共查询到20条相似文献,搜索用时 15 毫秒
1.
Reaction of salicyldehyde thosemicarbazone (H2L1), 2-hydroxyacetophenone thiosemicarbazone (H2L2) and 2-hydroxynapthaldehyde thiosemicarbazone (H2L3) (general abbreviation H2L, where H2 stands for the two dissociable protons, one phenolic proton and one hydrazinic proton) with K2[PtCl4] afforded a family of polymeric complexes of type [{Pt(L)}n]. Reaction of the polymeric species with two monodentate ligands (D), viz. triphenylphosphine (PPh3) and 4-picoline (pic), yielded complexes of the type [Pt(L)(D)]. These mixed-ligand complexes were also obtained from the reaction of the thiosemicarbazones with [Pt(PPh3)2Cl2] and [Pt(pic)2Cl2]. The crystal structure of [Pt(PPh3)(L2)] has been determined. The thiosemicarbazone ligands are coordinated, via dissociation of the two protons, as dianionic tridentate O,N,S-donors. The [Pt(L)(D)] complexes show characteristic 1H NMR spectra and intense absorptions in the visible and ultraviolet region. They also fluoresce in the visible region at ambient temperature. 相似文献
2.
Semanti Basu Rama Acharyya William S. Sheldrick Heike Mayer-Figge Samaresh Bhattacharya 《Structural chemistry》2007,18(2):209-215
Reaction of thiosemicarbazones of salicylaldehyde and 2-hydroxyacetophenone (H2L1 and H2L2) with [Ir(PPh3)3Cl] affords complexes of type [Ir(PPh3)2(L)(H)] (L = L1 or L2) in ethanol. A similar reaction carried out in toluene affords the [Ir(PPh3)2(L)(H)] complexes along with complexes of type [Ir(PPh3)2(L)Cl], where a chloride is coordinated to iridium instead of the hydride. The structure of the [Ir(PPh3)2(L2)(H)] and [Ir(PPh3)2(L2)Cl] complexes has been determined by X-ray crystallography. Crystal data for [Ir(PPh3)2(L2)(H)]: space group, P21/c; crystal system, monoclinic; a=12.110(2) Å, b=17.983(4) Å, c=18.437(4) Å, β=103.42(3)°, Z=4; R 1=0.0591, wR 2=0.1107. Crystal data for [Ir(PPh3)2(L2)Cl]: space group, P21/c; crystal system, monoclinic; a=17.9374(11) Å, b=19.2570(10) Å, c=24.9135(16) Å, β=108.145(5)°, Z=4; R 1=0.0463, wR 2=0.0901. In all the complexes the thiosemicarbazones are coordinated to the metal center as dianionic tridentate O, N, S-donors and the two triphenylphosphines are trans. The complexes are diamagnetic (low-spin d? 6, S=0) and show intense MLCT transitions in the visible region. Cyclic voltammetry on all the [Ir(PPh3)2(L)(H)] and [Ir(PPh3)2(L)Cl] complexes shows a quasi-reversible Ir(III)–Ir(IV) oxidation within 0.55–0.78 V vs. SCE followed by an irreversible oxidation of the thiosemicarbazone within 0.91–1.27 V vs. SCE. An irreversible reduction of the thiosemicarbazone is also observed within ?1.10 to ?1.23 V vs. SCE. 相似文献
3.
V. K. Khamylov T. S. Pochekutova B. I. Petrov G. K. Fukin S. P. Lukina 《Russian Journal of Coordination Chemistry》2008,34(12):884-890
The alkaline-earth metal complexes [M(Pta)2(15C5)] (M = Ca, Sr, and Ba; Pta is the 1,1,1-trifluoro-5,5-dimethylhexane-2,4-dionate anion; 15C5 is 15-crown-5) were obtained from PtaH and 15C5 in toluene. The complexes were characterized by IR and 1H NMR spectra and TGA data. The structures of [Ca(Pta)2(15C5)] and [Ba(Pta)2(15C5)] were confirmed by X-ray diffraction analysis. The volatility and thermal stability decrease in the order [Ca(Pta)2(15C5)] > [Sr(Pta)2(15C5)] > [Ba(Pta)2(15C5)]. 相似文献
4.
