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21.
Garcia F Goodman JM Kowenicki RA McPartlin M Riera L Silva MA Wirsing A Wright DS 《Dalton transactions (Cambridge, England : 2003)》2005,(10):1764-1773
The 1 : 1 reactions of [ClP(mu-NtBu)]2 with the difunctional aromatic amines 1,2-1-YH-2-NH2-C6H4 in the presence of Et3N give the dimeric phosph(III)azane macrocycles [{P(mu-NtBu)2(1-Y-2-HN-C6H4)]2, predominantly as the cis isomer in the case of Y=O (1.cis) and as the trans isomer for Y=S (2.trans). Model M.O. calculations suggest that the selection of the cis and trans isomers is not thermodynamically controlled. The alternative isomers 1.trans and 2.cis are generated exclusively by the deprotonation of the model intermediates [(1-Y-2-NH2-C6H4)P(mu-NtBu)]2[Y=O (3), S (4)] with nBuLi followed by cyclisation with [ClP(mu-NtBu)]2. The solid-state structures of 1.cis/trans(50 : 50), 2.cis, 3 and 4 are reported. 相似文献
22.
The discovery and design of new materials with competitive optical frequency conversion efficiencies can accelerate the development of scalable photonic quantum technologies. Metal–organic framework (MOF) crystals without inversion symmetry have shown potential for these applications, given their nonlinear optical properties and the combinatorial number of possibilities for MOF self-assembly. In order to accelerate the discovery of MOF materials for quantum optical technologies, scalable computational assessment tools are needed. We develop a multi-scale methodology to study the wavefunction of entangled photon pairs generated by selected non-centrosymmetric MOF crystals via spontaneous parametric down-conversion (SPDC). Starting from an optimized crystal structure, we predict the shape of the G(2) intensity correlation function for coincidence detection of the entangled pairs, produced under conditions of collinear type-I phase matching. The effective nonlinearities and photon pair correlation times obtained are comparable to those available with inorganic crystal standards. Our work thus provides fundamental insights into the structure–property relationships for entangled photon generation with metal–organic frameworks, paving the way for the automated discovery of molecular materials for optical quantum technology.The discovery and design of new materials with competitive optical frequency conversion efficiencies can accelerate the development of scalable photonic quantum technologies. 相似文献
23.
Bond AD Doyle EL García F Kowenicki RA McPartlin M Riera L Wright DS 《Chemical communications (Cambridge, England)》2003,(24):2990-2991
The in situ reaction of the phosphazane dimer [CIP(mu-N-2-NC5H4)]2 (2) with CuCl in the presence of CsH5N/H2O gives the title complex [(P(mu-N-2-NC5H4))2(mu-O)]2(CuCl x (C5H5N)2)4 (1), containing a tricyclic [(P(mu-N-2-NC5H4))2(mu-O)]2 ligand which is isoelectronic with species of the type [(P(mu-NR))2NR]2. 相似文献
24.
Doyle EL García F Humphrey SM Kowenicki RA Riera L Woods AD Wright DS 《Dalton transactions (Cambridge, England : 2003)》2004,(5):807-812
The reaction of [ClP(mu-NtBu)]2 (1) with H2O (1 : 2 equivalents) in the presence of excess Et3N gives the new chain compound [(mu-O)[P(mu-NtBu)2P(H)=O]2] (3), consisting of two P2N2 rings linked by a mu-O atom and terminating in P(V)(H)=O groups. A similar chain species is obtained from the reaction of the lithiate of [(tBuNH)P(mu-NtBu)2P(H)=O] (5) with [ClP(mu-NtBu)2P(NHtBu)] (2), the product being [(mu-O)[P(mu-NtBu)2P(NHtBu)]2] (6). Compounds 3 and 6 are the first examples of O-bridged chain phosphazanes and potential precursors to new phosphorus-nitrogen macrocycles. The syntheses and X-ray structures of 3, 5 and 6 are reported. 相似文献
25.
Dodds F García F Kowenicki RA McPartlin M Steiner A Wright DS 《Chemical communications (Cambridge, England)》2005,(29):3733-3735
The reaction of [ClP(mu-NtBu)]2 with 1,5-diamino-naphthalene [1,5-(NH2)2C10H6] in Et3N-thf gives the trimeric macrocycle [{P(mu-NtBu)}2{1,5-(NH)2C10H6}]3(1); the X-ray structure of the toluene solvate 1.3toluene reveals a cone-shaped (calixarene-like) arrangement in which toluene guest molecules are trapped within the cavity. 相似文献
26.
