Figure-eight Structure Research Articles

Inner-Bond-Cleavage Approach to Figure-Eight Macrocycles from Planar Aromatic Hydrocarbons.

Figure-eight-shaped nonplanar π-systems adopt distinctive chiral D2-symmetric structures, which are ideal for realizing efficient circularly polarized luminescence (CPL). However, the short-step and enantioselective synthesis of figure-eight π-systems represents a considerable challenge for the conventional bottom-up synthetic strategy. Herein, we report that the oxidative cleavage of the internal double bond of a commercially available polycyclic aromatic hydrocarbon, i.e., dibenzo[g,p]chrysene (DBC), catalytically affords a figure-eight electron-accepting macrocycle, i.e., cyclobisbiphenylenecarbonyl (CBBC), with high scalability (up to 3.3 g) and excellent enantioselectivity (94% ee). This inner-bond-cleavage approach also applies to larger PAHs, affording highly distorted molecular frameworks that comprise two figure-eight subunits. Furthermore, we demonstrate that the peripheral functionalization of CBBC with carbazole afforded donor-acceptor-type emitter, which shows thermally activated delayed fluorescence and emits CPL with a g value of 1.0 × 10-2. This g value is ten times higher than those of previously reported chiral TADF-active emitters for circularly polarized organic light-emitting diodes. These results demonstrate that oxidative inner-bond cleavage is a powerful synthetic strategy for creating innovative materials that incorporate molecules with figure-eight structures.

Synthesis and physical properties of doubly-annulated [10]cycloparaphenylene

Abstract A doubly annulated cycloparaphenylene (CPP), in which two [N]paraphenylenes share one benzene unit by meta (m)-connection, m-,m-phenylene-[2N]CPP with N = 5 (2a), was synthesized by double annulation between a CPP precursor and 1,5-dibromo-2,4-diiodobenzene followed by reductive aromatization. The structure of 2a was confirmed by NMR, mass spectroscopy, and single crystal X-ray diffraction analysis. As 2a has a figure-eight structure, it can have a twisted Möbius topology. However, the X-ray analysis clearly reveals a non-twisted Hückel topology in a solid state. The photophysical and electrochemical properties of 2a were also clarified. The studies proved that, while 2a can also be seen as ortho (o)-,o- or para (p)-,p-connected [10]CPP, 2a has an meta (m)-,m-connected electronic structure. The theoretical calculations also support this conclusion.

L-band Wavelength-Switchable Dissipative Soliton Resonance Er-doped Fiber Laser

The experiment reports a kind of L-band dissipative soliton resonance (DSR) nanosecond Er-doped fiber laser. The passive mode-locked L-band DSR pulse is achieved in a figure-eight structure by using the nonlinear-amplifying-loop-mirror (NALM). The repetition rate of pulse is 468 kHz. At the maximum pump power of 398 mW, the output power is 25 mW with a pulse energy of 45 nJ. By adjustment of polarization state in cavity, the output pulse can be switched among 4 different DSR states with central wavelength of 1572, 1585, 1590 and 1605 nm discretely, presenting different peak power and pulse width. We can determine that the adjustment of polarization state changes the loss spectra of cavity and the 4 DSR states operate in different balance points. The tunable DSR pulse duration is from 120 to 150 ns by increasing the central wavelength.

Figure-eight Octaphyrin Bis-Ge(IV) Complexes: Synthesis, Structures, Aromaticity, and Chiroptical Properties.

Highly twisted structures of expanded porphyrin provide a prominent basis to unravel the relationship between aromaticity and chirality. Here we report the synthesis of bis-Ge(IV) complexes of [38]octaphyrin that display rigid figure-eight structures. Two bis-Ge(IV) [38]octaphyrin isomers with respect to the stereochemistry of the axial hydroxy groups on the germanium ions were obtained and found to be aromatic. Upon oxidation with MnO2 , these [38]octaphyrin complexes were converted to a single syn-type isomer of [36]octaphyrin with retained figure-eight conformation. The enantiomers have been successfully separated by HPLC equipped with a chiral stationary phase. While aromatic [38]octaphyrin Ge(IV) complexes showed quite large molar circular dichroism of up to Δϵ=1500 M-1 cm-1 with a dissymmetry factor gabs of 0.035, weakly antiaromatic [36]octaphyrin Ge(IV) complexes underscored moderate values; Δϵ=540 M-1 cm-1 with gabs of 0.023. Thus, the figure-eight octaphyrin scaffold has been proved to be an attractive platform for novel chiroptical materials with tunable aromaticity.