The title compound is a bifunctional receptors including a thiourea group and a crown ether ring. Due to many possible potentials as a new class of reagents for membrane transports,ion-selective electrodes as well as reaction catalysts, the design and synthesis of bifunctional receptors for simultaneous binding of cations and anions is of ongoning interest in srprarnolecular chemistry1-5. In bifunctional receptors, the binding sites for anions and cations are covalently linked so as to exhibit allosteric or cooperative complexation where the binding affinity for anions(cations)is modified as a result of the cation(anion) complexation.Literature[6] reported that the ability of the thiourea group to bind anions is significantly enhanced when Na+ is bound to the crown moiety. To date, however only a few receptors of this class have been reported.6-8In this paper, we report an improved procedure under microwave irradiation that gives higher yields of title compound and needs fewer reaction times than traditional method.The structure of this compound was determined by IR ,element analysis and X-ray analysis.Scheme 1 The reaction equationThe crystal belongs to triclinic crystal system, P-1 space group, a=0.9547(0)nm, b=1.3637(3)nm,c=1.6029(3)nm, α =75.33(3) , β =83.62(3) , γ =70.99(3) ,Z=4,Dc=1.335g/cm3,F(000)=816,R1= 0.0557 ,wR2=0.1281. It is assembled into a three-dimensionalsupramolecule by intermolecular hydrogen bonds. 相似文献
5.
Current efforts and success of nanoscale science and technology are related to the fabrication of functional materials and devices in which the individual units and their spatial arrangement are engineered down to the nanometer level. One promising way of achieving this goal is by assembling colloidal inorganic nanocrystals as the novel building blocks of matter. This trend has been stimulated by significant advances in the wet-chemical syntheses of robust and easily processable nanocrystals in a wide range of sizes and shapes. The increase in the degree of structural complexity of solution-grown nanostructures appears to be one of the natural directions towards which nanoscience will increasingly orient. Recently, several groups have indeed devised innovative syntheses of nanocrystals through which they have been able to group inorganic materials with different properties in the same particle. These approaches are paving the way to the development of nanosized objects able to perform multiple technological tasks. In this critical review (165 references), we will summarize the recent advances in the synthesis of colloidal nanocrystals, with emphasis on the strategies followed for the fabrication of nano-heterostructures, as well as on their properties and the perspectives in this field. 相似文献
6.
7.
Cengiz Soykan brahim Erol 《Journal of polymer science. Part A, Polymer chemistry》2003,41(13):1942-1951
A new type of maleimide monomer, N‐(4‐acetylphenyl)maleimide (NAPMI), was synthesized. The oxime, carbazone, and thiosemicarbazone derivatives of NAPMI were prepared with hydroxylamine hydrochloride, semicarbazide hydrochloride, and thiosemicarbazide hydrochloride, respectively. Radical homopolymerization of NAPMI and its derivatives were prepared at 60 °C in dimethyl sulfoxide solution with azobisisobutyronitrile as an initiator. The monomers and theirs homopolymers were characterized with Fourier transform infrared and NMR techniques. The glass‐transition temperatures, thermal stability, and ultraviolet stability of the polymers are compared. The activation energies of the thermal degradation of polymers were calculated by the Kissinger method. The antibacterial and antifungal effects of the monomers and polymers were also investigated on various bacteria and fungi. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1942–1951, 2003 相似文献
8.
