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Fine structural tuning of fluorescent copolymer sensors for methamphetamine vapor detection

Fluorescent sensors with high sensitivity, selectivity and fast response for trace detection of methamphetamine (MA) have been rarely reported. Herein, three fluorene-based sensory materials were synthesized and used for MA detection. The fine structural tuning could control both the energy level and bonding force to MA. Their fluorescence quenching responses to different amines were due to photo-induced electron transfer (PET) from MA donor to the photoexcited state of sensing polymers. Meanwhile, the fine-tuning of the bonding force resulted in different sensitivity and selectivity of the polymers. Among them, polymer with benzothiadiazole showed the best selectivity and sensitivity to MA vapor with a detection limit of 180 ppb. And ?20% fluorescence could be quenched/recovered within 2 s upon exposure to MA and air in sequence.

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Are molecular 5,8-pi-extended quinoxaline derivatives good chromophores for photoluminescence applications?

The synthesis of a new series of photoluminescent compounds, namely 5,8-diaryl quinoxaline derivatives (aryl = phenyl, 4-fluorophenyl, 4-methoxyphenyl, and 4-cyanophenyl), was achieved by a direct Suzuki cross-coupling reaction with the employment of a NCP-pincer palladacycle. The electrochemical and photophysical properties of these compounds were also investigated. Four new 4,8-diaryl-2,1,3-benzothiadiazoles were also synthesized in order to enable a comparison between the two types of nitrogen-containing pi-extended heterocycles. The substitution of a hydrogen atom at the 4-position of the aryl that is groups attached to the quinoxaline or benzothiadiazole base by either electron-donating or -withdrawing groups results in an increase in the bandgap energy (from 2.21 to 2.52 eV) of pi-extended 5,8-quinoxaline derivatives and a decrease in the bandgap energy (from 2.65 to 2.40 eV) of pi-extended 2,1,3-benzothiadiazoles. Moreover, pi-extension at the 5- and 8-positions of the quinoxaline core is not essential for the photoluminescence of these compounds and 4,7-pi-extended 2,1,3- benzothiadiazole derivatives are far better candidates for luminescence applications than are the quinoxaline derivatives. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

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CONJUGATED POLYMERS CONTAINING SPIROBIFLUORENE UNITS AND THE USE THEREOF

The present invention relates to novel conjugated polymers comprising spirobifluorene units and their use in optoelectronic devices, preferably in, for example, displays based on polymeric organic light-emitting diodes.

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Optical bandgaps and fluorescence resonance energy transfer studies of a series of poly(phenyleneethynylene) derivatives

In this paper, research work focuses on the synthesis of a series of PPE-based polymers with commonly used conjugated units, including thiophene, benzo[c][1,2,5]thiadiazole (BT), benzo[c][1,2,5]selenadiazole (BSe), etc. The optical bandgaps of these polymers were tuned in the range of 2.10-2.76 eV. The order of bandgap-lowering ability of these units in PPE-derivatives is: M-3 > M-6 > M-5 > M-4 > M-9 ? M-7, M-8 > M-2. Their FRET applications in polymer solar cell and TNT detection were studied respectively, and the results indicated that all these PPE-derivatives were good candidate materials for polymer solar cells or detecting TNT in solution. Furthermore, if electron-acceptor units had structures similar to the diphenylquinoxaline in the PPE-derivatives chain, the polymers would give a better fluorescence quenching in response to TNT compound. Polymers PPE-7 and PPE-8 were chosen as representative samples to investigate their photo-oxidative stability compared with that of PPVs or PTs. The results demonstrated that both polymers PPE-7 and PPE-8 were more photo-oxidatively stable than MEH-PPV or P3HT.

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Benzodipyrrole-based donor?acceptor boron complexes were designed and synthesized as near-infrared-absorbing materials. The electron-rich organic framework combined with the Lewis acidic boron co-ordination enabled us to tune the LUMO energy level and the HOMO?LUMO gap (i.e.,the absorption wavelength) by changing the organic acceptor units, the number of boron atoms, and the substituents on the boron atoms.

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Five fluorene-based co-oligomers have been prepared to study their self-assembly in a wide range of concentrations, from dilute solutions to the solid state. Subtle changes to the chemical structures, introduced to tune the emission colours over the entire visible range, induce strong differences in aggregation behaviour. Only two of the fluorescent co-oligomer derivatives self-assemble to form soluble fibrils from which fluorescent organogels emerge at higher concentrations. In contrast, the other compounds form precipitates. Mixed fluorescent co-oligomer systems exhibit partial energy transfer, which allows the creation of white-light-emitting gels. Finally, a mechanism for the hierarchical self-assembly of this class of materials is proposed based on experimental results and molecular modelling calculations.

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The accessibility of nitrogen sites makes a difference in selective CO2 adsorption of a family of isostructural metal-organic frameworks

By using three rigid diisophthalate organic linkers incorporating different numbers and orientations of Lewis basic nitrogen atoms into the spacers between two terminal isophthalate moieties, namely, 5,5?-(quinoline-5,8-diyl)-diisophthalate, 5,5?-(isoquinoline-5,8-diyl)-diisophthalate, and 5,5?-(quinoxaline-5,8-diyl)-diisophthalate, a family of isostructural copper-based metal-organic frameworks, ZJNU-43, ZJNU-44 and ZJNU-45, were successfully solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The three MOFs, after activation, exhibited almost the same porosities but distinctly different CO2 adsorption properties. At room temperature and 1 atm, the adsorption capacities for CO2 reached 103, 116 and 107 cm3 (STP) g-1 for ZJNU-43a, ZJNU-44a and ZJNU-45a, respectively. Furthermore, Ideal Adsorbed Solution Theory (IAST) and simulated breakthrough analyses indicated that ZJNU-44a bearing much more easily accessible nitrogen sites is the best among the three MOFs for the separation of the following two binary gas mixtures at 296 K, i.e., 50/50 CO2/CH4 and 15/85 CO2/N2 gas mixtures, indicating that the accessibility of nitrogen sites plays a much more crucial role, which is further confirmed by comprehensive quantum chemical calculations. The work demonstrates that the CO2 adsorption properties of MOFs depend not only on the number of Lewis basic nitrogen sites but also more importantly on their accessibility.

