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Ziling Xue

Publications and source records attributed to Ziling Xue.

14 recordsLinked to original sources
PubMed2005

A second-order nonlinear optical material prepared through in situ hydrothermal ligand synthesis.

The in situ hydrothermal reactions of ZnCl(2) with benzonitrile, 2-amino-5-cyanopyridine, and trans-2,3-dihydro-2-(4' '-cyanophenyl)-benzo[e]indole in the presence of NaN(3) and water afford two 3D-diamond-like networks, (CN(4)-C(6)H(5))(2)Zn (1) and (NH(2)-C(5)H(3)N-CN(4))(2)Zn (2), and one 2D square grid network, [(CN(4)-C(6)H(4)-C(12)H(7)N-C(5)H(4)N)(2)Zn].1.5H(2)O (3), in which these ligands gradually involve a noncenter-A-D (acceptor-donor) system, a one-center-A-D system, and a two-center-A-D system, respectively. All three compounds crystallize in noncentrosymmetric space groups (I2d for 1 and 2 and Fdd2 for 3) and display strong second harmonic generation (SHG) responses. Among the three new complexes, 3 shows the largest SHG effect, which is about 50 and 500 times that of urea and KDP (KH(2)PO(4)), respectively. The two-center-A-D system (multicenter push-pull electronic effect) in 3 may be responsible for it having the largest SHG effect. Interestingly, the three compounds exhibit strong fluorescent emissions at different wavelengths, 1 and 2 with blue fluorescent emissions at 390 and 415 nm and 3 with yellow-green fluorescent emissions at 495 and 532 nm.

Journal Article↗
PubMed2005

The first metal (Nd3+, Mn2+, and Pb2+) coordination compounds of 3,5-dinitrotyrosine and their nonlinear optical properties.

The reactions of 3,5-dinitrotyrosine (H2DNTY) with Nd(NO3)3.6H2O, Mn(ClO4)2.6H2O, and Pb(OAc)2 afforded three homochiral compounds: discrete [Nd(Hdnty)2(NO3)(H2O)5].3H2O (1) and two- and three-dimensional coordination polymers, [Mn(Hdnty)2] (2) and [Pb(dnty)(0.5 H2O)] (3), respectively. The Nd atom in 1 displays a tricapped trigonal prism and supramolecular weak interactions, such as pi-pi stacking and H-bonds, between amino and nitro groups result in the formation of a three-dimensional network through these interactions. 2 has a two-dimensional square-grid topological net while 3 has the first three-dimensional homochiral ThSi2 net. To the best of our knowledge, these are the first metal coordination compounds with 3,5-dinitrotyrosine. Preliminary second harmonic generation (SHG) investigations indicated that 1 and 2 are SHG active with estimated responses 5 and 6 times larger than that of urea, respectively, while 3 is SHG non-active (obeying the Klainman symmetry requirement). Strong enhancement of their SHG efficiency, compared with H2DNTY, may be due to 1) the addition of a good donor-pi-acceptor organic chromophore into the compound resulting in superior qualities of both inorganic and organic materials and 2) the H-bonds that persist in them. Crystal data: 1: C18H32N7O25Nd, Mr = 890.75 g mol(-1), monoclinic, P2(1), a=7.0179(7), b=27.060(3), c=8.3097(8) A, alpha=gamma=90.00, beta=95.646(2) degrees , V=1570.4(3) A(3), Z=2, rho(calcd)=1.884 Mg m(-3), R(1)=0.0489, wR(2)=0.1223, mu=17.67 mm(-1), S=0.811, Flack value=0.003(13); 2: C(18)H(16)N(6)O(14)Mn, M(r)=595.31 g mol(-1), orthorhombic, P2(1)2(1)2, a=8.4381(14), b=13.639(2), c=19.697(3) A, alpha=beta=gamma=90.00 degrees , V=2266.9(6) A(3), Z=4, rho(calcd)=1.744 Mg m(-3), R(1)=0.0866, wR(2)=0.2030, mu=6.72 mm(-1), S=1.095, Flack value=0.02(6); 3: C(9)H(8)N(3)O(7.5)Pb, M(r)=485.37 g mol(-1), tetragonal, P4(1)2(1)2, a=12.8136(12), b=12.8136(12), c=14.931(2), alpha=beta=gamma=90.00 degrees , V=2451.5(5) A(3), Z=8, rho(calcd)=1.885 Mg m(-3), R(1)=0.0564, wR(2)=0.1323, mu=6.942 mm(-1), S=0.878, Flack value=0.03(2). For space group P4(3)2(1)2: R(1)=0.0672, wR(2)=0.1656, S=1.034, Flack value=1.02(3); this suggests the chosen space group P4(1)2(1)2 is correct.

