Two Fluorescent Complexes Assembled by Schiff Base 2-Methoxy-6-(phenyliminiomethyl) Phenolate Ligand

Two d10 metal complexes Zn（NCS）2（C14HI3NO2）2 （1） and [Cd（NO3）2（CI4HI3NO2）2]. 4H20 （2） assembled by 2-methoxy-6-（phenyliminiomethyl） phenolate ligand （C14H13NO2, HL） have been synthesized and characterized by elemental analysis, IR and TG The single-crystal X-ray diffraction studies demonstrated that complex 1 crystallizes in monoclinic, P21/c space group with a = 17.321（7）, b = 11.781（0）, c = 15.593（2） A, fl = 110.273（6）°, V = 2984.95 A3, Z = 4, C30H26N404SzZn, Mr = 636.04, F（000） = 1312, Dc = 1.415 g/cm3,μ（MoKa） = 1.004 mm＂1, the final R = 0.0403 and wR = 0.0900 for 21441 observed reflections with I 〉 20（/）. Complex 2 is of monoclinic system, space group C2/c with a = 16.7767（2）, b = 10.8989（2）, c = 17.4928（2） A, fl = 90.614（9）°, V= 3198.37 A3, Z = 4, C28H34N4O14Cd, Mr= 731.25, F（000） = 1528, Dc = 1.568 g＇cm^-3, μ（MoKa） = 0.757 mm-1, the final R = 0.0361 and wR = 0.0857 for 19811 observed reflections with I 〉 2σ（I）. The two complexes were formed by Schiff base 2-methoxy-6-（phenyliminiomethyl） phenolate ligand and formed a 3D supramolecular architecture by π-πstacking interactions. Moreover, the complexes are luminescent in the solid state. These observations indicate that the complexes are promising system for the development of potential photoactive materials.

SVNTHESES AND CHARACTERIZATION OF TWO HIGH VALENCE VANADIUM COMPLEXES (?) SCHIFF-BASE LIGAND WITH RICH PHENOLATE OXVGEN AND THEIR CONVERSION

Two vanadium complexes of schiff base vith rich phenolate oxygen,o-(?)-salicylideneamino- methylphenol,had been synthesized and characterized.One is a V(Ⅳ)complex with an interaction via vanadyl oxygen and the other is a novel dinuclear V(V,V)complex with an oxo bridge.The conversion between the two complexes had been discussed.

Synthesis, Characterization, and Reactivity of Amine Bis(phenolato) Cyclopentadienyl Lanthanide Complexes

（C5H5）3Ln（THF）reacted with amine bis（phenol） LH2 [ L = Me2NCH2CH2N {CH2-（2-O-C6H2-But^1-3-Me- 5）}2 ] in a 1：1 molar ratio in THF to generate the amine bis（phenolato） cyclopentadienyl lanthanide complexes LLn（C5H5） （THF）·（THF）,（Ln = La （1）, n =0; Ln = Sm（2）, n = 1） in high yields. Complexes 1 and 2 were fully characterized by elemental analysis, NMR （for 1） and IR spectra, and X-ray structural determination. The crystal data of complex 1 are monoclinic, P21/c space goup, a= 1.1595（1） nm, b = 1.8588（2） nm, c = 1.6647（1） nm, β = 98.490（2）°, V =3.5486（5） nm^3, Z =4, Dc = 1.338 mg· m^3,μ = 1240 mm^-1, F（000）= 1488, R =0.0249, wR = 0.0568. The crystal data of complex 2 are monoclinic, P21/c sp ace goup, a = 0.9692 （1） nm, b = 1.4583 （2） nm, c = 2.8192 （3） nm, = 96.805 （2）°, V = 3.9584 （7） nm^3, Z=4, Dc =1.340 mg · ma, μ = 1.524 mm^-1, F（000）= 1668, R =0.0346, wR =0.0756. The attempts failed to synthesize the amine bis（phenolate） lanthanide alkoxides by the reactions of complexes 1 and 2 with alcohols. The preliminary results revealed that complex 1 can initiate ε-caprolactone polymerization.

