPs not only increases the active sites of the reaction but also restrains the recombination of photoinduced charge carriers, so ameliorating the photocatalytic performance of CdS photocatalysts. This work provides a novel standpoint for designing non-noble metal co-catalyst/semiconductor photocatalysts for efficient solar energy conversion.

A crystalline, bi-photoelectric structural unit 2D periodic square lattice covalent organic framework was designed and target synthesized by the Schiff base condensation between 1,1,2,2-tetra(4-formyl-(1,1 '-biphenyl)) ethene and 5,10,15,20-tetrakis(4-amino phenyl)-21H,23H-porphyrin with AA stacking structures, named as TP-COF. The TP-COF exhibited good photoelectric response combined with good crystallinity and high specific surface area (1812 m(2) g(-1)). TP-COF with an optical bandgap of 1.80 eV can be used as a visible light responsive photocatalyst, and the speed of hydrogen evolution by TP-COF could achieve up to 58.4 mu mol g(-1)h(-1) under visible light irradiation. The efficient photocatalysis performance could be attributed to the photogenerated charge separation and transport of TP-COF by the fluorescence resonance energy transfer (FRET) from tetra-phenylethylene to porphyrin. The successful preparation of this type of COF according to the designed structure provides a new way to realize photocatalyst targeting synthesis for better photocatalysis.

Conjugated microporous polymers (CMPs) with redox-active sites have attracted extensive notice in rechargeable lithium-ion batteries (LIBs) due to their extended pi-conjugated structure, uniform porosity, and low solubility. However, poor electrical conductivity and low utilization of active sites limit their application in large-scale energy storage systems (ESS). Herein, we synthesized two carbonyl-rich imine-based CMPs by the polycondensation reaction between tetromino-benzoquinone and aldehydes, and integrated them with carbon nanotubes (TB-CMP@CNT and TBP-CMP@CNT). The composites display good electrochemical performances as anode-active materials of LIBs, which benefits from abundant redox-active units, stable pi-conjugated framework, and fast Li+ diffusion kinetics. Especially, TBP-CMP@CNT has a high reversible capacity of 954.6 mAh g(-1) at 50 mA g(-1), a long cycle stability at 1 A g(-1) with no decrease in capacity after 1000 cycles, and superior rate performance of 221.5 mAh g(-1) at 2 A g(-1).

CdS-based nanomaterials received much attention since it was synthesized and used as photocatalysts in HER reaction and degradations of organic pollutants. However, it is still an urgent issue to improve the stability and catalytic performance of these kinds of materials before they meet the requirements of the practical applications. Therefore, A novel nano-photocatalyst named as NC-15 was prepared in this paper by loading Ni3C nanosheets (NSs) and Ni nanoparticles (NPs) to the surface of CdS nanowires (NWs). Using a 300 W Xe-lamp (>= 400 nm) as the illumination source, NC-15 could accelerate the H2-evolution reaction (HER) in aqueous solution of lactic acid (10 vol%) with the rates of 15247 mu mol center dot g-1h-1 which is ca. 381-time higher than that of CdS NWs, and OTC (LEF) could be ca. 91 % (89 %) degenerated as its aqueous solution (40 ppm) were irradiated 60 mins. The electrochemical analysis indicates that NC-15 should be an n-type semiconductor with the overpotential of-1.08 V vs. Ag/AgCl, which is much lower than those of CdS NWs (-1.20 V), Ni3C/CdS (-1.18 V) and Ni/CdS (-1.13 V) and indicates a faster-photogenerated electrons transfer rate of NC-15. The theoretical simulations confirm that the Ni NPs should supply the active sites during the photocatalytic procedure and the internal electric field at the interfaces of CdS/Ni3C and Ni3C/Ni could accelerate the photogenerated carriers' separation and migration. In a word, CdS-based ternary nano-photocatalysts possess great potential in the practical application of HER and photodegradation reactions.

In this study, a phthalocyanine indium (InPcOH) and three porphyrin derivatives (Por2a, Por2b, Por2c) were successfully synthesized. Three kinds of novel four-arm star-shaped poly(propylene oxide) (PPO) with core of InPcOH and chain-end of porphyrin derivatives, named InPc-(PPOx-Por2n)(4) (n = a-c), were achieved through the InPcOH as initiator by ring-opening polymerization. From fluorescence spectra, InPc-(PPOx-Por2n)(4) polymers revealed weaker emission intensity at 704 nm in comparison with InPc-(PPO29)(4), proving energy transfer (ET) pathway from Por2a-2c to InPc, which could be established by theoretical study. Due to ET pathway, InPc-(PPOx- Por2n)(4) polymers showed stronger nonlinear optical (NLO) performance than InPc-(PPO29)(4) polymer. Among InPc-(PPOx-Por2n)(4), InPc-(PPO33-Por2b)(4) obtained the most outstanding NLO performance exhibiting imaginary third-order susceptibility (Im[chi((3))]) of 6.25 x 10(-11) esu, which could ascribe the efficient ET pathway from Por2b to InPc based on the appropriate spatial structure and small energy gap of Por2b. Moreover, the InPc-(PPO33-Por2b)(4)/polymethyl methacrylate (PMMA) composites were prepared for applying actually, and it displayed a prominent Im[chi((3))] value of 22.4 x 10(-11) esu and an outstanding limiting threshold of 0.14 J/cm(2). The remarkably enhanced NLO performance exhibited by InPc-(PPO33-Por2b)(4)/PMMA composites in comparison with that in methyl methacrylate solution prove a feeblish aggregation effect in PMMA matrix, which indicate the great potential of our polymers for real application in NLO field. This research could furnish a novel designing approach in terms of NLO materials that exhibit great performance.

