Dynamic Variation of Excitonic Coupling in Excited Bilayer Graphene Quantum Dots?

The intermolecular interaction determines the photophysical properties of the organic aggregates, which are critical to the performance of organic photovoltaics. Here, excitonic coupling, an important intermolecular interaction in organic aggregates, between the π-stacking graphene quantum dots is studied by using transient absorption spectroscopy. We find that the spectral evolution of the ground state bleach arises from the dynamic variation of the excitonic coupling in the excited π-stacks. According to the spectral simulations, we demonstrate that the kinetics of the vibronic peak can be exploited as a probe to measure the dynamics of excitonic coupling in the excited π-stacks.     

Preparation, structure and properties of novel 1,3-dithiol-2-ylidene derivatives containing bis(ethynylpyridine) units

1,3-Dithiol-2-ylidene derivatives containing bis(ethynylpyridine) units were synthesized using a Pd-catalyzed reaction of the corresponding dibromide. X-Ray crystal analysis revealed unique crystal structures depending on the aromatic groups. The absorption spectra and redox properties indicated intramolecular charge-transfer interactions between the 1,3-dithiole unit and the pyridyl parts.     

NDMAP: the best material to study the Haldane's prediction

As predicted by Haldane, spin, S=1 one-dimensional (1D) Heisenberg antiferromagnet (HAF) has an energy gap between the singlet ground state and first excited triplet. On application of magnetic field, the triplet state Zeeman splits and the energy of one of the triplet state becomes zero at a critical field, H_c. Above H_c the system recovers magnetism. Then, we expect that a quasi-1D HAF will show a magnetic long-range ordering (LRO) at low temperatures due to the inter-chain coupling. This field-induced LRO has not been observed before due to complication of the crystal structure in the materials studied so far and/or technical difficulty.From a heat capacity measurement on a single crystal of an S=1 quasi-Q1D HAF, Ni(C₅H₁₄N₂)₂N₃(PF₆), we found an anomaly at a temperature in finite fields indicating a field-induced phase transition. A magnetic LRO is confirmed by a neutron diffraction measurement on the same sample. The temperature versus magnetic field phase diagram of this compound is constructed and discussed.     

Experimental and quantum chemical study of pyrrole self-association through N-H?π hydrogen bonding

An FT-IR study of pyrrole self-association in CCl₄ solutions was carried out. According to the IR measurements, pyrrole forms self-associated dimeric species via N-H?π hydrogen bonding. This was also confirmed by quantum chemical calculations for pyrrole monomer and dimer at B3LYP/6-31++G(d,p) level of theory. A T-shaped minimum was located on B3LYP/6-31++G(d,p) PES of pyrrole dimer characterized with a hydrogen bond of an N-H?π type, with centers-of-mass separation of monomeric units of 4.520 Å, H?π distance of 2.475 Å, the interplanar angle between the two monomeric units being 72.9°. The anharmonic vibrational frequency shift upon dimer formation calculated on the basis of 1D DFT vibrational potentials is in excellent agreement with the experimental data (84 vs. 87 cm⁻¹). Harmonic vibrational analysis predicts somewhat smaller shift (68 cm⁻¹). On the basis of NIR spectroscopic data, anharmonicity constants for the 2ν(N-H) and 2ν(N-H?π) vibrational transitions were calculated. The orientational dynamics of monomeric and self-associated pyrrole species was studied within the framework of the transition dipole moment time correlation function formalism. The period of essentially free rotation in the condensed phase reduces from 0.05 ps for the monomeric pyrrole to 0.02 ps for the proton-donor molecule within the dimer.     