CATALYTIC BEHAVIOR OF A SILICA-SUPPORTED POLYTITAZANE-PLATINUM COMPLEX FOR THE HYDROGENATION OF PHENOL

A new kind of inorganic polymer, viz, silica-supported polytitazane (Ti-N), and its platinum complex (Ti-N-Pt) were prepared. Cyclohexanone can be obtained in a maximum yield of about 62.2% in the hydrogenation of phenol over Ti-N-Pt at room temperature under atmospheric pressure. The effects of mole ratio of N/Pt in the complex, concentration of the catalyst and reaction temperature on the catalytic activity and selectivity have been studied. The complex can be reused several times without loss in its catalytic activity.

Biodegradation of Complex Bacteria on Phenolic Derivatives in River Water

Objective To isolate, incubate, and identify 4-chlorophenol-degrading complex bacteria, determine the tolerance of these bacteria to phenolic derivatives and study their synergetic metabolism as well as the aboriginal microbes and co-metabolic degradation of mixed chlorophenols in river water. Methods Microbial community of complex bacteria was identified by plate culture observation techniques and Gram stain method. Bacterial growth inhibition test was used to determine the tolerance of complex bacteria to toxicants. Biodegradability of phenolic derivatives was determined by adding 4-chlorophenol-degrading bacteria in river water. Results The complex bacteria were identified as Mycopiana, Alcaligenes, Pseudomonas, and Flavobacterium. The domesticated complex bacteria were more tolerant to phenolic derivatives than the aboriginal bacteria from Qinhuai River. The biodegradability of chlorophenols, dihydroxybenzenes and nitrophenols under various aquatic conditions was determined and compared. The complex bacteria exhibited a higher metabolic efficiency on chemicals than the aboriginal microbes, and the final removal rate of phenolic derivatives was increased at least by 55% when the complex bacteria were added into river water. The metabolic relationship between dominant mixed bacteria and river bacteria was studied. Conclusion The complex bacteria domesticated by 4-chlorophenol can grow and be metabolized to take other chlorophenols, dihydroxybenzenes and nitrophenols as the sole carbon and energy source. There is a synergetic metabolism of most compounds between the aboriginal microbes in river water and the domesticated complex bacteria, 4- chlorophenol-degrading bacteria can co-metabolize various chlorophenols in fiver water.

HYDROGENATION OF PHENOL AND CRESOLS CATALYZED BY CHITOSAN SUPPORTED PALLADIUM COMPLEX AT MILD CONDITIONS

A natural polymer catalyst, silica-supported chitosan palladium complex (abbr. as SiO2-CS-Pd) was found to catalyze the hydrogenation of phenol and cresols to corresponding cyclohexanones in high yield and 100% selectivity at 70 degrees C and 1.01325 x 10(5) Pa mild conditions. N/Pd molar ratio in the complex, temperature and solvents have much influence on the reaction. The reactivity order of reactants was found to be: phenol >m->p->o- The catalyst is stable during the reaction and could be repeatedly used for several times without much decrease in its catalytic activity.

SPECTRAL STUDY ON A NEW 3d_z^2 TYPE COPPER(Ⅱ)COMPLEX OF PHENOLIC POLYMERIC CROWN ETHER

ESR and IR measurements have been carried out for a copper(Ⅱ)complex of phenolic polymeric crown ether,As a result,the triplet ESR spectrum(S=1)of 3d_z2 ground state copper(Ⅱ)ions was first observed for the powder sample.It indicated that there existed intramolecular spin-spin interaction betweeen 3d_Z2 ground state copper(Ⅱ)and copper(Ⅱ)ions.In this binuclear triplet cluster,the axial ligntion of one water molecule in a sandwich position to two adjacent copper(Ⅱ) ions was also confirmed by IR spectra,All things considered,a possible structure for the complex was proposed.

Mixed Pyridine-phenol Boron Complex Encapsulated in Polymer/Silica Hybrid Sol-gel Matrix

A novel pyridine-phenol boron complex[（dppy）BF] was encapsulated into polymer/silica composite matrix by sol-gel process. UV-Vis absorption spectra show that this process can control the aggregation structure of complex （dppy）BF. The results of photoluminescence of （dppy）BF in sol-gel composite film indicate that both fluorescence intensity and photostability are markedly increased using this method compared with other methods, which increases the practical significance of such composite film.