High-power 1.6 μm noise-like square pulse generation in an all-fiber mode-locked laser

We demonstrate generation of high-power and large-energy noise-like square pulses at 1612 nm in an all-fiber dumbbell-shaped mode-locked Er: Yb co-doped double-clad fiber (EYDF) laser. The custom couplers with high power handling keep the laser function well. Large-mode-area EYDF with high power handling and enough high pump power make it possible to obtain high output power in the oscillator. Compared with figure-eight structure, strictly all-fiber dumbbell-shaped structure without isolator and optimizing splicing loss could reduce intra-cavity loss and improve optical to optical efficiency, which could reduce heat accumulation and enhance the power carrying capacity of EYDF. In order to study the influence of in-band absorption on output wavelength, EYDF1 and EYDF2 with different in-band absorption coefficients are accessed to intracavity, respectively. It is directly demonstrated that regulation of in-band absorption is an effective way to control the output wavelength. Strong in-band absorption could restrain the emission of C-band and make the wavelength range above 1.6 μm obtain enough gain. Linear insertion loss is another important factor to affect the emission wavelength in EYDF fiber laser. At pump power of 8 W, maximum average output power with emission wavelength above 1.6 μm can reach 1.16 W, corresponding to a single pulse energy of 1.26 μJ. SNR of output pulse is 70 dB which indicates the high stability of mode-locking. In order to verify and evaluate influence of insertion loss on the output characteristics of mode-locked laser, a variable attenuator is inserted in experimental setup, allowing us adjust the linear loss of the cavity. By increasing pump power and adjusting PCs, mode-locked pulses could be obtained on the condition of large additional insertion loss. Even though ~ 10 dB additional insertion loss is introduced, the oscillation still could function at 1612 nm and keep stable mode-locked state. This result demonstrates our oscillation could bear strong additional loss and own strong robustness. If excessively large additional insertion loss is added, 1566 nm becomes the central emission wavelength and wavelength component at 1612 nm almost disappears. Our investigation supplies a direct guideline to design high-power fiber laser with emission wavelength above 1.6 μm.

Theoretical Study on the Conformation and Aromaticity of Regular and Singly N-Confused [28]Hexaphyrins

Structures and electronic states of regular and singly N-confused [28]hexaphyrins(1.1.1.1.1.1) were thoroughly studied with the aid of DFT calculations. To obtain systematic information, all the conceivable structures (450 structures in total) were examined. Unlike the [26]hexaphyrins(1.1.1.1.1.1) reported previously (J. Org. Chem. 2010, 75, 8213-8223), the electronic states of [28]hexaphyrins were highly affected by their conformations. The planar conformers (dumbbell, rectangular, triangular) show Hückel antiaromaticity, while the singly twisted conformers show Möbius aromaticity. Figure-eight structures correspond to the doubly twisted structures and show nonaromaticity. Disruption of annulenic circuits in singly N-confused [28]hexaphyrins caused weakening of both aromatic and antiaromatic characteristics. Relative stabilities among conformers were mainly governed by the intramolecular hydrogen bonds and secondarily affected by the steric factors. In addition, interconversion pathways among conformers were proposed on the basis of calculations on singly N-confused [28]hexaphyrins.