Complexes in polymers IV. FTIR microscopic characterization of thin organic polymer films containing embedded transition-metal carbonyl complexes

Thin films of polystyrene (PS), poly(methyl methacrylate) (PMMA) and polystyrene-polyacrylonitrile copolymer (PS-AN), containing various embedded transition-metal complexes, have been studied by FTIR microscopy. The spatial distributions of the transition-metal carbonyl complexes throughout the thin organic polymer films have been determined by a two-dimensional IR mapping procedure. The spectral variations observed in the distribution of the metal carbonyls throughout the different polymer films are discussed. The IR data show that the technique used to prepare the organometallic-embedded thin films (viz. freeze-drying of solutions followed by hot mechanical pressing of the residues) does in general lead to homogeneous films which may eventually find industrial application, e.g. as membrane sensors for small molecules.     

Applications of fast atom bombardment mass spectrometry (FAB MS) to organometallic and coordination chemistry

This article describes the technique of fast atom bombardment mass spectrometry (FAB MS) and its applications to the analysis of organometallic and coordination complexes. Sections on ion generation and matrices are followed by a Periodic Group-based review of FAB MS results obtained from Transition Metal and Main Group compounds, organometallic cluster carbonyls and their derivatives, and salts of poly-oxo-anions. The literature has been surveyed from 1981 to approximately mid-1986.     

偶氮苯衍生物三阶非线性的四波混频研究

用皮秒Ｎｄ：ＹＡＧ激光器的倍频光（５３２ｎｍ）对具有离域π－共轭电子云结构的偶氮苯类样品材料作简并四波混频补给，测得三阶非线性电极化率ｘ＾（３）和它们的时间响应分别为１０＾－９ｅｓｕ和２０ｐｓ，并对影响ｘ＾（３）的瞬时光栅作用和ｘ＾（３）的响应时间人了讨论。     

A convenient microwave assisted arylzinc generation-Negishi coupling protocol

Arylzinc reagents were readily prepared from aryl iodides using a Zn-Cu couple in a microwave environment. A sequential arylzinc formation-Negishi cross-coupling protocol suitable for parallel high-throughput synthesis has been developed.     

Organometallic complexes in ascidian embryonic development: II. Effects on different stages and larvae

The effects of the organometallic compounds Bu₂Sn-D -(?;)sorbitol, Bu₂Sn-D -(+)glucose, Bu₂Sn-D -(?)fructose and Bu₂Sn-D -(+)glyceraldehyde were tested in vivo on different stages of Ascidian development, larval movement and metamorphosis. Organotin(IV) complexes are organometallic compounds widely used as industrial biocides, antifouling agents and agricultural fungicides and are toxic to a range of organisms. Two-cell stage embryos, if incubated for one hour in the organotin (IV) solutions, stopped the cleavage, which was restored when they were transferred into normal sea water. The gastrula stage was seriously affected in 10^?4mol dm^?3 solutions of the above-mentioned complexes: 85% of the embryos were anomalous neurulae with open neural folds, 5% were twisted larvae. The gastrulae, when incubated for 1 h in 10^?5mol dm^?3 solutions, developed twisted larvae in ovular envelopes and immobile larvae with twisted tails. Larvae treated with 10^?4mol dm^?3 and 10^?5 mol dm^?3 Bu₂Sn-D -(?)sorbitol, Bu₂Sn-D -(+)glucose and Bu₂Sn-D -(+)glyceraldehyde solutions stopped swimming, did not metamorphose and afterwards underwent cytolysis. An initial hyperactivity of circular movements, followed by immobility, was observed in the larvae incubated in Bu₂Sn-D -(?;)fructose.     

镍 钴 钯 铁2—（二苯基膦基）吡啶配合物的合成及其催化羰基化反应

众所周知,铑催化剂是醇类羰基化的有效催化剂,但是铑价格昂贵且对设备有腐蚀性,因此,寻找出对醇类羰基化催化活性好的非贵金属催化剂,对醇类羰化的工业化有十分重要的意义。 本文在温和条件下,合成了四种含有相同配体(Ph_2PPy)不同金属的有机配合物(金属基分别为Ni、Co、Pd、Fe),并探索了它们对乙醇羰基化反应的催化活性。