A series of 6,12-bis[(trialkylsilyl)ethynyl]indeno[1,2-b]fluorene-5,11-diones has been synthesized. X-ray crystallographic analysis of these compounds reveals that triisopropylsilyl (TIPS) substitution on the alkyne terminus affords the largest number of intermolecular π-π interactions in the solid state. Conversely, use of trialkylsilyl groups smaller or larger than TIPS furnishes a variety of crystal-packing motifs that contain fewer π-π interactions. Electrochemical and photophysical data suggest that these molecules are excellent electron-accepting materials. 相似文献
9.
Kuo CK Chang JC Yeh CY Lee GH Wang CC Peng SM 《Dalton transactions (Cambridge, England : 2003)》2005,(22):3696-3701
A series of triruthenium complexes with arylacetylide axial ligands Ru(3)(dpa)(4)(C(2)X)(2)(BF(4))(y)(dpa = dipyridylamido; X = Fc, y= 0 (1); X = Ph, y= 0 (2); X = PhOCH(3), y= 1 (3); X = PhC(5)H(11), y= 1 (4); X = PhCN, y= 0 (5); X = PhNO(2), y= 0 (6)) have been synthesized. The crystal structures show that the Ru-Ru bond lengths (2.3304(9)-2.3572(5)A) of these compounds are longer than those of Ru(3)(dpa)(4)Cl(2)(Ru-Ru=2.2537(1)A). This is ascribed to the formation of the stronger pi-backbonding from metal to axial ligand which weakens the Ru-Ru interactions and the bond order is reduced in the triruthenium unit. Cyclic voltammetry and differential pulse voltammetry show that compound exhibits electronic coupling between the two ferrocenyl units with DeltaE(1/2) close to 100 mV. Compounds 2-6 display three triruthenium-based reversible one-electron redox couples, two oxidations and one reduction, and the electrode potentials shift upon varying the substituents. A linear relationship is observed when the Hammett constants are plotted against the redox potentials. 相似文献
10.
The copper(II)-gadolinium(III) and copper(II)-terbium(III) complexes studied in this report derive from disymmetric trianionic ligands abbreviated H3Li (i = 4-6). These ligands are obtained through reaction of different aldehydes with "half-units" having an amide function, the latter resulting from the monocondensation of different diamines with phenyl 2-hydroxy-3-methoxybenzoate. Upon deprotonation, the Li ligands (i = 4-10) possess an inner N2O2 coordination site with one amido, one imine, and two phenoxo functions, an outer O2O2 or O2O coordination site, and an amido oxygen atom positioned out of these two sites. The trianionic character of such ligands yields original anionic complexes in the presence of copper(II) or nickel(II) ions, with a 1/1 L/M stoichiometry. The crystal and molecular structures of four complexes, two 3d (1, 5) and two 3d-4f (12, 13) complexes, have been determined. Complex 1 crystallizes in the monoclinic space group C2/c: a = 27.528(2) A, b = 7.0944(7) A, c = 22.914(2) A, beta = 92.130(6) degrees , V = 4471.9(7) A(3), Z = 8 for C(21.5)H(27)CuKN(2)O(6.5). Complex 5 crystallizes in the monoclinic space group P2(1)/n (No. 14): a = 11.0760(9) A, b = 21.454(2) A, c = 15.336(1) A, beta = 101.474(1) degrees , V = 3571.5(5) A(3), Z = 4. Complex 12 crystallizes in the triclinic space group P (No. 2): a = 8.682(2) A, b = 11.848(2) A, c = 11.928(2) A, alpha = 81.77(3) degrees , beta = 89.17(3) degrees , gamma = 85.49(3) degrees , V = 1210.6(4) A(3), Z = 2 for C20H22CuN5O11Tb. Complex 13 belongs to the monoclinic space group C2/c: a = 25.475(5)A, b = 12.934(3)A, c = 15.023(3) A, beta = 91.06(3) degrees , V = 4949.02A3, Z = 8 for C21H25CuN4O12Tb. The structural determinations confirm that the dinuclear entities involved in 12 and 13 are disposed in a head-to-tail arrangement to give tetranuclear complexes in which the copper and lanthanide ions are positioned at the vertexes of a rectangle. In the [Cu-Gd]2 species, there are two different ferromagnetic Cu-Gd interactions. The stronger one is supported by the double phenoxo bridge (CuO2Gd) while the weaker one corresponds to the single amido bridge (Cu-N-C-O-Gd). Replacement of gadolinium ions with anisotropic terbium ions yields tetranuclear entities showing slow relaxation of magnetization and magnetization hysteresis. Detailed relaxation and hysteresis loop studies establish single-molecule magnet (SMM) behavior which is influenced by weak intermolecular interactions. 相似文献
11.
