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A benzo[rst]pentaphene (BPP) substituted by two bis(methoxyphenyl)amino (MeOPA) groups (BPP-MeOPA) was synthesized and clearly characterized by NMR and single-crystal X-ray analysis. Detailed investigations of its photophysical properties, including transient absorption spectroscopy analyses, revealed that the introduction of the MeOPA groups breaks the symmetry of the BPP core, improving its absorption and emission from an S1 state with both excitonic and charge-transfer character.

In contrast to zero-bandgap graphene, nanostructures of graphene, such as graphene quantum dots (GQDs) and graphene nanoribbons (GNRs) have open bandgaps due to the quantum confinement effect, and are thus highly interesting for semiconductor applications, for example in nanoelectronics and optoelectronics. While conventional methods cannot provide GQDs and GNRs with chemically precise structures, large polycyclic aromatic hydrocarbon (PAH) molecules can be regarded as atomically precise GQDs. Moreover, extension of the PAH synthesis can lead to GNRs with well-defined chemical structures. In this account, we summarize our recent achievements in our synthetic exploration of PAHs and GNRs with novel structures and properties. For example, we have developed new PAHs having zigzag edges, such as dibenzo[hi,st]ovalene derivatives with strong red luminescence and stimulated emission, which are promising for light-emitting devices and bioimaging applications. We have also accomplished a synthesisof magnetic GNRs through edge functionalization with organic radicals, which can be interesting for spintronicas well as quantum computing applications. Moreover, incorporation of zigzag edges in GNR structures, through on-surface syntheses under ultrahigh (UHV) vacuum conditions, allowed for significant modulations of the electronic structures of GNRs, leading to the emergence of topological quantum phases. On the other hand, we have also explored onsurface synthesisof GNRs without UHV, namelyusing a setup for chemical vapor deposition (CVD). Scalable fabrication of GNR films could thus be achieved on goldonmica substrates, which couldbe integrated into field-effect transistor devices. These results highlight the importance of developing novel PAHs and GNRs and their potentials for various applications, including quantum technologies, energy and optoelectronic devices, and bioimaging.

We report the synthesis of a dibenzodinaphthocoronene (DBDNC) derivative as a novel nanographene with armchair, zigzag, and fjord edges, which was characterized by NMR and X-ray crystallography as well as infrared (IR) and Raman spectroscopies. Ultrafast transient absorption (TA) spectroscopy revealed the presence of stimulated emission signals at 655 nm and 710 nm with a relatively long lifetime, which resulted in dual amplified spontaneous emission (ASE) bands under ns-pulsed excitation, indicating the promise of DBNDC as a near-infrared (NIR) fluorophore for photonics. Our results provide new insight into the design of nanographene with intriguing optical properties by incorporating fjord edges. This work was financially supported by the Okinawa Institute of Science and Technology Graduate University (OIST), the Max Planck Society, JSPS KAKENHI Grant No. JP19K24686, and the European Union’s Horizon 2020 Research and Innovation program under grant agreement no. 101017821 (LIGHT-CAP). G. M. P thanks Fondazione Cariplo (Grant no. 2018-0979) for financial support. Researchers from the University of Alicante acknowledge support from the Spanish Ministerio de Ciencia e Innovación and the European Union (Next Generation EU) through grant no. PID2020-119124RB-I00; and to the Conselleria de Innovación, Universidades y Sociedad Digital de la Comunidad Valenciana (Grant No. AICO/2021/093).

We report the on-surface synthesis and gas-phase theoretical studies of two novel nanographenes, namely, dibenzohexacenohexacene and dibenzopentaphenoheptaphene, using 8,8′-dibromo-5,5′-bibenzo[rst]pentaphene as a precursor. These nanographenes display a combination of armchair and zigzag edges, as shown by noncontact atomic force microscopy (nc-AFM), and their electronic properties are elucidated by density functional theory (DFT) calculations which reveal relatively low HOMO-LUMO energy gaps of about 1.75 eV.

Polymer light-emitting diodes (PLEDs) based on thermally activated delayed fluorescence (TADF) emitters show great potential in developing high-efficiency solution-processed light-emitting devices ...

