Versatility of dithiophosphates in the syntheses of copper(I) complexes with bis(diphenylphosphino)alkanes: abstraction of chloride from dichloromethane

Reactions of [Cu(CH(3)CN)(4)]X (X = PF(6), BF(4)) with bis(diphenylphosphino)methane (dppm = Ph(2)PCH(2)PPh(2)) and ammonium dialkyldithiophosphates, (NH(4))[S(2)P(OR)(2)] (R = Et, (i)Pr), yield a series of novel Cu(I) polynuclear complexes, trinuclear [Cu(3)(mu-dppm)(3)(mu(3)-Cl){S(2)P(OEt)(2)}] (PF(6)) 1 and [Cu(3)(mu-dppm)(2){S(2)P(OR)(2)}(2)](PF(6)) (R = Et, 2; (i)Pr, 3), tetranuclear [Cu(4)(mu-dppm)(2) {S(2)P(OEt)(2)}(4)] 4, and hexanuclear [Cu(6)(mu-dppm)(2)(mu(4)-Cl){S(2)P(O(i)()Pr)(2)}(4)](BF(4)) 5. Similarly, the reaction of [Cu(2)(mu-L-L)(2)(CH(3)CN)(2)](PF(6))(2) (L-L, dppm, dppe = Ph(2)PCH(2)CH(2)PPh(2)) with (NH(4))[S(2)P(OR)(2)] yields dinuclear [Cu(2)(mu-dppm)(2){S(2)P(OR)(2)}(2)] 6 (R= (i)Pr, 6A; Et, 6B), trinuclear [Cu(3)(mu-dppe)(3)(mu-Cl)(2){S(2)P(O(i)Pr)(2)}] 9, and polymeric [Cu(mu(2)-dppe){S(2)P(OR)(2)}](n) (R = Et, 7; (i)Pr, 8) complexes. The formation of 1 and 5 involved the abstraction of chloride from dichloromethane when the Cu/S(2)P(OR)(2) ratio exceeded 1, but when ratio was 1:1, no Cl abstraction occurred, as in compound 4. Compound 9, however, was obtained as a 12% byproduct in the synthesis of 8 using a 1:1:1 ratio of Cu/dppe/S(2)P(O(i)Pr)(2). The chloride binds to Cu atoms in a mu(3)-Cl mode by capping one face of the Cu(3) triangle of cluster 1. A mu(4)-Cl caps a single tetragonal face of the trigonal prism of cluster 5, and in the cluster 9, two chlorides bond in mu(2)-Cl modes. Both clusters 2 and 3 exhibit the mu(3)-S mode of bonding for dtp ligands. Only cluster 5 exhibited close Cu...Cu contacts (2.997-3.0238 A). All of compounds were characterized by single-crystal X-ray diffraction and pertinent crystallographic data for 1, 5, and 9 are are follows: (1) C(79)H(76)ClCu(3)F(6)O(2)P(8)S(2), triclinic, P, a = 11.213(1) A, b = 14.142(1) A, c = 25.910(2) A, alpha = 95.328(2) degrees , beta = 99.594(2) degrees , gamma = 102.581(2) degrees , V = 3918.2(6) A(3), Z = 2; (5) C(74)H(100)BClCu(6)F(4)O(8)P(8)S(8), monoclinic, P2(1)/n, a = 25.198(4) A, b = 15.990(3) A, c = 25.421(4) A, beta = 106.027(3) degrees , V = 9845(3)A(3), Z = 4; (9) C(84)H(86)Cl(2)Cu(3)O(2)P(7)S(2), monoclinic, C2/c, with a = 24.965(3) A, b = 17.058(2) A, c = 20.253(2) A, beta = 95.351(4) degrees , V = 8587.4(17)A(3), Z = 4.     

TUMOR DESTRUCTION IN PHOTODYNAMIC THERAPY

Abstract The effects of photodynamic therapy (PDT) on the tumor microvasculature in the first few hours after treatment was studied at the light microscope (LM) and electron microscope (EM) levels in DBA/2Ha mice bearing SMT-F tumors. Animals received intraperitoneal injections of 10 mg kg⁻ of Photofrin II and 24 h later tumors were treated with 100 J cm⁻² of light (630 nm). Animals were sacrificed and their tumors removed at time 0, 30 min, 1, 2, 4, 8, 16 and 24 h after treatment. The results indicate that the effects of PDT are initially direct destruction of the microfibrils in the subendothelial zone of the tumor capillaries with subsequent tumor cell death secondary to hemorrhage and vascular collapse.     