Syntheses of the four mixed phenol-pyridine derivatives 1,6-bis(2-hydroxyphenyl)pyridyl boron naphthalene (1), 1,6-bis(2-hydroxy-5-methylphenyl)pyridyl boron naphthalene (2), 1,6-bis(2-hydroxyphenyl)pyridyl boron 2-methoxylbenzene (3), and 1,6-bis(2-hydroxy-5-methylphenyl)pyridyl boron 2-methoxylbenzene (4) are reported. The structures of the boron compounds 1, 3, and 4 were determined by single-crystal X-ray diffraction. The molecular packing is characterized by intermolecular pi...pi and hydrogen-bonding interactions. DSC analysis demonstrates that 1 and 2 have good thermal stability with higher glass transition temperatures (Tg) and melting points (Tm) than 3 and 4. Boron complexes 1-4 display bright blue luminescence in solution and the solid state. White and blue electroluminescent (EL) devices were fabricated successfully using these boron compounds. 相似文献
12.
S. K. Balenko V. P. Rybalkin N. I. Makarova S. O. Bezuglyi E. N. Shepelenko L. L. Popova V. V. Tkachev S. M. Aldoshin A. V. Metelitsa V. A. Bren’ V. I. Minkin 《Russian Chemical Bulletin》2008,57(7):1435-1443
New 3-indolylfulgides, viz., 3-[1-(1-aryl-5-methoxy-2-methyl-1H-indol-3-yl)ethylidene]-4-(1-methylethylidene)tetrahydro-2,5-furandiones, were synthesized. These compounds were obtained
as E-isomers, as demonstrated by X-ray diffraction, electronic spectroscopy, and 1H NMR spectroscopy. Fulgides exhibit photochromic properties in solution. The cyclic dihydrocarbazole photoisomers of indolylfulgides
show fluorescence properties and are characterized by high thermal stability.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1417–1423, July, 2008. 相似文献
13.
A macroreticular polystyrene-based chelating resin with oxime and diethylamino functional groups has been synthesized. The resin is stable in acid and alkaline solutions; no decrease in nitrogen content or capacity for sorption of copper(II) is observed when it is exposed to 3M hydrochloric acid and 1M sodium hydroxide for 7 days. The resin has higher selectivity for copper(II) than for other metal ions tested and the time required for 50% uptake of copper(II) is 15 min. The highest capacity for copper(II) is 2.0 mmole/g at pH 6.0. In a column operation, quantitative recovery of copper(II) is achieved by elution with 1M hydrochloric acid, and the resin can be used repeatedly. 相似文献
14.