Anion-Controlled Circular Dichroism Spectral Changes in Hg2+ Complexes with a Chiral Bidentate Ligand

Anion-controlled circular dichroism (CD) spectral changes in Hg(2+) complexes with a chiral bidentate ligand are reported. Although the Hg(CF(3)SO(3))(2) and Hg(CF(3)CO(2))(2) complexes with (R)-(-)-1-(naphthalen-1-yl)-N,N-bis(pyridin-4-ylmethyl)ethanamine, (R)-(-)-1, show significant CD spectral changes, no CD spectral changes were observed in the HgCl(2), HgBr(2), Hg(CN)(2), or Hg(CH(3)CO(2))(2) complexes. X-ray analysis indicates that both the (R)-(-)-1-Hg(CF(3)SO(3))(2) and (R)-(-)-1-HgCl(2) complexes form a coordination polymer and a discrete 2:3 [=(R)-(-)-1/HgCl(2)] complex with a figure-eight structure. X-ray crystallography revealed that (i) the Hg-Hg distances bridged by anions vary depending on the anions used and (ii) a coordination polymer cannot be formed when the Hg-Hg distances are too short. Therefore, the formation of a coordination polymer is required to give the observed significant CD spectral changes.

Structural Dependence on Excitation Energy Migration Processes in Artificial Light Harvesting Cyclic Zinc(II) Porphyrin Arrays

A series of covalently linked cyclic porphyrin arrays CNZ that consist of N/2 of meso-meso directly linked zinc(II) porphyrin dimer subunits Z2 bridged by 1,3-phenylene spacers have been prepared by Ag(I)-promoted oxidative coupling reaction. We have investigated the excitation energy migration processes of CNZ in toluene by using femtosecond transient absorption anisotropy decay measurements by taking 2Z2 composed of two Z2 units linked by 1,3-phenylene as a reference molecule. On the basis of the excitation energy transfer rate determined for 2Z2, we have revealed the excitation energy hopping rates in the cyclic arrays CNZ by using a regular polygon model. The number of excitation energy hopping sites N(flat) calculated by using a regular polygon model is close to the observed N(expt) value obtained from the transient absorption anisotropy decays for C12Z-C18Z with circular and well-ordered structures. On the other hand, a large discrepancy between N(flat) and N(expt) was found for smaller or larger arrays (C10Z, C24Z, and C32Z). In the case of C10Z, m-phenylene linked 2Z2 motif with the interchromophoric angle of 120 degrees is not well suited to make a cyclic pentagonal array C10Z based on planar pentagonal structure. This geometrical factor inevitably causes a structural distortion in C10Z, leading to a discrepancy between N(expt) and N(flat) values. On the contrary, the presence of highly distorted conformers such as figure-eight structures reduces the number of effective hopping sites N(expt) in large cyclic arrays C24Z and C32Z. Thus, our study demonstrates that not only the large number of porphyrin chromophores in the cyclic arrays CNZ but the overall rigidity and three-dimensional orientation in molecular architectures is a key factor to be considered in the preparation of artificial light harvesting porphyrin arrays.

Observation of Equilibria with a Double Magnetic Axis in LHD

Finite-beta equilibria with a double magnetic axis have been realized in the Large Helical Device (LHD). Since the rotational transform is weak in the central region of the LHD, the effect of an externally applied quadrupole field is more pronounced in the central region than in the periphery. Consequently, the magnetic axis splits due to a moderate elongation. In the case of vertical elongation, the figure-eight structure of the magnetic surfaces has been observed in a soft X-ray image. Degradation of confinement due to the appearance of the separatrix is suggested in the case of horizontal elongation, which is closely related to the equilibrium beta limit. The three-dimensional magnetohydrodynamic equilibrium code HINT, which does not assume the existence of nested flux surfaces, provides physical pictures consistent with the experimental observations.

Theoretical considerations of doublet-like configuration in LHD

In order to investigate the separatrix structure inside the plasma, the magnetohydrodynamic (MHD) equilibrium and the high-energy particle orbit are studied for the Large Helical Device plasmas with two magnetic axes located within the two lobes of a figure-eight magnetic separatrix. Magnetic axes are split for strongly elongated cross section by the external quadrupole field. MHD equilibria without assuming existence of nested flux surfaces are obtained from the HINT code. For the vertical elongation, the figure-eight structure evolves due to the finite beta effect and the structure of magnetic field lines outside the separatrix is ergodized. For the horizontal elongation, the Shafranov shift is very large Δ/a > 0.5. To see MHD equilibrium beta limit, high beta equilibrium (∼5%) is studied. The magnetic axis shifts extremely to the outside of the torus and a new figure-eight separatrix appears. The particle orbit on the separatrix is studied by solving the guiding-centre drift equation on the rectangular grid. If the reflecting point of the trapped particle is close to the separatrix, the banana width is very large implying large, nonlocal neoclassical transport.