Ladder-type conjugated polymers (LCPs) have attracted extensive attention in rechargeable lithium-ion batteries (LIBs) due to their inherent stability, poor solubility, tunable structure, and strong π—π intermolecular interactions. Herein, we describe the synthesis of two heteroatom nitrogen/oxygen-rich LCPs (TABQ-NTCDA, named TNL, and TABQ-PMDA, named TPL) by the polycondensation reaction of tetromino-benzoquinone (TABQ) and aromatic dianhydride. Benefiting from the rigid backbone, the large conjugated skeleton and the heteroatom-driven superlithiation process in polycyclic aromatic systems, heteroatom nitrogen/oxygen-rich LCPs acting as organic anode materials for LIBs display high specific capacity and long-term cycle stability. In particular, TNL displays a high reversible capacity of 1063.5 mA h g −1 at 0.05 A g −1 , good cyclic performance with a capacity retention of 75.2% after 1000 cycles at 1 A g −1 , and excellent rate capability of 260.6 mA h g −1 even at 2 A g −1 . In addition, the superlithiation storage mechanism was further confirmed by theoretical calculations, suggesting multiple active sites of C=O, C=N, and aromatic rings for lithium-ion storage. Furthermore, a full cell is also assembled by pairing a TNL anode with a LiCoO 2 cathode, indicating the feasibility of practical application.

The development of new pi-d conjugated metal coordination polymers (CCPs) provides broad prospects for exploring a new generation of energy storage materials. Here, we report the synthesis, characterization and lithium-ion storage properties of carbonyl-containing pi-d CCPs, which use tetraaminobenzoquinone (TABQ) as the organic ligand and M2+ (M = Co, Ni, and Cu) as the metal ligands. Among them, Ni-TABQ shows the higher conductivity and best electrochemical performance, when used as a cathode material in lithium-ion batteries (LIBs), it delivers a high initial discharge specific capacity of 318.7 mAhg-1 at 50 mA g(-1) and good rate performance (even 237.2 mAhg-1 at 2 Ag-1). The reason for the superior performance of Ni-TABQ as well as its lithium-ion storage mechanism is verified by density functional theory (DFT) and spectroscopic characterization. Encouragingly, Ni-TABQ can be served as both cathode and anode materials to construct high-performance all -organic symmetric LIBs, which delivers high energy density up to 142 Wh kg(-1) with stable cyclability for 100 cycles at 200 mA g-1. More importantly, the flexible all-organic pouch LIBs assembled by Ni-TABQ also show stable electrochemical properties under different bending states, demonstrating its great potential in the field of flexible wearable devices. These research results will highlight the vigorous application of pi-d CCPs in LIBs and provide new insights for the rational design of similar advanced electrode materials in other energy storage systems.

Narrowband electroluminescence from multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters have attracted much attention owing to their potential in developing high-resolution organic light emitting diode (OLED) displays. However, host materials used for MR-TADF emitters are mainly focused on small molecules that are relying on vacuum deposition for device fabrication. Here, we demonstrate the design of novel host materials with dendritic structures consisting of a non-conjugated adamantane core and four alkoxycapped carbazole dendrons in periphery for solution-processed MR-TADF OLEDs with highly efficient narrow band electroluminescence. By introducing electron-donating n-butoxy capping groups to carbazole units and using the second-generation dendrons instead of the first-generation ones, triplet energies for the dendritic hosts are kept at higher than 2.80 eV, but the highest occupied molecular orbital (HOMO) levels can be considerably elevated from-5.51 to-5.19 eV, leading to barrier-free hole injection from anode to emissive layer. Solution processed OLEDs based on the alkoxy-capped dendritic host and B,N-containing MR-TADF emitter reveal narrowband emission with full-width at half-maximum of 42 nm, together with low turn-on voltage of 2.8 V, maximum external quantum efficiency of 24.2% and power efficiency of 95.0 lm W-1, which represent the promising device efficiencies for narrowband electroluminescence by solution process.