The pseudo-hollandite chromium sulfides, ACr5S8 (A=K, Rb, Cs) and A′0.5Cr5S8 (A′=Sr, Ba), have been synthesized and investigated in structural and magnetic properties. All the compounds crystallize in the isostructure with a monoclinic C2/m. Its crystal structure has triangular lattices and double chains made of Cr3+ (d3; S=3/2) triangles. The magnetic susceptibilities of all compounds behave as Curie-Weiss types in high temperature region. From magnetic susceptibility and specific heat measurements, all the compounds have antiferromagnetic ground states. The Néel temperatures are rather low compared to Weiss temperatures, reflecting magnetic frustration in the triangular lattices and double chains. The magnetic transitions in KCr5S8 and Ba0.5Cr5S8 are a two-step transition around 50 and 60 K, respectively, while RbCr5S8 shows a sharp magnetic transition at 42 K, accompanied by magnetoelastic behavior. CsCr5S8 shows a structural transition around 100 K, followed by a magnetic transition at 10 K. In Sr0.5Cr5S8, ferromagnetic interaction develops below 100 K and then a three-dimensional antiferromagnetic order takes place at 30 K. These magnetic properties are discussed from A-cation dependences of local structures and a model of magnetic structure for RbCr5S8 is proposed on the basis of the arguments of magnetic interactions and neutron diffraction data. It is different from the known magnetic structure of TlCr5Se8. 相似文献
15.
Javier Martínez José M. Antelo Ma Teresa Pereira José M. Vila 《Journal of organometallic chemistry》2006,691(13):2891-2901
Treatment of the thiosemicarbazones 4-FC6H4C(Me)NN(H)C(S)NHR, (R = Me, a; Ph, b) and 2-ClC6H4C(Me)NN(H)C(S)NHR (R = Ph, c) with lithium tetrachloropalladate(II) in methanol or palladium(II) acetate in acetic acid gave the tetranuclear cyclometallated complex [Pd{4-FC6H3C(Me)NNC(S)NHR}]4 (1a, 1b) and [Pd{2-ClC6H3C(Me)NNC(S)NHPh}]4 (1c). Reaction of these tetramers with the diphosphines dppe, t-dppe, dppp or dppb in a 1:2 molar ratio gave the dinuclear cyclometallated complexes [(Pd{4-FC6H3C(Me)NNC(S)NHR})2(μ-Ph2P(CH2)nPPh2)], (n = 2, 2a, 2b; 3, 4a, 4b; 4, 5a, 5b), [(Pd{4-FC6H3C(Me)NNC(S)NHPh})2(μ-Ph2PCHCHPPh2)], (3a, 3b) and [(Pd{2-ClC6H3C(Me)NNC(S)NHR})2(μ-Ph2P(CH2)nPPh2)], (n = 2, 2c, 2d; 3, 4c, 4d; 4, 5c, 5d), [(Pd{2-ClC6H3C(Me)NNC(S)NHPh})2(μ-PPh2CHCHPPh2)], (3c, 3d). The X-ray crystal structure of the ligand b and the complexes 3c, 4a and 4d were determined. The structures of complexes 4a and 4d show that the different disposition of the chain cyclometallated of the thiosemicarbazones (in the same orientation or in the opposite one) is due to the different H bonds produced. 相似文献
16.
Chen-I Yang Kai-Hung Cheng Motohiro Nakano Gene-Hsiang Lee Hui-Lien Tsai 《Polyhedron》2009,28(9-10):1842-1851
The reaction of salicylaldoxime (H2salox) with Mn(ClO4)2 · 6H2O, NaN(CN)2 and NEt3 in MeOH affords a MnIII6 hexanuclear complex of [Mn6O2(salox)6(MeOH)6(NCNCONH2)2] (1), while reaction of H2salox with MnCl2 · 4H2O and NEt4OH in EtOH affords a MnIII6 hexanuclear complex of [Mn6O2(salox)6(EtOH)4(H2O)2Cl2] (2). Both complexes 1 and 2 contain a [MnIII6(μ3-O)2]14+ core, which is a known structural type in the family of Mn6 complexes. Variable temperature magnetic susceptibilities and magnetization measurement of complexes 1 and 2 have been carried out. Exchange interactions of metal centers for complexes 1 and 2 are fitted by a full diagonalization matrix method. The fitting results indicate that both complexes 1 and 2 have the ground-state spin value of S = 4, and the ground state of complex 1 has the much closer energy to low-lying spin states than that of complex 2. Magnetization measurements at 2.0–4.0 K and 10–70 kG confirm that the ground state is S = 4, with significant magnetoanisotropy as gauged by the D value of ?0.82 cm?1 and ?1.18 cm?1, for 1 and 2, respectively. The frequency dependence of the out-of-phase component in alternating current magnetic susceptibilities for both complexes 1 and 2 indicates the slow magnetic relaxation of superparamagnetic behaviour with a Ueff of 27.0(1) K and τ0 = 3.8(2) × 10?9 s for complex 1, and Ueff of 25.1(6) K and τ0 = 4.6(1) × 10?8 s for complex 2. 相似文献
17.
