Peculiar Photoinduced Electron Transfer in Porphyrin–Fullerene Akamptisomers

Porphyrin–fullerene dyads are promising candidates for organic photovoltaic devices. The electron-transfer (ET) properties of the molecular devices depend significantly on the mutual position of the donor and acceptor. Recently, a new type of molecular isomerism (akamptisomerism) has been discovered. In the present study, we explore how photoinduced ET can be modulated by passing from one akamptisomer to another. To this aim, four akamptisomers of the quinoxalinoporphyrin–[60]fullerene complex are selected for computational study. The most striking finding is that, depending on the isomer, the porphyrin unit in the dyad can act as either electron donor or electron acceptor. Thus, the stereoisomeric diversity allows one to change the direction of ET between the porphyrin and fullerene moieties. To understand the effect of akamptisomerism on the photoinduced ET processes, a detailed analysis of initial and final states involved in the ET is performed. The computed rate for charge separation is estimated to be in the region of 1–10 ns⁻¹. The formation of a long-living quinoxalinoporphyrin anion radical species is predicted.     

云制造平台加工能力分享调度优化研究

云制造平台加工能力分享的调度优化是云制造模式的核心运营问题。为提高云制造平台对参与能力分享企业资源的利用率,解决实际云制造需求环境下企业级制造资源调度问题,达到云制造平台动态实时的要求,以最小化工期和成本为目标函数,构建了基于平台并面向分享的云加工能力调度模型。为快速求解多个云任务订单的最优调度序列,引入任务简易编码和随机权重,设计了改进的二阶粒子群算法,并提出可分享加工能力时间窗的更新策略。最后,通过算例验证云制造平台加工能力调度机制的可行性和有效性。     

Low band‐gap D–A conjugated copolymers based on anthradithiophene and diketopyrrolopyrrole for polymer solar cells and field‐effect transistors

Two conjugated copolymers PADT‐DPP and PADT‐FDPP based on anthradithiophene and diketopyrrolopyrrole, with thiophene and furan as the π‐conjugated bridge, respectively, were successfully synthesized and characterized. The number‐averaged molecular weights of the two polymers are 38.7 and 30.2 kg/mol, respectively. Polymers PADT‐DPP and PADT‐FDPP exhibit broad absorption bands and their optical band gaps are 1.44 and 1.50 eV, respectively. The highest occupied molecular orbital energy level of PADT‐DPP is located at ?5.03 eV while that of PADT‐FDPP is at ?5.16 eV. In field‐effect transistors, PADT‐DPP and PADT‐FDPP displayed hole mobilities of 4.7 × 10^?3 and 2.7 × 10^?3 cm²/(V s), respectively. In polymer solar cells, PADT‐DPP and PADT‐FDPP showed power conversion efficiency (PCE) of 3.44% and 0.29%, respectively. Atomic force microscopy revealed that the poor efficiency of PADT‐FDPP should be related to the large two‐phase separation in its active layer. If 1,8‐diiodooctane (DIO) was used as the solvent additive, the PCE of PADT‐DPP remained almost unchanged due to very limited morphology variation. However, the addition of DIO could remarkably elevate the PCE of PADT‐FDPP to 2.62% because of the greatly improved morphology. Our results suggest that the anthradithiophene as an electron‐donating polycyclic system is useful to construct new D–A alternating copolymers for efficient polymer solar cells. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1652–1661     

Approaching the Integer‐Charge Transfer Regime in Molecularly Doped Oligothiophenes by Efficient Decarboxylative Cross‐Coupling

A library of symmetrical linear oligothiophene was prepared employing decarboxylative cross‐coupling reaction as the key transformation. Thiophene potassium carboxylate salts were used as cross‐coupling partners without the need of co‐catalyst, base, or additives. This method demonstrates complete chemoselectivity and is a comprehensive greener approach compared to the existing methods. The modularity of this approach is demonstrated with the preparation of discreet oligothiophenes with up to 10 thiophene repeat units. Symmetrical oligothiophenes are prototypical organic semiconductors where their molecular electrical doping as a function of the chain length can be assessed spectroscopically. An oligothiophene critical length for integer charge transfer was observed to be 10 thiophene units, highlighting the potential use of discrete oligothiophenes as doped conduction or injection layers in organic electronics applications.     

Insights into the Control of Optoelectronic Properties in Mixed-Stacking Charge-Transfer Complexes

Although cocrystallization has provided a promising platform to develop new organic optoelectronic materials, it is still a big challenge to purposely design and achieve specific optoelectronic properties. Herein, a series of mixed-stacking cocrystals (TMFA, TMCA, and TMTQ) were designed and synthesized, and the regulatory effects of the acceptors on the co-assembly behavior, charge-transfer nature, energy-level structures, and optoelectronic characteristics were systematically investigated. The results demonstrate that it is feasible to achieve effective charge-transport tuning and photoresponse switching by carefully regulating the intermolecular charge transfer and energy orbitals. The inherent mechanisms underlying the change in these optoelectronic behaviors were analyzed in depth and elucidated to provide clear guidelines for future development of new optoelectronic materials. In addition, due to the excellent photoresponsive characteristics of TMCA, TMCA-based phototransistors were investigated with varying light wavelength and optical power, and TMCA shows the best performance among all reported cocrystals under UV illumination.     