Developing an ideal photothermal agent is one of the challenges for effective photothermal therapy (PTT). Herein, a green and simple yet versatile method is developed to construct a novel poly-(iron-dopamine coordination complexes) nanoparticles (P[Fe-DA]-NPs) based on polymerization and coordination synergistically by using Fe3+ ions and dopamine (DA) in aqueous solution, and simultaneously poly(vinylpyrrolidone) (PVP) is applied to improve dispersion stability. P[Fe-DA]-NPs can be laden into macrophages directly with no further purification required to target tumor tissue to perform cell-mediated strategy. P[Fe-DA]-laden macrophages as an ideal photothermal agent has the advantages of good biocompatibility, simple preparation process, high photothermal performance, and effective tumor targeting. Furthermore, the P[Fe-DA]-laden macrophages possess excellent photoacoustic imaging (PAI) capacity for guiding the precise PTT. The results show that the tumors are significantly suppressed after PTT with the help of the accurate PAI diagnosis. This cell-mediated strategy may be the most promising avenue for the future clinical cancer therapy.

In this work, a series of asymmetric and symmetric porphyrin derivatives (structure types: A4, A3B1, trans-A2B2, cis-A2B2, A1B3, and B4) have been synthesized via a one-pot method and characterized to identify their structures and properties.

4-(4-(1,2,2-triphenylvinyl)phenyl)benzoic acid (TPEPhCOOH) with Zn2+ ion induced solution emission (CISE) character was synthesized. The freshly prepared TPEPhCOOH film has the fluorescence (FL) at ca. 498 nm with the excited-state decay lifetime of 2.98 ns and the absolute luminescence quantum yield of 64.8%. The FL studies on the non-radiative TPEPhCOOH/THF solutions with different metal ions suggest that TPEPhCOOH could radiatively response to the presence of Zn2+ ions. The aggregation-induced emission character of TPEPhCOOH in the mixed water/THF solvent (ca. 10−5 mol/L), along with the molecular dynamic and the quantum mechanic calculations, suggests that the Zn2+ CISE of TPEPhCOOH should originate from the coordination between Zn2+ ions and the TPE moiety of TPEPhCOOH.

Organic carbonyl electrode materials are widely employed for alkali metal-ion secondary batteries in terms of their sustainability, structure designability and abundant resources. As a typical redox-active organic electrode materials, pyrene-4, 5, 9, 10-tetraone (PT) shows high theoretical capacity due to the rich carbonyl active sites. But its electrochemical behavior in secondary batteries still needs further exploration. Herein, PT-based linear polymers (PPTS) is synthesized with thioether bond as bridging group and then employed as an anode material for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). As expected, PPTS shows improved conductivity and insolubility in the non-aqueous electrolyte. When used as an anode material for LIBs, PPTS delivers a high reversible specific capacity of 697.1 mAh g -1 at 0.1 A g -1 and good rate performance (335.4 mAh g -1 at 1 A g -1 ). Moreover, a reversible specific capacity of 205.2 mAh g -1 at 0.05 A g -1 could be obtained as an anode material for SIBs.

In this report, a series of novel four-arm star-shaped polymethyl methacrylate with core of phthalocyanine indium polymers (InPc-(PMMA(x))(4)) were achieved with different molecular weights through Activator ReGenerated by Electron Transfer Atom Transfer Radical Polymerization, using the synthesized phthalocyanine indium (InPc-Br) as initiator. The InPc-(PMMA(x))(4) polymers were characterized by NMR, FT-IR, GPC, UV-Vis and PL spectroscopy. The nonlinear optical (NLO) properties of InPc-(PMMA(x))(4) polymers were investigated by the Z-scan technique and it revealed that InPc-(PMMA(16))(4) obtained satisfactory NLO properties with imaginary third order susceptibility (Im[chi((3))]) of 16.4 x 10(-12) esu. Furthermore, reacting polymer InPc-(PMMA(16))(4) with NaN3 and 1-(4-nitrophenyl)-2-(4-(prop-2-yn-1-yloxy) phenyl) diazene (Azo-yne) through click reaction, a novel InPc polymer InPc-(PMMA(16)-b-Azo)(4) was successfully synthesized. InPc-(PMMA(16)-b-Azo)(4) displayed a weak fluorescence at 707 nm compared to InPc-(PMMA(16))(4), demonstrating the energy transfer (ET) process between Azo and InPc, which could be proved by density functional theory. Because of the ET process, InPc-(PMMA(16)-b-Azo)(4) exhibited a better NLO performance than InPc-(PMMA(16))(4), with Im[chi((3))] of 20.7 x 10(-12) esu. In addition, the InPc-(PMMA(16)-b-Azo)(4)/PMMA complexes were prepared for the convenience of practical application, and it exhibited an excellent Im[chi((3))] value of 30.2 x 10(-12) esu and a satisfactory limiting threshold of 0.04 J/cm(2). The significantly enhanced NLO properties of InPc-(PMMA(16)-b-Azo)(4)/PMMA complexes demonstrate a weaker aggregation effect in polymethyl methacrylate matrix than in methyl methacrylate solution. Our study provides a promising design strategy to synthesize high performance NLO materials for practical applications.

One-pot synthesis of Co2P nanoparticles encapsulated into doped carbon nanotubes, which can be applied as ORR/OER bifunctional catalysts for Zn–air batteries.