Crystal‐smectic E mesophases in a series of 2‐(4‐n‐alkylphenyl)indenes

A series of 2‐(4‐n‐alkylphenyl)indenes (3) with different alkyl substituents (CH₃ to C₁₀H₂₁) were synthesized and systematically characterized using differential scanning calorimetry, polarizing optical microscopy and X‐ray diffraction compared with 2‐phenylindene (3a). Depending on the alkyl chain length, highly ordered crystal‐smectic E mesophases were observed and confirmed by X‐ray diffraction for the derivatives 3h–3k with heptyl to decyl chains (n = 6?9). For 3f with a pentyl side chain (n = 4), an X‐ray crystal structure analysis was carried out.     

Quantifying the measurement uncertainty of results from environmental analytical methods

The Eurachem–CITAC Guide Quantifying Uncertainty in Analytical Measurement was put into practice in a public laboratory devoted to environmental analytical measurements. In doing so due regard was given to the provisions of ISO 17025 and an attempt was made to base the entire estimation of measurement uncertainty on available data from the literature or from previously performed validation studies. Most environmental analytical procedures laid down in national or international standards are the result of cooperative efforts and put into effect as part of a compromise between all parties involved, public and private, that also encompasses environmental standards and statutory limits. Central to many procedures is the focus on the measurement of environmental effects rather than on individual chemical species. In this situation it is particularly important to understand the measurement process well enough to produce a realistic uncertainty statement. Environmental analytical methods will be examined as far as necessary, but reference will also be made to analytical methods in general and to physical measurement methods where appropriate. This paper describes ways and means of quantifying uncertainty for frequently practised methods of environmental analysis. It will be shown that operationally defined measurands are no obstacle to the estimation process as described in the Eurachem/CITAC Guide if it is accepted that the dominating component of uncertainty comes from the actual practice of the method as a reproducibility standard deviation.     

Copper(I) complexes of heterocyclic thiourea ligands

The coordination of heterocyclic thiourea ligands (L = N-(2-pyridyl)-N′-phenylthiourea (1), N-(2-pyridyl)-N′-methylthiourea (2), N-(3-pyridyl)-N′-phenylthiourea (3), N-(3-pyridyl)-N′-methylthiourea (4), N-(4-pyridyl)-N′-phenylthiourea (5), N-(2-pyrimidyl)-N′-phenylthiourea (6), N-(2-pyrimidyl)-N′-methylthiourea (7), N-(2-thiazolyl)-N′-methylthiourea (8), N-(2-benzothiazolyl)-N′-methylthiourea (9), N,N′-bis(2-pyridyl)thiourea (10) and N,N′-bis(3-pyridyl)thiourea (11)) with CuX (X = Cl, Br, I, NO₃) has been investigated. CuX:L product stoichiometries of 1:1–1:5 were found, with 1:1 being most common. X-ray structures of four 3-coordinate mononuclear CuXL₂ complexes (CuCl(6)₂, CuCl(7)₂, CuBr(6)₂, and CuBr(9)₂) are reported. In contrast, CuBr(1)₂ is a 1D sulfur-bridged polymer. CuIL structures (L = 7, 8) are 1D chains with corner-sharing Cu₂(μ-I)₂ and Cu₂(μ-S)₂ units, and CuCl(10) is a 2D network having μ-Cl and N-/S-bridging L. Two [CuL₂]NO₃ structures are reported: a mononuclear 4-coordinate copper complex with chelating ligands (L = 10) and a 1D link-chain with N-/S-bridging L (L = 3). Two ligand oxidative cyclizations were encountered during crystallization. CuI crystallized with 6 to produce zigzag ladder polymer [(CuI)₂(12)]·½CH₃CN (12 = N-(pyrimidin-2-yl)benzo[d]thiazol-2-amine) and CuNO₃ crystallized with 10 to form [Cu₂(NO₃)(13)₂(MeCN)]NO₃ (13 = dipyridyltetraazathiapentalene).     

Note on the Monotonicity of Coefficients for Some q-Series Arising from Ramanujan's Lost Notebook

In this note, we shall give a partition-theoretic interpretation which explains the non-negativity of the coefficients of some q-series arising from Ramanujan's Lost Notebook and prove the almost-increasingness of the coefficients via a vector partition generating function.     

Analysis of wave packet motion in frequency and time domain: oxazine 1

Wave packet motion in the laser dye oxazine 1 in methanol is investigated by spectrally resolved transient absorption spectroscopy. The spectral range of 600-690 nm was accessible by amplified broadband probe pulses covering the overlap region of ground-state bleach and stimulated emission signal. The influence of vibrational wave packets on the optical signal is analyzed in the frequency domain and the time domain. For the analysis in the frequency domain an algorithm is presented that accounts for interference effects of neighbored vibrational modes. By this method amplitude, phase and decay time of vibrational modes are retrieved as a function of probe wavelength and distortions due to neighbored modes are reduced. The analysis of the data in the time domain yields complementary information on the intensity, central wavelength, and spectral width of the optical bleach spectrum due to wave packet motion.     