The construction of DNA molecules of figure-eight structure

Using DNA molecules to construct a structural scaffold for nanotechnology is largely accepted. In this article, we report on two methods for constructing a figure-eight structure of DNA molecules having a relatively high yield that could be used further as a scaffold for nanotechnology applications. In the first method, two plasmids were constructed that, on digestion with a restriction endonuclease producing nicks in the corresponding sites and after heating, produced complementary single-stranded sequences, enabling the plasmids to hybridize to each other and forming a figure-eight structure. The formation of the figure-eight structure was analyzed by restriction analysis and gel electrophoresis as well as by atomic force microscopy. The second method makes use of the bacteriophage M13 that is obtained as either a single- or double-stranded circular DNA molecule. Two M13 molecules harboring complementary sequences were constructed and produced a figure-eight structure on hybridization. The methods described here could be used further for the construction of nanoelectronic devices

Helical Superstructures of Fullerene Peapods and Empty Single-Walled Carbon Nanotubes Formed in Water

Aqueous dispersions of fullerene C70-filled carbon nanotubes (C70@SWNTs or peapods) and empty single-walled carbon nanotubes (empty SWNTs) were prepared with the aid of trimethyl-(2-oxo-2-pyrene-1-yl-ethyl)-ammonium bromide (1), which is a carbon nanotube solubilizer. This is the first report describing the preparation and characterization of the transparent dispersion/dissolution of the peapods. The UV-vis-near-IR spectra of C70@SWNTs-1 and empty SWNTs-1 were almost identical. We found by means of transmission electron microscopy and atomic force microscopy that the empty SWNTs and C70-peapods form helical nanostructures in the shapes of rings, irregular rings, lassos, handcuffs, catenanes, pseudorotaxanes, and figure-eight structures. The mechanism of the superstructure formation has been discussed in relation to the unique characteristics of stiff polymer chains with the aid of an off-lattice Monte Carlo simulation.

Tight and loose shapes in flat entangled dense polymers.

We investigate the effects of topological constraints (entanglements) on two-dimensional polymer loops in the dense phase, and at the collapse transition (theta-point). Previous studies have shown that in the dilute phase the entangled region becomes tight, and is thus localised on a small portion of the polymer. We find that the entropic force favouring tightness is considerably weaker in dense polymers. While the simple figure-eight structure, created by a single crossing in the polymer loop, localises weakly, the trefoil knot and all other prime knots are loosely spread out over the entire chain. In both the dense and theta conditions, the uncontracted-knot configuration is the most likely shape within a scaling analysis. By contrast, a strongly localised figure-eight is the most likely shape for dilute prime knots. Our findings are compared to recent simulations.

Enzymatic formation of biparental figure-eight molecules from plasmid DNA and their resolution in E. coli

A key intermediate in general genetic recombination is a structure in which two double-stranded DNA molecules are covalently linked by a single-strand crossover characteristic of a Holliday junction. When the DNA molecules are circular, the recombinant structures take the form of a figure eight. We have used purified E. coli enzymes to construct biparental figure-eight DNA molecules in vitro from the DNA of two partially homologous plasmids. When purified figure-eight structures are transfected into recA − E. coli cells, they are resolved to produce monomeric or dimeric plasmid progeny, apparently by the cutting and joining of the Holliday crossover. The maturation of figure-eight molecules in bacteria is characterized by the formation and recovery of both parental and recombinant types, crossing-over at a frequency of up to 50% and the capability for mismatch repair at regions of hybrid DNA. In these three regards, the products of figure-eight maturation resemble recombinant chromosomes formed at meiosis. These observations show that biparental figure eights behave as recombination intermediates that can be resolved into mature recombinants without need for a functional recA + gene product.