Based on oligocarbazole, a carbazole/acridine hybrid and oligoacridine as the dendron, a series of solution processible triphenylphosphine-oxide-cored dendrimers denoted as 3CzCz-PO, 3AcCz-PO, and 3AcAc-PO have been designed and synthesized, respectively. With increasing electron-donating ability from the peripheral dendron, the singlet–triplet splitting (ΔEST) is found to be gradually reduced from 0.35 eV for 3CzCz-PO to 0.22 eV for 3AcCz-PO and 0.20 eV for 3AcAc-PO while retaining high triplet energy (T1) around 2.9 eV. As a result, 3AcAc-PO exhibits an obvious thermally activated delayed fluorescence (TADF) with a lifetime of 1.0 μs. When used as the host for the blue phosphor Ir(mpim)3, the corresponding solution-processed devices reveal a peak power efficiency of 46.4 lm W−1. And about 57% improvement is obtained for 3AcAc-PO compared with the non-TADF host H2 (29.6 lm W−1). The results clearly manifest the superiority of solution processible dendritic TADF hosts in power-efficient blue electrophosphorescent devices.

A deep-blue emitting poly(2′,3′,6′,7′-tetraoctyl-2,7-spirosilabifluorene), namely PSSiBF, has been newly developed for PLEDs. Unlike the previously-reported alkyl-functionalized P27SiF, the unwanted aggregation can be effectively prevented in PSSiBF due to the perpendicular arrangement between two spiro-linked dibenzosilole moieties. Compared with P27SiF (ΦPL = 0.62), consequently, an improved PLQY of 0.84 is obtained for the film of PSSiBF accompanied by a significant reduction of the long-wavelength emission in the range of 450–550 nm. Based on a double-layer device configuration, PSSiBF gives a bright deep-blue electroluminescence, revealing a state-of-art EQE of 2.8% and CIE coordinates of (0.16, 0.06). The simultaneous realization of good color purity and high EQE clearly implies that the silicon-containing polymers do have the great potential in efficient PLEDs.

Starting from poly(2,7-spirosilabifluorene) (PSSiBF), deep-blue emitting poly(5′-(5′′-hexylundecyl)-2,7-dibenzoazasiline-10′,9-silafluorene) (PSDBASiF) has been newly demonstrated for power-efficient PLEDs, where dibenzoazasiline instead of dibenzosilole is spiro-linked to the poly(dibenzosilole) backbone. Owing to the electron-donating nature of dibenzoazasiline, the HOMO and LUMO energy levels are found to be upshifted from −6.10/−2.40 eV of PSSiBF to −5.61/−2.16 eV of PSDBASiF. Simultaneously, hypsochromic absorption and emission maxima are observed for PSDBASiF, while its film photoluminescence quantum yield (PLQY) remains close to that of PSSiBF (0.84). PLEDs based on PSDBASiF realize a record-high power efficiency of 1.16 lm W−1 together with a peak EQE of 2.74% and CIE coordinates of (0.16, 0.06). Compared with PSSiBF (

Single white light-emitting polymers (SWPs) represent a high-fidelity system for generating white light emission from polymers without phase separation compared to polymer blend systems. However, their device performance so far has been limited because of the unwanted hole scattering caused by an energy-level mismatch between emitters and hosts, and the large injection barrier at the polymer/anode interface. Here, we report novel poly(arylene phosphine oxide)-based all-phosphorescent SWPs by using the combination of a high-HOMO-level blue phosphor and high-HOMO-level poly(arylene phosphine oxide) host to achieve a low turn-on voltage of 2.8 V, high external quantum efficiency of 18.0% and remarkable power efficiency of 52.1 lm W−1, which makes them the most efficient SWPs so far. This record power efficiency is realized by using the high-HOMO-level blue phosphor to eliminate the hole scattering effect and by using the high-HOMO-level polymer host to reduce the hole injection barrier. This result represents an important progress in SWPs to achieve efficiency surpassing that of the polymer blends currently used for solution-processed white organic light-emitting diodes (WOLEDs) and even comparable with that of the small molecules used for vacuum-deposited WOLEDs.