Crystallography, X-Ray↗
PubMed2004

Noncentrosymmetric organic solids with very strong harmonic generation response.

The molten reaction of 2-naphthol, 4-(aminomethyl)pyridine, and 4-pyridinecarboxaldehyde at about 180 degrees C yields trans-2,3-dihydro-2,3-di(4'-pyridyl)benzo[e]indole (1) which possesses two chiral centers, rather than an expected Betti-type reaction product with only one chiral carbon center. The same reactions, using 3-pyridinecarboxaldehyde, 4-cyanobenzaldehyde, or 3- cyanobenzaldehyde instead of 4-pyridinecarboxaldehyde produce the related compounds trans-2,3-dihydro-2-(4'-pyridyl)-3-(3"-pyridyl)benzo[e]indole (2), trans-2,3-dihydro-2-(4'-pyridyl)-3-(4"-cyanophenyl)benzo[e]indole (3), and trans-2,3-dihydro-2-(4'-pyridyl)-3-(3"-cyanophenyl)benzo[e]indole (4), respectively. This reaction proceeds with a high degree of stereoselectivity with a trans/cis ratio of about 98:2 at elevated temperature. Compounds 1, 2, and 4 crystallize in a noncentrosymmetric space group (Pca2(1), Pca2(1), and Cc), while compound 3 has a chiral space group (P2(1)). These successfully acentric packing arrangements are probably due to the molecule bearing both two chiral centers and potential hydrogen-bonding groups. Furthermore, the reaction of racemic 6-hydroxy-2'-methyl-2-naphthaleneacetic acid with ethyl-2-cyano-1-(4'-pyridyl)acrylic acetate in the presence of piperidine gives 1-pyridyl-2-ethoxycarbonyl-3-amino-1H-naphtho[2,1-b]pyran-2'-methylacetic acid (5), which likewise crystallizes in a chiral space group. All of compounds are second harmonic generation (SHG) active, and have a very strong SHG response approximately about 8.0, 5.0, 12.0, 6.0, and 1.4 (for 1-5 compounds) times that of urea. Ferroelectric property measurements indicate that compounds 1, 2, 4, and 5 may display ferroelectric behavior.

Journal Article↗
PubMed2004

Unusual equilibria involving group 4 amides, silyl complexes, and silyl anions via ligand exchange reactions.

Silyl anion SiButPh2- (2) was found to substitute an amide ligand in Zr(NMe2)4 (3) to give the disilyl complex Zr(NMe2)3(SiButPh2)2- (1a) and Zr(NMe2)5- (1b) in THF. The reaction is reversible, and nucleophilic amide NMe2- attacks the Zr-SiButPh2 bonds in 1a or Zr(NMe2)3(SiButPh2) in the reverse reaction, leading to an unusual ligand exchange equilibrium 2 3 + 2 2 right harpoon over left harpoon 1a + 1b (eq 1). The silyl anion 2 selectively attacks the -N(SiMe3)2 ligand in Zr(NMe2)3[N(SiMe3)2] (6) to give 1a and N(SiMe3)2- (7). Reversible reaction occurs as well, where 7 selectively substitutes the silyl ligand in Zr(NMe2)3(SiButPh2)2- (1a) or Zr(NMe2)3(SiButPh2), giving the equilibrium 6 + 2 2 right harpoon over left harpoon 1a + 7 (eq 3). The thermodynamics of these equilibria has been studied: For eq 1, DeltaH degrees = -8.3(0.2) kcal/mol, DeltaS degrees = -23.3(0.9) eu, and DeltaG degrees 298K = -1.4(0.5) kcal/mol at 298 K; for eq 3, DeltaH degrees = -1.61(0.12) kcal/mol, DeltaS degrees = -2.6(0.5) eu, and DeltaG degrees 298K = -0.8(0.3) kcal/mol. In both equilibria, the enthalpy changes for the forward reactions outweigh the entropy changes, and therefore the substitutions of amide ligands in Zr(NMe2)4 (3) and Zr(NMe2)3[N(SiMe3)2] (6) to afford the disilyl complex 1a are thermodynamically favored. The following equilibria were also observed and studied: Zr(NMe2)3[N(SiMe3)2] (6) + Si(SiMe3)3- (9) right harpoon over left harpoon Zr(NMe2)3[Si(SiMe3)3] (10) + N(SiMe3)2- (7) and Zr(NMe2)4 (3) + 9 right harpoon over left harpoon 10 + Zr(NMe2)5- (1b).

Journal Article↗
PubMed2003

Synthesis, characterization, and theoretical studies of group 4 amido hydrotris(pyrazolyl)borate complexes.