Degradation kinetics and mechanisms of phenolin photo－Fenton process

Phenol degradation in photochemically enhanced Fenton process was investigated in this work. UV-VIS spectra of phenol degradation showed the difference between photo-Fenton process and UV/H2O2, which is a typical hydroxyl radical process. A possible pathway diagram for phenol degradation in photo-Fenton process was proposed, and a mathematical model for chemical oxygen demand (COD) removal was developed. Operating parameters such as dosage of H2O2 and ferrous ions, pH, suitable carrier gas were found to impact the removal of COD significantly. The results and analysis of kinetic parameters calculated from the kinetic model showed that complex degradation of phenol was the main pathway for removal of COD: while hydroxyl radicals acted weakly in the photo-Fenton degradation of phenol.

Ti and Zr amino-tris(phenolate) catalysts for the synthesis of cyclic carbonates from CO_(2) and epoxides

Herein,we report the application of four amino-tris(phenolate)-based metal complexes incorporating Ti(IV)or Zr(IV)centres(2a-3b)as homogeneous catalysts for the conversion of CO_(2)and epoxides into cyclic carbonates.The four complexes were synthesised,characterised and then evaluated in combination with tetrabutylammo-nium iodide,bromide or chloride as binary catalytic systems for the reaction of CO_(2)with 1,2-epoxyhexane as epoxide substrate at 12 bar CO_(2)pressure and 90?C for 2 h.The catalytic systems comprising the two Ti(IV)complexes(2a and 2b)showed similar performance.One notable exception was the catalytic system consisting of titanium complex 2b,bearing an axial Cl-ligand,and tetrabutylammonium chloride,which displayed higher catalytic activity compared to other titanium-based systems.Even higher activity was achieved with Zr(IV)complex 3a,bearing an axial isopropoxide ligand,which reached turnover numbers(TON metal)up to 1920 for the reaction of CO_(2)with 1,2-epoxyhexane at 12 bar CO_(2)pressure and 90?C for 2 h.This performance is comparable with that of state-of-the-art catalysts for this reaction.The catalytic system consisting of complex 3a and tetra-butylammonium bromide was explored further by investigating its applicability with a broad substrate scope,achieving quantitative conversion of several epoxides with CO_(2)into cyclic carbonate products at 90?C and 12 bar CO_(2)pressure for 18 h.The selectivity towards the cyclic carbonate products was?98%for all studied terminal epoxides and?80%for all examined cyclohexene-type epoxides.

Jasmonic acid regulates the biosynthesis of medicinal metabolites via the JAZ9-MYB76 complex in Salvia miltiorrhiza

Jasmonic acid(JA)signaling pathway plays an important role in tanshinone and phenolic acid biosynthesis in Salvia miltiorrhiza.However,the specific regulatory mechanism remains largely unclear.Previous work showed that a JASMONATE ZIM-domain(JAZ)protein,SmJAZ9,acted as a repressor of tanshinone production in S.miltiorrhiza.In this study,we revealed that SmJAZ9 reduced both phenolic acid accumulation and related biosynthetic gene expression,confirming that SmJAZ9 also negatively affected phenolic acid biosynthesis.Then,we identified a novel MYB transcription factor,SmMYB76,which interacted with SmJAZ9.SmMYB76 repressed phenolic acid biosynthesis by directly downregulating SmPAL1,Sm4CL2,and SmRAS1.Further investigation demonstrated that JA mediated phenolic acids biosynthesis via SmJAZ9-SmMYB76 complex.Taken together,these findings state the molecular mechanism that SmJAZ9-SmMYB76 regulated phenolic acid biosynthesis at the transcriptional and protein levels,which provided new insights into JA signaling pathway regulating plant metabolism.

Synthesis and Photochemical Properties of a New Substituted Phenol Covalently Linked to Ruthenium (Ⅱ) Tris-bipyridine Containing Four Ester Groups as Sensitizer

As photosensitizer for solar cell, a new ruthenium (Ⅱ) complex with four ester groups hadbeen synthesized, in which a phenol substituted by {[(2-hydroxy-5-tert-butylbenzyl)(pyridyl-2-methyl)amino]methyl} is covalently linked to ruthenium (Ⅱ) tris-bipyridine. The structures ofthe new compounds were confirmed by NMR and ESI-MS spectra. The electrochemical andphotochemical properties were also studied.