Helicene-based therapeutic agents for organelle-targeted photodynamic therapy (PDT) involving both type I and II are challenging and still underexplored. Herein, water-soluble nanoparticles containing twisted double [7]carbohelicene (D7H-NPs) are prepared through self-assembly with 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-2000] by a nanoprecipitation method. D7H-NPs display high water solubility with an average size of 46 ± 2 nm. Notably, D7H-NPs can generate efficient singlet oxygen (1 O2 ) and superoxide anion (O2· - ) upon white light irradiation, forming the basis of PDT. Moreover, the typical accumulation in lysosomes of 4T1 cancer cells paves the way to use D7H-NPs for lysosome-targeted cancer phototherapeutics. This paper reports a promising helicene-based phototherapeutic agent involving both type I and II PDT for organelle-targeted biotherapy.

Allelopathic rice can release allelochemicals from roots to inhibit neighboring plant species, but little is currently known about their fate and impact on microorganisms in paddy soil. This study showed that allelopathic rice P1312777 released much higher concentrations of allelochemical (5,7,4'-trihydroxy-3',5'-dimethoxyflavone) than non-allelopathic rice Liaojing-9 in field. When quantitative 5,7,4'-trihydroxy3',5'-dimethoxyflavone was added into soil, flavone gave a short half-life of 18.27 +/- 2.32 h (r(2) = 0.94) and could easily be degraded into benzoic acid. Benzoic acid with a half-life of 29.99 +/- 2.19 h (r(2) = 0.96) was more resistant toward degradation in paddy soil. Furthermore, both the culturable microbial population and the entire microbial community structure of soil incubated with flavone and benzoic acid were evaluated using the soil dilution plate method and phospholipid fatty acid (PLFA) analysis, respectively. It appeared from the results that flavone could reduce microorganisms especially for fungi present in paddy soil, while benzoic acid could induce a higher response for soil microorganisms especially for bacteria. Consequently, flavone would be responsible for the dynamics of soil microorganisms during the early period, and any observed effect during the late period would be very likely due to its degradation product. benzoic acid rather than flavone itself. These results suggested that allelopathic rice varieties could modify soil microorganisms to their advantage through the release of allelochemicals. The concentration and fate of discriminating 5,7,4'-trihydroxy-3',5'-dimethoxyflavone between allelopathic and non-alleloparhic varieties tested in rice soil would result in the different patterns of microbial population and community structure in paddy ecosystems.

Two flavone O-glycosides were isolated from allelopathic rice seedlings and have been identified as 5,4'-dihydroxy-3',5'-dimethoxy-7-O-beta-glucopyranosylflavone and 7,4'-dihydroxy-3',5'-dimethoxy-5-O-beta-glucopyranosylflavone. Considerable levels of these glycosides could be found in allelopathic rice tissues. They could not be detected in the soils growing these allelopathic rice seedlings. Only their aglycone, 5,7,4'-trihydroxy-3',5'-dimethoxyflavone, could be found in the soil. Further experiments showed that two flavone O-glycosides were exuded from allelopathic rice roots to the rihzosphere and then transformed into their aglycone form, that is, 5,7,4'-trihydroxy-3',5'-dimethoxyflavone, with a great diversity of biological activities on associated weeds and microbes by soil interactions once released. The glycosides degraded rapidly (t1/2 < 2 h), whereas their aglycone was more resistant toward degradation in paddy soils, in which the half-life (t1/2) at low (25 mug/g) and high (200 mug/g) doses reached 19.86 +/- 3.64 h (r 2 = 0.97) and 28.78 +/- 3.72 h (r 2 = 0.98), respectively. Furthermore, the mobility of both glycosides and their aglycone in paddy soil was evaluated by soil TLC with bioassay. The mobility of the glycosides (Rf = 0.418 +/- 0.069, n = 18) is higher than that of the aglycone (Rf = 0.361 +/- 0.048, n = 18). The results suggested that two flavone O-glycosides are formed in rice biosynthesis and that storage of the allelochemicals and their aglycone 5,7,4'-trihydroxy-3',5'-dimethoxyflavone is the agent of alleloapthic rice which interferes with weeds or microbes in paddy soil.