The synthesis and spectral characterization of novel neutral and cationic organotin complexes with pyruvic acid thiosemicarbazone, H2pt (1), [SnPh2(pt)] (2), [SnMe2(Hpt)(H2O)]Cl (3) and [SnPh2(Hpt)(H2O)]Cl (4) are reported. The crystal structure of the complexes [SnPh2(pt)] (2) and [SnMe2(Hpt)(H2O)]Cl (3) have been solved by single-crystal X-ray diffraction. The crystal structure of complex 2 showed that the ligand is doubly deprotonated at the oxygen and amide nitrogen atoms and is coordinated to the SnPh2 fragment via two five-membered chelate rings. The monomers of 2 are linked through intermolecular hydrogen bonds of C−H–O type and through π−π intermolecular interactions. The crystal structure of [SnMe2(Hpt)(H2O)]Cl (3) showed that the ligand is mono-deprotonated at the oxygen atom and is coordinated to the SnMe2 fragment via two five-membered chelate rings. The counter ion chloride is participated in intermolecular hydrogen bonds. An extended network of intermolecular hydrogen bonds leads to aggregation and a supramolecular assembly. The IR and NMR spectroscopic data of the complexes are reported. The in vitro cytotoxic activity has been evaluated against the cells of three human cancer cell lines: MCF-7 (human breast cancer cell line), T-24 (bladder cancer cell line), A-549(non-small cell lung carcinoma) and a mouse L-929 (a fibroblast-like cell line cloned from strain L). The most active of all was found the diorganotin complex 2. The cytotoxic activity shown by these compounds against all these cancer cell lines indicates that coupling of 1 with R2Sn(IV) metal center result in metallic complexes with important biological properties and remarkable cytotoxic activity, since they are display IC50 values in a μM range the same or better to that of the antitumor drug cisplatin. Compound 2 is considered as agent with potential antitumor activity, and can therefore be candidate for further stages of screening in vitro and/or in vivo. 相似文献
18.
JAVAD Iqbal 《中国科学B辑(英文版)》2011,(2)
Two novel quinacridone (QA) cyclophanes with intrinsic intramolecular dye-dye interactions have been designed and synthesized.X-ray crystal structures as well as detailed photophysical properties have been well demonstrated.These two dyes have a major advantage that efficient fluorescence quenching can be observed even in their dilute solutions.A comparison of photophysical properties between the dimeric QA cyclophane and its reference monomeric counterpart indicates that the dimerization is predominant for... 相似文献
19.
20.
Elena I. Klimova Tatiana Klimova Berestneva Daniel Méndez Iturbide Marcos Martínez García 《Journal of organometallic chemistry》2005,690(14):3333-3339
Synthesis of diferrocenylcyclopropenyl tetrafluoroborates with hetero-substituents in the three-membered ring, viz., ethoxy, trityloxy, ferrocenyl(phenyl)methoxy, N,N-diethylamino, piperidino, and morpholino, is described. The spatial structure of diferrocenyl(morpholino)cyclopropenyl tetrafluoroborate was established based on the data from X-ray diffraction analysis. Under the action of potassium tert-butoxide, all the diferrocenylcyclopropenyl tetrafluoroborates undergo three-membered ring-opening with formation of the corresponding 2,3-diferrocenylacrylic acid derivatives. A mechanism of the ring-opening is suggested. 相似文献