Titanium and zirconium amido complexes containing a hydrotris(pyrazolyl)borate (Tp) or hydrotris(3,5-dimethylpyrazolyl)borate (Tp*) ligand TpM(NMe(2))(3) (M = Ti, 1; M = Zr, 2) and Tp*M(NMe(2))(3) (M = Ti, 3; M = Zr, 4) were prepared by the reactions of M(NMe(2))(3)Cl (M = Ti, Zr) with sodium hydridotris(pyrazol-1-yl)borate and potassium hydridotris(3,5-dimethylpyrazol-1-yl)borate, respectively. The structures of 1, 2, and 4.CH(2)Cl(2) were determined by X-ray diffraction and show octahedral coordination geometry around the metal centers. Density functional theory calculations at the B3PW91 level were performed to understand the orientations and the rotational behavior of amido ligands in these metal complexes.

Journal Article↗
PubMed2002

High-basicity determination in mixed water-alcohol solutions by a dual optical sensor approach.

The activity of NaOH is known to be significantly affected by the presence of an alcohol in aqueous solutions. A novel linear relationship between (deltaA/deltaC(alcohol)) and C(base) was found in the highly alkaline, mixed H2O-ROH solutions (R = Me, Et, i-Pr). The use of this linear relationship led to a dual-transducer approach to decompose the optical signals of optical base sensors and to give base and alcohol concentrations in concentrated NaOH-H2O-ROH solutions ([OH-] = 0.05-3.6 M). The scope of the new dual-sensor approach was evaluated, and errors in C(base) and C(alcohol) were analyzed. The optical base sensors consist of sol-gel SiO2-ZrO2-organic polymer composites doped with high-pKa indicators. The pKa(s) of the indicators encapsulated in the composite films were determined and found to be affected by the composition of the sol-gel composites. Optical sensors and their uses in multicomponent systems are of intense current interest.( 1-7) In the multicomponent systems, the activity of the analyte and sensor response are often affected by change in ionic strength. For optical sensors that are based on indicator equilibria involving the analyte as their transducing mechanism, such effect is particularly significant. The concentrations of both the analyte and other chemicals affect ionic strength, and the sensor response to concentration of the analyte is thus often indistinguishable from those of other chemicals. An accurate measurement of each component in these multicomponent systems is actively studied. Several approaches have been developed to correct ionic strength in optical sensing for the pH region and solutions of low-to-medium ionic strength. (1-9) We recently reported a dual-transducer approach to measure acid concentrations (2-9 M HCl) in salt-containing, concentrated strong acids such as MClx-HCl (M = Li, Ca, Al) solutions. (10) This approach was shown to reduce the error in C(acid) from, for example,

Journal Article↗
PubMed2002

Unusual magnetic property associated with dimerization within a nickel tetramer.

A new ion-pair complex, 1-benzyl-4-aminopyridinium bis(maleonitriledithiolato)nickelate(III) (1), has been synthesized. The variable magnetic susceptibility results of 1 show a discontinuity around 184 K, which is phenomenologically similar to that observed for first-row transition metal complexes undergoing a spin crossover transition. The crystal structure analyses of 1 at high and low temperatures indicate that this unusual magnetic property is associated with a packing structure that changes from tetrameric spin clusters to dimers between neighboring spin carriers.

Journal Article↗
PubMed2002

High-acidity determination in salt-containing acids by optical sensors. The scope of a dual-transducer approach and the Hammett acidity function.

A dual-transducer approach based on sol-gel optical sensors was recently reported to measure acid and salt concentrations, C(acid) and C(salt), in concentrated aqueous LiCl-HCl, CaCl2-HCl, and AlCl3-HCl solutions (C(acid) at 5-6 M; C(salt) < or = 2 M). The scope of this new approach has been studied in salt-containing HCl solutions with C(acid) at 2-9 M, and factors that influence sensor responses and accuracy have been investigated. A linear relationship between (deltaA/deltaC(salt))C(acid) and (dA/dC(acid))C(salt)=0, which is the basis of this dual-transducer approach, was found to lead to an empirical linear relationship between (deltaH0)C(acid) and (deltaC(salt))C(acid) (H0: Hammett acidity function of the indicator encapsulated in the sensor).

Journal Article↗
PubMed2002

Direct observation of eta 2-imine formation through beta-H abstraction between amide ligands. Neutron and X-ray diffraction structure of a dihydride imine ditantalum complex.

Reactions of Ta(NMe2)5 with D2SiR'Ph (R' = Me, Ph) were found to give a dideuteride eta 2-imine complex (Me2N)3Ta(mu-D)2(mu-N-eta 2-N,C-CH2NMe)Ta(NMe2)3(1-d2) through C-H activation of an amide ligand via beta-H abstraction, and the structure of 1 was confirmed by single crystal neutron and X-ray diffraction.

Journal Article↗