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91.
Brayshaw SK Schiffers S Stevenson AJ Teat SJ Warren MR Bennett RD Sazanovich IV Buckley AR Weinstein JA Raithby PR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(16):4385-4395
We introduce a new highly efficient photochromic organometallic dithienylethene (DTE) complex, the first instance of a DTE core symmetrically modified by two Pt(II) chromophores [Pt(PEt(3))(2)(C≡C)(DTE)(C≡C)Pt(PEt(3))(2)Ph] (1), which undergoes ring-closure when activated by visible light in solvents of different polarity, in thin films and even in the solid state. Complex 1 has been synthesised and fully photophysically characterised by (resonance) Raman and transient absorption spectroscopy complemented by calculations. The ring-closing photoconversion in a single crystal of 1 has been followed by X-ray crystallography. This process occurs with the extremely high yield of 80%--considerably outperforming the other DTE derivatives. Remarkably, the photocyclisation of 1 occurs even under visible light (>400 nm), which is not absorbed by the non-metallated DTE core HC≡C(DTE)C≡CH (2) itself. This unusual behaviour and the high photocyclisation yields in solution are attributed to the presence of a heavy atom in 1 that enables a triplet-sensitised photocyclisation pathway, elucidated by transient absorption spectroscopy and DFT calculations. The results of resonance Raman investigation confirm the involvement of the alkynyl unit in the frontier orbitals of both closed and open forms of 1 in the photocyclisation process. The changes in the Raman spectra upon cyclisation have permitted the identification of Raman marker bands, which include the acetylide stretching vibration. Importantly, these bands occur in the spectral region unobstructed by other vibrations and can be used for non-destructive monitoring of photocyclisation/photoreversion processes and for optical readout in this type of efficiently photochromic thermally stable systems. This study indicates a strategy for generating efficient solid-state photoswitches in which modification of the Pt(II) units has the potential to tune absorption properties and hence operational wavelength across the visible range. 相似文献
92.
We demonstrate the power of high resolution, two dimensional laser induced fluorescence (2D-LIF) spectroscopy for observing rovibronic transitions of polyatomic molecules. The technique involves scanning a tunable laser over absorption features in the electronic spectrum while monitoring a segment, in our case 100 cm(-1) wide, of the dispersed fluorescence spectrum. 2D-LIF images separate features that overlap in the usual laser induced fluorescence spectrum. The technique is illustrated by application to the S(1)-S(0) transition in fluorobenzene. Images of room temperature samples show that overlap of rotational contours by sequence band structure is minimized with 2D-LIF allowing a much larger range of rotational transitions to be observed and high precision rotational constants to be extracted. A significant advantage of 2D-LIF imaging is that the rotational contours separate into their constituent branches and these can be targeted to determine the three rotational constants individually. The rotational constants determined are an order of magnitude more precise than those extracted from the analysis of the rotational contour and we find the previously determined values to be in error by as much as 5% [G. H. Kirby, Mol. Phys. 19, 289 (1970)]. Comparison with earlier ab initio calculations of the S(0) and S(1) geometries [I. Pugliesi, N. M. Tonge, and M. C. R. Cockett, J. Chem. Phys. 129, 104303 (2008)] reveals that the CCSD∕6-311G?? and RI-CC2∕def2-TZVPP levels of theory predict the rotational constants, and hence geometries, with comparable accuracy. Two ground state Fermi resonances were identified by the distinctive patterns that such resonances produce in the images. 2D-LIF imaging is demonstrated to be a sensitive method capable of detecting weak spectral features, particularly those that are otherwise hidden beneath stronger bands. The sensitivity is demonstrated by observation of the three isotopomers of fluorobenzene-d(1) in natural abundance in an image taken for a supersonically cooled sample. The ability to separate some of the (13)C isotopomers in natural abundance is also demonstrated. The equipment required to perform 2D-LIF imaging with sufficient resolution to resolve the rotational features of large polyatomics is available from commercial suppliers. 相似文献
93.
John J. Porter Joel Luke Murray Kenneth B. Takvorian 《Journal of heterocyclic chemistry》1973,10(1):43-46
The complexing ability of derivatives of azobenzene (I) is well known (I) and responsible for the production of a wide variety of dyestuffs and analytical chemicals. While the azo group generally participates in the coordination, the determination of the degree of its interaction is complicated by other functional groups which are also coordinated with the transition metal. In a previous publication (2), we reported the preparation of the silver and palladium complexes of benzo[c]cinnoline (II) and proposed that these results might be used to explain the electron donor properties of azobenzene. We are now reporting the preparation of some additional complexes with ligands containing the azo group. 相似文献
94.
95.
