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Patrick E. Hartnett Scott M. Dyar Eric A. Margulies Leah E. Shoer Andrew W. Cook Samuel W. Eaton Tobin J. Marks Michael R. Wasielewski 《Chemical science》2015,6(1):402-411
The photophysics of a covalently linked perylenediimide–diketopyrrolopyrrole–perylenediimide acceptor–donor–acceptor molecule (PDI–DPP–PDI, 1) were investigated and found to be markedly different in solution versus in unannealed and solvent annealed films. Photoexcitation of 1 in toluene results in quantitative charge separation in τ = 3.1 ± 0.2 ps, with charge recombination in τ = 340 ± 10 ps, while in unannealed/disordered films of 1, charge separation occurs in τ < 250 fs, while charge recombination displays a multiexponential decay in ∼6 ns. The absence of long-lived, charge separation in the disordered film suggests that few free charge carriers are generated. In contrast, upon CH2Cl2 vapor annealing films of 1, grazing-incidence X-ray scattering shows that the molecules form a more ordered structure. Photoexcitation of the ordered films results in initial formation of a spin-correlated radical ion pair (electron–hole pair) as indicated by magnetic field effects on the formation of free charge carriers which live for ∼4 μs. This result has significant implications for the design of organic solar cells based on covalent donor–acceptor systems and shows that long-lived, charge-separated states can be achieved by controlling intramolecular charge separation dynamics in well-ordered systems. 相似文献
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Z Zhu AC Fahrenbach H Li JC Barnes Z Liu SM Dyar H Zhang J Lei R Carmieli AA Sarjeant CL Stern MR Wasielewski JF Stoddart 《Journal of the American Chemical Society》2012,134(28):11709-11720
Two redox-active bistable [2]catenanes composed of macrocyclic polyethers of different sizes incorporating both electron-rich 1,5-dioxynaphthalene (DNP) and electron-deficient 4,4'-bipyridinium (BIPY(2+)) units, interlocked mechanically with the tetracationic cyclophane cyclobis(paraquat-p-phenylene) (CBPQT(4+)), were obtained by donor-acceptor template-directed syntheses in a threading-followed-by-cyclization protocol employing Cu(I)-catalyzed azide-alkyne 1,3-dipolar cycloadditions in the final mechanical-bond forming steps. These bistable [2]catenanes exemplify a design strategy for achieving redox-active switching between two translational isomers, which are driven (i) by donor-acceptor interactions between the CBPQT(4+) ring and DNP, or (ii) radical-radical interactions between CBPQT(2(?+)) and BIPY(?+), respectively. The switching processes, as well as the nature of the donor-acceptor interactions in the ground states and the radical-radical interactions in the reduced states, were investigated by single-crystal X-ray crystallography, dynamic (1)H NMR spectroscopy, cyclic voltammetry, UV/vis spectroelectrochemistry, and electron paramagnetic resonance (EPR) spectroscopy. The crystal structure of one of the [2]catenanes in its trisradical tricationic redox state provides direct evidence for the radical-radical interactions which drive the switching processes for these types of mechanically interlocked molecules (MIMs). Variable-temperature (1)H NMR spectroscopy reveals a degenerate rotational motion of the BIPY(2+) units in the CBPQT(4+) ring for both of the two [2]catenanes, that is governed by a free energy barrier of 14.4 kcal mol(-1) for the larger catenane and 17.0 kcal mol(-1) for the smaller one. Cyclic voltammetry provides evidence for the reversibility of the switching processes which occurs following a three-electron reduction of the three BIPY(2+) units to their radical cationic forms. UV/vis spectroscopy confirms that the processes driving the switching are (i) of the donor-acceptor type, by the observation of a 530 nm charge-transfer band in the ground state, and (ii) of the radical-radical ilk in the switched state as indicated by an intense visible absorption (ca. 530 nm) and near-infrared (ca. 1100 nm) bands. EPR spectroscopic data reveal that, in the switched state, the interacting BIPY(?+) radical cations are in a fast exchange regime. In general, the findings lay the foundations for future investigations where this radical-radical recognition motif is harnessed in bistable redox-active MIMs in order to achieve close to homogeneous populations of co-conformations in both the ground and switched states. 相似文献
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Simple Zeros of the Riemann Zeta-Function 总被引:1,自引:0,他引:1
Assuming the Riemann Hypothesis, Montgomery showed by meansof his pair correlation method that at least two-thirds of thezeros of Riemann's zeta-function are simple. Later he and Taylorimproved this to 67.25 percent and, more recently, Cheer andGoldston increased the percentage to 67.2753. Here we proveby a new method that if the Riemann and Generalized LindelöofHypotheses hold, then at least 70.3704 percent of the zerosare simple and at least 84.5679 percent are distinct. Our methoduses mean value estimates for various functions defined by Dirichletseries sampled at the zeros of the Riemann zeta-function. 1991Mathematics Subject Classification: 11M26. 相似文献
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Quantum Zeno and anti-Zeno paradoxes 总被引:1,自引:0,他引:1
Continuous observation of a time independent projection operator is known to prevent change of state (the quantum Zeno paradox).
We discuss the recent result that generic continuous measurement of time dependent projection operators will in fact ensure
change of state: an anti-Zeno paradox. 相似文献
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DC magnetization, neutron depolarization and neutron diffraction (with both polarized and unpolarized neutrons) measurements
have been reported for the Co1.1−x
Zn
x
Ge0.1Fe1.2O1 spinels with x=0.5, 0.6 and 0.7. Neutron depolarization and neutron diffraction measurements confirm the presence of a long range ferrimagnetic
ordering of the local canted spins in these ferrite samples. The observed features of low field magnetization have been explained
under the framework of thermally activated domain wall movement of ferrimagnetic arrangement of local canted spins. An important
role of magnetic anisotropy (due to the presence of Co2+ ions) in establishing the magnetic ordering and domain kinetics in these ferrites has been observed. 相似文献
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粉粒体两相流的电容层析成象测量 总被引:4,自引:0,他引:4
粉粒体系统中的固相浓度分布的在线测量是十分困难的问题.电容层析成象技术是一种近年来发展起来的非侵入式快速浓度场测量技术.它不干扰流场,不受流动中颗粒浓度、加速度、不透明等因素的制约.本文讨论其测量原理、应用、近期进展、存在的主要问题及其解决的对策. 相似文献
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ac Conductivity measurements are carried out across the metal to insulator transition in NiAl0.7Cr0.7Fe0.6O4. The low frequency data is analyzed using Summerfield scaling theory for hopping conductivity. The exponent of the scaling
behavior has significantly different values in the conducting and insulating regimes. The hopping frequency and the zero frequency
conductivity are found to increase with temperature, slowly in the metallic regime and rapidly in the insulating regime. 相似文献