Synthesis,Structure and Photoluminescence of Cocrystal of Bis[2-(benz(oxa/imida)zol-2-yl)phenolato-к~2N,O]zinc(Ⅱ) Being Site Occupancy Disorder with a Heteroatom Ratio of NH to O(0.408/0.592)

The zinc（Ⅱ） complex with Hpbx （Hpbx = 2-（benzoxazol-2-yl）phenol） and Hpbm （Hpbm = 2-（benzimidazol-2-yl）phenol）, namely [Zn（pbm）2]1.633[Zn（pbx）212.367·DMF·2H2O 1, has been synthesized and characterized by X-ray crystallography, FTIR and elemental analysis. The coordination structures are statistically disordered and can be regarded as a co-crystal of [Zn（pbm）2] and [Zn（pbx）2] with the ratio of ca. 0.408/0.592. Solvate water and DMF molecules are also present in the lattice. Crystal data for 1; monoclinic, space group P21/c, Mr= 2049.02, Z = 2, α = 9.7571（6）, b = 25.6415（16）, c = 19.8675（10） A, β= 111.342（2）°, V = 4629.7（5） A^3, Dc = 1.470 g/cm^3,μ = 1.100 mm^-1, F（000） = 2104, R = 0.0575 and wR = 0.1282 for 5528 observed reflections （I〉2σ（I））. The photoluminescent spectra for this compound have also been studied.

Synthesis and Crystal Structure of a Dinuclear Cu(Ⅱ) Complex [Cu(C_(13)H_9N_2O)Cl]_2·(CH_3CN)_2 with Ligand 2-Benzimidazol

A new dinuclear copper complex, [Cu（C13HgN2O）Cl]2.（CH3CN）2 （C30H24C12Cu2N6O2）, has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclirile system, space group P1, with a = 7.6677（14）, b = 9.2375（17）, c = 11.227（2） ]A, α = 81.338（3）,β = 88.173（4）, γ = 66.199（3）°, V = 718.9（2） ]A^3, Z = 1, Mr = 698.53, F（000） = 354, Dc = 1.613 g/cm^3, μ（MoKa） = 1.705 mm^-1, the final R = 0.0645 and wR = 0.1364 for 2474 unique reflections with 1809 observed ones （I 〉 20（I））. In the title complex, each copper（H） atom is located at the center of a distorted tetrahedron consisting of four coordinate atoms （one nitrogen atom, two oxygen anions, and one chlorine atom）. Two copper（Ⅱ） atoms are bridged by two oxygen anions （O（1） and O（la）） of two phenolates to form a Cu（Ⅱ）-Cu（Ⅱ） binuclear entity, and the distance between two copper（Ⅱ） atoms is 3.0144（15） A.

Synthesis, Structure and Geometrical Calculation of a Novel Co-crystal of {[4-Bromo-2-(benzimidazol-2-yl)phenolato][2-(1-butylbenzimidazol-2-yl)phenolato]zinc(Ⅱ)] and Bis[μ-2-(1-butylbenzimidazol-2-yl)phenolato]-1κN^3:2κO;1κO:2κN^3-bis{[2-(1-butylbe

The title compound has been synthesized and characterized crystallographicaUy. It is a co-crystal consisting of two different neutral zinc（H） complexes with Hbpbm （Hbpbm = 4- bromo-2-（benzimidazol-2-yl）phenol） and Hnpbm （Hnpbm = 2-（1-butylbenzimidazol-2-yl）phenol）. One is a monomeric mixed-ligand complex of [Zn（bpbm）（npbm）] 1 and the other a dimer of [Zn2（npbm）4] 2 with their ratio of 2：1. Thus the overall formula for the title compound is 21.2. Adjacent 1 and 2 are connected to each other by intermolecular hydrogen bonding interactions in the lattice. The crystal data： monoclinic, space group P21/c, a = 15.0141（12）, b = 20.9941（17）, c = 18.4686（15） A, β = 97.445（2）°, V = 5772.4（8） A^3, Mr= 2429.68, Z = 2, Dc = 1.398 g/cm^3,μ = 1.579 -1 mm , F（000） = 2504, R = 0.0637 and wR = 0.1771 for 6464 observed reflections （I 〉 2σ（I））. The geometrical structure for 1 has also been theoretically optimized and compared with the experimental one.