Mario H. Gutierrez Warren T. Ford 《Journal of polymer science. Part A, Polymer chemistry》1986,24(4):655-663
Glass transition temperatures have been determined for polystyrenes crosslinked with 1–10% divinylbenzene and swollen with toluene, chloroform, N,N-dimethylformamide, and tetrahydrofuran to as high as 0.7 weight fraction solvent. The Tg′s depend approximately on the weight fractions and the Tg′s of the components according to the empirical equation 1nTg = m1 1nTg1 + m2 1nTg2 of Pochan. The Tg′s of the networks swollen with toluene also fit approximately a quasithermodynamic equation of Karasz based on the Tg′s and the ΔCp′s at Tg of the components. 相似文献
96.
The reactions between h5-CpFe(CO)2R (R = CH2CHCH2; CH2CMe=CH2; CH2CHCHMe; CH2CHCMe2) and stannous chloride in tetrahydrofuran afford the insertion products h5-CpFe(CO)2SnCl2R. When treated with stannous chloride in methanol or with excess stannous chloride in tetrahydrofuran, h5-CpFe(CO)2CH2CMeCH2 affords primarily h5-CpFe(CO)2SnCl3. The allenyl, 2-butynyl or cationic isobutylene complexes (R = CHCCH2; CH2 CCMe; CH2CMe+2) yield only h5-CpFe(CO)2SnCl3. Stannous iodide reacts with h5-CpFe(CO)2CH2CHCH2 in benzene to form h5-CpFe(CO)2I. Plumbous chloride in methanol fails to react with the above complexes. 相似文献
97.
Yin H Chacon A Porter NA Masterson DS 《Journal of the American Society for Mass Spectrometry》2007,18(5):807-816
Protein identification is routinely accomplished by peptide sequencing using mass spectrometry (MS) after enzymatic digestion.
Site-specific chemical modification may improve peptide ionization efficiency or sequence coverage in mass spectrometry. We
report herein that amino group of lysine residue in peptides can be selectively modified by reaction with a peroxycarbonate
and the resulting lysine peroxycarbamates undergo homolytic fragmentation under conditions of low-energy collision-induced
dissociation (CID) in electrospray ionization (ESI) and matrix-assisted laser desorption and ionization (MALDI) MS. Selective
modification of lysine residue in peptides by our strategy can induce specific peptide cleavage at or near the lysine site.
Studies using deuterated analogues of modified lysine indicate that fragmentation of the modified peptides involves apparent
free-radical processes that lead to peptide chain fragmentation and side-chain loss. The formation of a-, c-, or z-types of
ions in MS is reminiscent of the proposed free-radical mechanisms in low-energy electron capture dissociation (ECD) processes
that may have better sequence coverage than that of the conventional CID method. This site-specific cleavage of peptides by
free radical- promoted processes is feasible and such strategies may aid the protein sequencing analysis and have potential
applications in top-down proteomics. 相似文献
98.
A series of air- and water-stable tertiary phosphine-stabilized arsenium salts of the type R(3)P-->AsR(2)(+)PF(6)(-) has been isolated. In the crystal structures of two chiral triarylphosphine complexes of prochiral methylphenylarsenium hexafluorophosphate, the stereochemistry around arsenic is trigonal pyramidal with the phosphorus atom occupying the apical position, the As-P bond being orthogonal to the plane of the trigonal (lone-pair included) arsenium ion: Ph(3)P-->AsMePh(+) PF(6)(-), P2(1)/c, a = 10.7775(2) A, b = 17.7987(3) A, c = 13.3797(2) A, beta = 109.066(1) degrees, V = 2425.78(7) A(3), T = 200 K, Z = 4; Ph(2)(2-MeOC(6)H(4))P-->AsMePh(+) PF(6)(-), P1, a = 10.8077(2) A, b = 10.9741(2) A, c = 13.5648(2) A, alpha = 99.0162(9) degrees, beta = 105.2121(9) degrees, gamma = 116.4717(9) degrees, V = 1318.11(5) A(3), T = 200 K, Z = 2. The arsenium ion in each case appears to be further stabilized by conjugation of the lone pair with the phenyl group, with which the arsenic and methyl-carbon atoms are almost coplanar. In the crystal structure of the 2-(methoxymethylphenyl)diphenylphosphine adduct of methylphenylarsenium hexafluorophosphate, there operates a counteractive chelate effect in which anchimeric oxygen coordination to arsenic destabilizes the arsenic-phosphorus bond in the six-membered chelate ring. Although they are stable, phosphine-stabilized arsenium salts undergo rapid phosphine exchange and attack at arsenic by anionic carbon and oxygen nucleophiles to give tertiary arsines and arsinous acid esters, respectively, with liberation of the phosphine. 相似文献
99.
100.