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51.
G. Grabner N. Getoff TS. Gantchev † D. Angelov M. Shopova 《Photochemistry and photobiology》1991,54(5):673-681
Nanosecond (lambda exc = 266, 355 and 532 nm) and picosecond (lambda exc = 355 nm) laser flash photolysis of hematoporphyrin (Hp) was performed in neutral (pH 7.4) and alkaline (pH 12) aqueous solution, as well as in the presence of 0.1% Triton X-100. The dependence of the yield of photoproduced hydrated electrons (e-aq) on laser pulse energy was studied over a wide range of energies (0.2 to greater than 1000 mJ cm-2). The results show that e-aq are predominantly formed in a two-photon process at lambda exc = 266 and 355 nm. One-photon quantum yields are higher at lambda exc = 266 nm than at lambda exc = 355 nm. Both one-photon and two-photon pathways are less efficient at higher Hp concentration, reflecting the influence of Hp self-aggregation. Two-photon e-aq formation is more efficient when 30 ps pulses are used for excitation, as compared to 10 ns pulses. No e-aq could be detected at lambda exc = 532 nm. Nanosecond pulse-induced transient spectra obtained at pH 7.4 are also discussed. 相似文献
52.
Lobana Tarlok S. Verma Renu Singh Randhir Castineiras Alfonso 《Transition Metal Chemistry》1997,23(1):25-28
Reaction of cis-RuCl2(dppp)2 with pyridine-2–thiol (HpyS) in the presence of Et3N in dry benzene replaces both the chloro groups and a diphosphine molecule to form Ru(dppp)(pyS)2 (1) [dppp=Ph2P(CH2)3PPh2], whose crystal and molecular structure has been determined with the help of single crystal X-ray crystallography. The discrete molecules of (1) adopt a distorted octahedral structure containing chelating pyridine-2–thiolato and dppp ligands with trans-S, cis-N and cis-P atom dispositions. The important interatomic parameters are: Ru-S, 2.443(2), 2.339(2); Ru-N, 2.133(5), 2.129(5); Ru-P, 2.274(2), 2.279(2)Å; trans-bond angles, S-Ru-S, 153.89(6); N-Ru-P, 172.76(13), 163.51(14)°; bite angles: P-Ru-P, 90.71(6); N-Ru-S, 67.18(14), 67.72(14)°. The n.m.r. spectra (1H, 13C, 31P) of (1) are also reported in order to compare solution phase behaviour with the solid state structure. The 13C-n.m.r. spectrum of the complex shows the presence of non-equivalent phenyls in the Ph2P-moiety. 相似文献
53.
The reactions of silver(I) halides (Cl or Br) with thiophene-2-carbaldehyde N1-methyl thiosemicarbazone (HttscMe) in the presence of Ph3P (1:1:1 molar ratio) yield halogen-bridged dimers, [Ag2(μ-X)2(η1-S-HttsMe)2(PPh3)2] (X = Cl, 1; Br, 2). The use of 2,2′-bipyridine in lieu of Ph3P in the reaction of silver(I) chloride with HttscMe yields the sulfur-bridged dimer, [Ag2(μ-S-HttscMe)2(η1-HttsMe)2] · 2CHCl3 3. The substituents have altered the nature of bridge between the two silver atoms. The Ag···Ag separation (3.4867(5) Å) in complex 3 is less than that in the halogen-bridged dimers (3.734(4) Å 1; 3.746(5) Å 2). Unlike PPh3 the co-ligand 2,2′-bipyridine did not coordinate to the silver center, but was necessary for crystallization in the reaction with the thio-ligand. NMR spectroscopy revealed that the complexes remained unchanged in the solution state (CDCl3). 相似文献
54.