Zucolotto V Faceto AD Santos FR Mendonça CR Guimarães FE Oliveira ON 《The journal of physical chemistry. B》2005,109(15):7063-7066
The fabrication of varied molecular architectures in layer-by-layer (LbL) films is exploited to control the photoluminescence (PL) of poly(p-phenylene vinylene) (PPV) in an unprecedented way. This was achieved by controlling the F?rster energy transfer between PPV layers (donors) and layers of a commercial azodye, Brilliant Yellow (BY) (acceptors). Energy transfer was controlled by inserting spacer layers of inert polymers between PPV and BY layers and by photoaligning the BY molecules via trans-cis-trans isomerization. The PPV/BY LbL films displayed polarized PL whose intensity could be varied almost continuously by changing the time of photoalignment, which was carried out by impinging a linearly polarized laser light simultaneously to the PL experiments. For PPV/BY films with no spacer layers, PL was completely quenched, but its intensity increased with the number of spacing layers. Further increase in PL was obtained by photoaligning the BY molecules perpendicularly to the PPV molecules. This minimizes energy transfer, since F?rster processes are directional, dipole-dependent resonant transfers. Energy transfer is also controlled by imparting a preferential orientation of the PPV chains on PPV/BY LbL films deposited onto flexible Teflon substrates that may be stretched. 相似文献
27.
Miguel A. Esteso Luis Fernandez-Merida Felipe F. Hernandez-Luis 《Journal of Electroanalytical Chemistry》1987,230(1-2)
Values of the emf for the cell: Na-glass|Na2Succ(m), Hg2Succ|Hg, have been measured. These values of E have been used with Hückel's extended Debye and Hückel equation to obtain the mean ionic activity coefficient values for Na2Succ in aqueous solutions of several concentrations, m. The values of γ± thus obtained have been adjusted to Pitzer's equation, with b = 1.2 and α = 2.0 to find Pitzer's parameters and then the values for both the osmotic coefficients and the activity of water. Finally, the standard potential of the Hg2Succ|Hg electrode has been determined and from this value the solubility-product equilibrium constant for mercurous succinate has also been calculated. 相似文献
28.
Sanchiz J Esparza P Villagra D Domínguez S Mederos A Brito F Araujo L Sánchez A Arrieta JM 《Inorganic chemistry》2002,41(23):6048-6055
The coordinating ability of the ligands 3,4-toluenediamine-N,N,N',N'-tetraacetate (3,4-TDTA), o-phenylenediamine-N,N,N',N'-tetraacetate (o-PhDTA), and 4-chloro-1,2-phenylenediamine-N,N,N',N'-tetraacetate (4-Cl-o-PhDTA) (H4L acids) toward lead(II) is studied by potentiometry (25 degrees C, I = 0.5 mol x dm(-3) in NaClO4), UV-vis spectrophotometry, and 207Pb NMR spectrometry. The stability constants of the complex species formed were determined. X-ray diffraction structural analysis of the complex [Pb4(mu-3,4-TDTA)4(H2O)2]*4H2O (1) revealed that 1 has a 2-D structure. The layers are built up by the polymerization of centrosymmetric [Pb4L2(H2O)2] tetranuclear units. The neutral layers have the aromatic rings of the ligands pointing to the periphery, whereas the metallic ions are located in the central part of the layers. In compound 1, two types of six-coordinate lead(II) environments are produced. The Pb(1) is coordinated to two nitrogen atoms and four carboxylate oxygens from the ligand, whereas Pb(2) has an O6 trigonally distorted octahedral surrounding. The lead(II) ion is surrounded by five carboxylate oxygens and a water molecule. The carboxylate oxygens belong to four different ligands that are also joined to four other Pb(1) ions. The selective uptake of lead(II) was analyzed by means of chemical speciation diagrams as well as the so-called conditional or effective formation constants K(Pb)eff. The results indicate that, in competition with other ligands that are strong complexing agents for lead(II), our ligands are better sequestering agents in acidic media. 相似文献
29.
Ostash B Rix U Rix LL Liu T Lombo F Luzhetskyy A Gromyko O Wang C Braña AF Méndez C Salas JA Fedorenko V Rohr J 《Chemistry & biology》2004,11(4):547-555
A 3 kb DNA fragment from the Streptomyces globisporus 1912 landomycin E (LaE) biosynthetic gene cluster (lnd) was completely sequenced. Three open reading frames were identified, lndGT4, lndZ4, and lndZ5, whose probable translation products resemble a glycosyltransferase, a reductase, and a hydroxylase, respectively. Studies of generated mutants from disruption and complementation experiments involving the lndGT4 gene allowed us to determine that LndGT4 controls the terminal L-rhodinose sugar attachment during LaE biosynthesis and that LndZ4/LndZ5 are responsible for the unique C11-hydroxylation of the landomycins. Generation of the novel landomycins F, G, and H in the course of these studies provided evidence for the flexibility of lnd glycosyltransferases toward their acceptor substrates and a basis for initial structure-activity relationships within the landomycin family of antibiotics. 相似文献
30.