Charge-Transfer versus Charge-Separated Triplet Excited States of [ReI(dmp)(CO)3(His124)(Trp122)]+ in Water and in Modified Pseudomonas aeruginosa Azurin Protein

A computational investigation of the triplet excited states of a rhenium complex electronically coupled with a tryptophan side chain and bound to an azurin protein is presented. In particular, by using high-level molecular modeling, evidence is provided for how the electronic properties of the excited-state manifolds strongly depend on coupling with the environment. Indeed, only upon explicitly taking into account the protein environment can two stable triplet states of metal-to-ligand charge transfer or charge-separated nature be recovered. In addition, it is also demonstrated how the rhenium complex plus tryptophan system in an aqueous environment experiences too much flexibility, which prevents the two chromophores from being electronically coupled. This occurrence disables the formation of a charge-separated state. The successful strategy requires a multiscale approach of combining molecular dynamics and quantum chemistry. In this context, the strategy used to parameterize the force fields for the electronic triplet states of the metal complex is also presented.     

Crystal structure of a novel interrupted aluminosilicate,CNU-1 with an unusual framework

The crystal structure of a novel interrupted aluminosilicate, CNU-1, was synthesized hydrothermally at 433 K and was found to have a hexagonal crystal system, P-62c, in which an unusual T–O–T angle of 180°, similar to that of MWW, was discovered. Further, one of the hydroxyl groups in the interrupted structure was disordered systematically.     

煤与生物质混烧灰荷电特性研究

对玉米秸分别与两种煤以不同比例混烧生成的混烧灰进行了荷电特性研究。利用法拉第杯荷电量检测系统和静电低压撞击器(ELPI)测量了混烧灰的总体荷质比及分级荷质比,并借助于成分分析及形貌分析结果讨论了其影响机理。结果表明,随着生物质掺入量在混烧燃料中的增加,混烧灰的成分组成发生变化,使得其介电常数变大,比电阻增大,表面吸附能力增强,从而使混烧灰的总体荷质比有一定的上升趋势。对混烧灰的分级荷质比测量结果表明,排除灰样粒径的影响,生物质的掺入使得混烧灰的荷电能力得以增强,但影响相对较小,颗粒粒径是影响混烧灰荷电能力的主要因素。     

Enhancement of Light Absorption Ability of Synthetic Chlorophyll Derivatives by Conjugation with a Difluoroboron Diketonate Group

The enhancement of the light absorption ability of synthetic chlorophyll derivatives is demonstrated. Chlorophyll derivatives directly conjugated with a difluoroboron 1,3‐diketonate group at the C3 position were synthesized from methyl pyropheophorbide‐d through Barbier acylmethylation of the C3‐formyl moiety, oxidation of the C3‐carbinol, and difluoroboron complexation of the diketonate. Electronic absorption spectra in a diluted solution showed that the synthetic conjugates gave an absorption band at λ=400–500 nm, with a Qy band shifted to a longer wavelength of λ≈700 nm. DFT calculations demonstrated that the absorption bands and redshifts were ascribable to the coupling of the LUMO of chlorin with that of the difluoroboron diketonate moiety. The introduction of a pyrenyl group at the C3³‐position of the conjugate afforded an additional charge‐transfer band over λ=500 nm, producing a pigment that bridged the green gap in standard chlorophylls.     

Structural distortion,charge modulation and local anisotropies in magnetite below the Verwey transition using resonant X‐ray scattering

The pattern of charge modulations and local anisotropies below the Verwey transition has been determined and quantified in high‐quality Fe₃O₄ single crystals and thin films grown on MgO by using resonant X‐ray scattering at the Fe K‐edge. The energy, polarization and azimuthal angle dependencies of an extensive set of reflections with potential sensitivity to charge or local anisotropy orderings have been analyzed to explore their origins. A charge disproportion on octahedral B sites of 0.20 ± 0.05 e^? with [0 0 1] and cubic periodicities has been confirmed, while no significant charge disproportion has been obtained with [0 0 1/2] cubic periodicity. Additional charge modulations in the monoclinic a–b plane are also present. In addition, the occurrence of new forbidden (1, 1, 0) and (0, 0, 2n + 1/2) cubic reflections that arise from the anisotropy of the local structure around different tetrahedral and octahedral Fe atoms is shown. This complex pattern of weak charge modulations and local anisotropies is fully compatible with the low‐temperature crystal structure refined in the non‐polar C2/c space group and disproves any bimodal charge disproportion of the octahedral Fe atoms.