The reaction of copper(I) iodide with 1, 3-imidazolidine-2-thione (SC3H6N2) in a 1:2 molar ratio (M/L) has formed unusual 1D polymers, {Cu6(mu3-SC3H6N2)4(mu-SC3H6N2)2(mu-I)2I4}n (1) and {Cu6(mu3-SC3H6N2)2(mu-SC3H6N2)4(mu-I)4I2}n (1a). A similar reaction with copper(I) bromide has formed a polymer {Cu6(mu3-SC3H6N2)2(mu-SC3H6N2)4(mu-Br)4Br2}n (3a), similar to 1a, along with a dimer, {Cu2(mu-SC3H6N2)2(eta1-SC3H6N2)2Br2} (3). Copper(I) chloride behaved differently, and only an unsymmetrical dimer, {Cu2(mu-SC3H6N2)(eta1-SC3H6N2)3Cl2} (4), was formed. Finally, reactions of copper(I) thiocyanate in 1:1 or 1:2 molar ratios yielded a 3D polymer, {Cu2(mu-SC3H6N2)2(mu-SCN)2}n (2). Crystal data: 1, C9H18Cu3I3N6S3, triclinic, P, a = 9.6646(11) A, b = 10.5520(13) A, c = 12.6177(15) A, alpha = 107.239(2) degrees , beta = 99.844(2) degrees , gamma = 113.682(2) degrees , V = 1061.8(2) A(3), Z = 2, R = 0.0333; 2, C(4)H(6)CuN(3)S(2), monoclinic, P2(1)/c, a = 7.864(3) A, b = 14.328(6) A, c = 6.737(2) A, beta = 100.07(3) degrees , V = 747.4(5), Z = 4, R = 0.0363; 3, C12H24Br2Cu2N8S4, monoclinic, C2/c, a = 19.420(7) A, b = 7.686(3) A, c = 16.706(6) A, beta = 115.844(6) degrees , V = 2244.1(14) A(3), Z = 4, R = 0.0228; 4, C12H24Cl2Cu2N8S4, monoclinic, P2(1)/c, a = 7.4500(6) A, b = 18.4965(15) A, c = 16.2131(14) A, beta = 95.036(2) degrees , V = 2225.5(3) A(3), Z = 4, R = 0.0392. The 3D polymer 2 exhibits 20-membered metallacyclic rings in its structure, while synthesis of linear polymers, 1 and 1a, represents an unusual example of I (1a)-S (1) bond isomerism. 相似文献
55.
Mallika Somayajulu-Ni?u Jagdeep K Sandhu Jerome Cohen Marianna Sikorska TS Sridhar Anca Matei Henryk Borowy-Borowski Siyaram Pandey 《BMC neuroscience》2009,10(1):88
Background
Parkinson's disease, for which currently there is no cure, develops as a result of progressive loss of dopamine neurons in the brain; thus, identification of any potential therapeutic intervention for disease management is of a great importance. 相似文献56.
Summary X-band e.s.r. and i.r. spectra of [Fe(NCS)3(Ph3PO)2](1) and [Fe(NCS)3(p-Tol3AsO)2](2), before and after heating to 100, 150 and 200° C (±2°C), were studied at room temperature. Reactions of (1) and (2) with HgCl2 in Me2CO form heteropolymetallic 13 (Fe:hg) complexes: [Fe(NCS)3(Ph3PO)2(HgCl2)3]·2Me2CO (3) and [Fe(NCS)3(p-Tol3AsO)2(HgCl2)3]·H2O (4). Room temperature i.r. and e.s.r. spectra of (3) and (4) have been studied. 相似文献
57.
Tarlok S. Lobana 《Transition Metal Chemistry》1991,16(1):57-59
Summary The analytical, molar conductance and spectroscopic studies of new complexes of copper(I) and copper(II) with bis(—phosphine chalcogenides), Ph2P(E)(CH2)n-P(E)Ph2(L-L) are reported. The complexes are of the types: (a) [CuX(L-L)](X, n, E: Cl, 2–4, Br, 2, S; Cl, Br, 1, Se); (b) [Cu2X2(L-L)] (X, n, E: Cl, Br, 2, 3, Se) and (c) [CuCl2(L-L)] (n, E: 2, 3, S). Possible structures have been derived. 相似文献
58.