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Light-emitting properties of donor-acceptor and donor-acceptor-donor dyes in solution, solid, and aggregated states: Structure-property relationship of emission behavior

In this paper, we report a systematic study on the light-emitting behavior of a series of triphenylamine-based donor-acceptor-type dyes in the solution and solid states as well as in the aggregated state in polar aqueous media. The emission band shifted bathochromically along with the decrease in the fluorescence quantum yield as the solvent polarity was increased from nonpolar cyclohexane to polar DMF. In a THF/water medium, the emission was quenched in a low water volume, whereas the emission was recovered and increased in a high water volume. In a low water volume, the dye molecules exist in a monomeric form, and the fluorescence quenching increases with increasing water fraction, similar to that observed in the solvent-polarity-dependence study. In contrast, the dye molecules aggregated in a high water volume. This is probably because the inside of aggregates is less polar than the outside, thus preventing nonradiative deactivation and recovering the emission. This unusual emission was achieved by triphenylamine-based dyes containing a relatively strong acceptor moiety such as quinoxaline, benzothiadiazole, and thiadiazolopyridine, providing longer-wavelength red and near-IR emission. In the benzothiadiazole-based dyes, when the phenyl groups in the donor moieties were replaced with methyl groups, the fluorescence quantum yield decreased, indicating that the triphenylamine donor moiety is suitable for emission in the aggregated state. The nonplanar structure of triphenylamine disrupts an ordered packing and produces a less-ordered spherical aggregate, leading to an efficient light emission even in polar aqueous media.

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New quinoxaline derivatives as accepting units in donor-acceptor type low-band gap polymers for organic photovoltaic cells

A series of new donor-acceptor-type low-band-gap semiconducting polymers were synthesized as electron donors for organic photovoltaic cells. The polymers comprised quinoxaline derivatives as the acceptors and a benzodithiophene (BDT) derivative as the donors. 5,8-Dibromoquinoxaline (Qx), 8,11-dibromobenzo[a] phenazine (BPz), 10,13-dibromodibenzo[a,c]phenazine (DBPz), and 8,11-dibromo-5-(9H-carbazol-9-yl)benzo[a]phenazine) (CBPz) were synthesized and polymerized with 2,6-bis(trimethyltin)-4,8-diethylhexyloxybenzo-[1,2-b;3,4-b] dithiophene (BDT) through Stille cross-coupling to produce four types of fully conjugated semiconducting polymers: PBDT-Qx, PBDT-BPz, PBDT-DBPz, and PBDT-CBPz, respectively. Intramolecular charge transfer between the electron donating and accepting units in the polymeric backbone induced a broad absorption from 300 to 800 nm. The optical band gap energies of the polymers were measured from their absorption onsets to be 1.54-1.80 eV depending on the polymer structure. Solution-processed field-effect transistors were fabricated to measure the hole mobilities of the polymers, and bulk hetero-junction photovoltaic devices were fabricated using the synthesized polymers as electron donors and fullerene derivatives as electron acceptors. One of these devices showed a high power conversion efficiency of 3.87% with an open-circuit voltage of 0.78 V, a short-circuit current of 9.68 mA/cm2, and a fill factor of 0.51 under air mass 1.5 global (AM 1.5 G) illumination conditions (100 mW/cm2).

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Molecular engineering of quinoxaline-based organic sensitizers for highly efficient and stable dye-sensitized solar cells

A series of quinoxaline based metal-free organic sensitizers has been designed and synthesized for dye-sensitized solar cells (DSSCs). The absorption, electrochemical, and photovoltaic properties for all sensitizers have been systematically investigated. It is found that the incorporation of quinoxaline unit instead of thienopyrazine unit results in a negative shift of the lowest unoccupied molecular orbital levels for FNE44, FNE45, FNE46, and FNE47, in comparison to FNE32, which induces a remarkable enhancement of the electron injection driving force from the excited organic sensitizers to the TiO2 semiconductor. Moreover, when the alkyl substituents are removed from the spacer part in FNE44 to the donor part in FNE45 and FNE46, a more conjugated system and a bathochromically shifted maximum absorption band can be realized, which consequently results in an increased light harvesting efficiency and photogenerated current. In addition, the length of the alkyl substituents on the donor part has a certain influence on the DSSC performance. Combining the three contributions, FNE46-based DSSC with liquid electrolyte displays the highest power conversion efficiency (eta) of 8.27%. Most importantly, a eta of 7.14% has been achieved for FNE46 based quasi-solid-state DSSC and remained at 100% of the initial value after continuous light soaking for 1000 h, which indicates that FNE46 is appropriate for promising commercial application. Our findings will facilitate the understanding of the crucial importance of molecular engineering and pave a new path to design novel metal-free organic dyes for highly efficient and stable DSSCs.

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