Structural, magnetic, and spectroscopic studies of YAgSn, TmAgSn, and LuAgSn

The rare earth-silver-stannides YAgSn, TmAgSn, and LuAgSn were synthesized from the elements by arc-melting and subsequent annealing. The three stannides were investigated by X-ray powder and single-crystal diffraction: NdPtSb type, P6₃mc, Z=2, a=468.3(1), pm, wR₂=0.0343, 353 F² values, 12 variables for YAgSn, and ZrNiAl type, P6¯2 m, a=726.4(2), , wR₂=0.0399, 659 F² values, 15 variables for TmAgSn, and a=723.8(2), , wR₂=0.0674, 364 F² values, 15 variables for LuAgSn. Besides conventional laboratory X-ray data with monochromatized Mo radiation, the structures were also refined on the basis of synchrotron data with , in order to clarify the silver-tin ordering more precisely. YAgSn has puckered, two-dimensional [AgSn] networks with Ag-Sn distances of 278 pm, while the [AgSn] networks of TmAgSn and LuAgSn are three-dimensional with Ag-Sn distances of 279 and 284 pm for LuAgSn. Susceptibility measurements indicate Pauli paramagnetism for YAgSn and LuAgSn. TmAgSn is a Curie-Weiss paramagnet with an experimental magnetic moment of 7.2 μ_B/Tm. No magnetic ordering is evident down to 2 K. The local environments of the tin sites in these compounds were characterized by ¹¹⁹Sn Mössbauer spectroscopy and solid-state NMR (in YAgSn and LuAgSn), confirming the tin site multiplicities proposed from the structure solutions and the absence of Sn/Ag site disordering. Mössbauer quadrupolar splittings were found in good agreement with calculated electric field gradients predicted quantum chemically by the WIEN2k code. Furthermore, an excellent correlation was found between experimental ¹¹⁹Sn nuclear magnetic shielding anisotropies (determined via MAS-NMR) and calculated electric field gradients. Electronic structure calculations predict metallic properties with strong Ag-Sn bonds and also significant Ag-Ag bonding in LuAgSn.     

Synthesis and dynamic random access memory behavior of a functional polyimide

The device under testing was a plastic dynamic random access memory based on a donor-functionalized polyimide (TP6F-PI), which exhibited the ability to write, read, erase, and refresh the electrical states. The device had an ON/OFF current ratio up to 105, promising minimal misreading error. Both the on and off states were stable under a constant voltage stress of 1 V and survived up to 108 read cycles at 1 V.     

Mononuclear Ni(III) complexes [NiIII(L)(P(C6H3-3-SiMe3-2-S)3)]0/1- (L = thiolate, selenolate, CH2CN, Cl, PPh3): relevance to the nickel site of [NiFe] hydrogenases

The stable mononuclear Ni(III)-thiolate complexes [NiIII(L)(P(C6H3-3-SiMe3-2-S)3)]- (L = SePh (2), Cl (3), SEt (4), 2-S-C4H3S (5), CH2CN (7)) were isolated and characterized by UV-vis, EPR, IR, SQUID, CV, 1H NMR, and single-crystal X-ray diffraction. The increased basicity (electronic density) of the nickel center of complexes [NiIII(L)(P(C6H3-3-SiMe3-2-S)3)]- modulated by the monodentate ligand L and the substituted groups of the phenylthiolate rings promotes the stability and reactivity. In contrast to the irreversible reduction at -1.17 V (vs Cp2Fe/Cp2Fe+) for complex 3, the cyclic voltammograms of complexes [NiIII(SePh)(P(o-C6H4S)3)]-, 2, 4, and 7 display reversible NiIII/II redox processes with E(1/2) = -1.20, -1.26, -1.32, and -1.34 V (vs Cp2Fe/Cp2Fe+), respectively. Compared to complex 2 containing a phenylselenolate-coordinated ligand, complex 4 with a stronger electron-donating ethylthiolate coordinated to the Ni(III) promotes dechlorination of CH2Cl2 to yield complex 3 (kobs = (6.01 +/- 0.03) x 10-4 s-1 for conversion of complex 4 into 3 vs kobs = (4.78 +/- 0.02) x 10-5 s-1 for conversion of complex 2 into 3). Interestingly, addition of CH3CN into complex 3 in the presence of sodium hydride yielded the stable Ni(III)-cyanomethanide complex 7 with a NiIII-CH2CN bond distance of 2.037(3) A. The NiIII-SEt bond length of 2.273(1) A in complex 4 is at the upper end of the 2.12-2.28 A range for the NiIII-S bond lengths of the oxidized-form [NiFe] hydrogenases. In contrast to the inertness of complexes 3 and 7 under CO atmosphere, carbon monoxide triggers the reductive elimination of the monodentate chalcogenolate ligand of complexes 2, 4, and 5 to produce the trigonal bipyramidal complex [NiII(CO)(P(C6H3-3-SiMe3-2-S)3]- (6).