Reaction of copper(I) chloride with thiophene-2-carbaldehyde thiosemicarbazone (Httsc) in acetonitrile in the presence of Ph3P yielded a sulfur-bridged dimer [Cu2Cl2(μ2-S-Httsc)2(PPh3)2] · 2CH3CN (1), while a similar reaction with isatin-3-thiosemicarbazone (H2itsc) formed a monomer, [CuCl(H2itsc)(Ph3P)2] · 2CH3CN (3). Furan-2-carbaldehyde thiosemicarbazone (Hftsc) also formed a compound of the composition [Cu2Cl2(Hftsc)2(PPh3)2] · 2H2O (2). Complexes 1–3 have been characterized using elemental analysis, IR, 1H and 31P NMR spectroscopy and single crystal X-ray crystallography (1 and 3). Acetonitrile is engaged in hydrogen bonding with the chlorine atom {NCCH2–H?Cl)}, which is necessary for the stabilization of the bridging sulfur in 1. In compound 3, however, acetonitrile is strongly hydrogen bonded to the NH hydrogen of the isatin ring {CH3CN?NH(isatin)} and not to the chlorine atom. The Cu?Cu contact of 2.7719(5) Å in dimer 1 is close to twice the van der Waals radius of the Cu atom (2.80 Å). 相似文献
59.
Tarlok S Lobana Amarjeet Singh Mandeep Kaur Alfonso Castineiras 《Journal of Chemical Sciences》2001,113(2):89-94
Reaction of mercury(II) diiodide with triphenyl selenophosphorane-Se (1:1 mole ratio) in acetone followed by recrystallisation
of the product from chloroform formed crystals of stoichiometry HgI2(Ph3PSe)(1). Compound1 exists as a centrosymmetric homobimetallic dimer, Hg(Μ-I)I(Ph3PSe)2, as monoclinic crystals of space group P21/n. The dimer comprises two Μ2-iodo atoms that form unequal Hg-I bonds 2.8230(10), 3.1135(9) ? and two equal terminal Hg-I bonds 2.6524(10) ?. The Se atom
of Ph3PSe forms terminal Hg-Se bond 2.5914(11)? and thus the geometry about each Hg centre is distorted tetrahedral and the range
of tetrahedral bond angles is 92.97(2) to 130.85(3)‡, the largest being that of Se(1)-Hg(1)-I(1) and the shortest, I(2)-Hg(1)-I(2)‡.
Hg-Hg and I-I separations of 4.0930(11)? and 4.3097(15)? are more than the sums of their respective van der Waal radii 3.00
? and 4.24 ?. 相似文献
60.
Rakesh Kumar Mahajan Rajiv Kumar Puri Gagandeep Bawa Tarlok Singh Lobana 《无机化学与普通化学杂志》2008,634(9):1626-1632
A ruthenium(II) complex [Ru(PPh3)2(pytsc)2] {Hpytsc = pyridine‐2‐carbaldehydethiosemicarbazone, (C5H5N)C2(H)=N3‐N2(H)‐C1(=S)N1H} has been used as an ion carrier for the selective determination of silver(I) ions in solution. Silver(I) ion‐selective coated graphite based (CGE) and PVC polymeric membrane based (PME) electrodes exhibit Nernstian slope for silver(I) ions over a wide concentration range from 1.0 × 10−1 M to 5.0 × 10−6 M (with CGE) and 1.0 × 10−1 M to 2.0 × 10−5 M (with PME). The working pH range of these electrodes has been found to be from 1.2 to 7.2 for CGE and 2.2 to 6.5 for PME. The proposed CGE sensor exhibits better analytical features like sensitivity and selectivity towards different secondary ions in comparison to the corresponding PME with no interference from mercury(II) ions . These electrodes also act as indicator electrodes in potentiometric titration and have been successfully used for the determination of silver content in solution of real samples (1 gm dissolved in 100 mL of dilute nitric acid) such as silver ornaments and thin silver foils. Silver content determined by the use of ion selective electrode was found to vary in the concentration range from 1.20 x 10−2 M to 7.45 x 10−2 M and results were found to be comparable with those obtained from the traditional volumetric method of analysis. It is the first report of a metal‐ligand complex used as an ion carrier in ion selective electrode, which is selective for a metal ion other than the one used in the complex. 相似文献