Analytical Application of Ion Associates of Molybdenum with Dithiolphenols and Aminophenols

The mixed-ligand complexes of molybdenum(VI) with dithiolphenols (DP) {2,6-dithiol-4-methylphenol (DTMP), 2,6-dithiol-4-ethylphenol (DTEP) and 2,6-dithiol-4-tert-butylphenol (DTBP)} in the presence of hydrophobic amines have been investigated by spectrophotometric method. The condition of complexing and extraction, physical-chemical and analytical characteristics of this complex have been found. As hydrophobic amine 2(N, N-dimethylaminomethyl)-4-methylrphenol (АP1) and 2(N, N-dimethylaminomethyl)-4-xlor-phenol (AP2), 2 (N, N-dimethylamino-methyl)-4-brom-phenol (AP3) were used. It has been found that mixed-ligand complex was formed in weakly acidic medium (pH 4.1 - 5.9). The maximum analytical signal when complexing Mo(V) is observed at 516 - 534 nm. The calculated molar absorption (εmax) belongs to the range (4.16 - 5.35) × 104. The Beer’s law was applicable in the range of 0.3 - 22 μg/ml. The extraction photometric methods of the molybdenum determination were processed. The influence of diverse ions on determination of molybdenum has been studied. The proposed method was applied successfully to determine amount of molybdenum in steel and in soil.

Microwave Synthesis and Crystal Structure of Bis{2-[(2,4-dichloro-phenylimino)methyl]-4,6-diiodo-phenol}-copper(Ⅱ)

Bis{2-[（2,4-dichloro-phenytimino）-methyl]-4,6-diiodo-phenol}-copper（II） （1） has been synthesized and its structure determined by X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 14.7558（17）, b = 20.770（2）, c = 20.3260（19） A, β = 90.6110（10）°, V= 6229.2（11） A3 and Z = 8. The Cu atom is surrounded by two O atoms and two N atoms from two 2-[（2,4-diehloro-phenylimino）-methyl]-4,6-diiodo-phenol molecules to form a tetrahedral coordination environment. The complex is linked into a column by weak intermolecular interactions.

蒽基取代含酚单茂催化剂在乙烯聚合中的应用

以蒽基取代的含酚单茂催化剂为主催化剂,三苯甲基四(五氟苯基)硼酸盐为助催化剂进行了乙烯均聚和乙烯/α-烯烃共聚反应,利用DSC,GPC等方法考察了该催化体系在不同聚合条件下的聚合性能。实验结果表明,该催化体系催化乙烯均聚的活性最高可达到3.36×10^(6)g/(mol·h)。适宜的聚合条件为:催化剂用量10μmol,n(Al)∶n(Ti)=150,n(B)∶n(Ti)=1.5,反应温度20℃,反应压力0.4 MPa,聚合时间10 min,液体总体积200 mL。在该条件下还可催化乙烯与α-烯烃共聚,其中,与1-辛烯共聚时,聚合活性最高可达2.00×10^(6)g/(mol·h),共聚物密度在0.859~0.876 g/cm3之间,玻璃化转变温度均低于-52℃,符合乙烯共聚弹性体的结构性能特征,且通过调节共聚单体浓度能有效控制乙烯共聚物链结构。

Efficient polymerization of acrylonitrile catalyzed by divalent lanthanide complex/sodium phenolate systems

Four divalent lanthanide complexes Sm(ArO)2 -(THF)4) Yb(ArO)2(THF)3, Eu(ArO)2(THF)3 (ArO=2,6-di-tert-butyl-4-methylphenolate) and (ButCp)2Sm(THF)2 were synthesized. Their catalytic activities on the polymerization of acrylonitrile were studied. The catalytic activities were influenced by the central metal ions involved. The catalytic activities of these divalent lanthanide complexes can be greatly increased by adding NaOC6H2-2,6-But2-4-Me, NaOC6H4-4-But, or NaOC10H6-2-Me. The amount of additive has apparent effect on the catalytic activity, but the additive has no effect on the tacticity of the resulting polyacryloni-trile.