A Simple and Convenient Method for Syntheses of Phenolic Amino Aldehyde Ligands,enalH2 and tnalH2

New efficient methods for synthesis of enalH₂ or 1,6-bis(2-pyridyl)-2,5-bis(2-hydroxy-3-formyl-5-methylbenzyl)-2,5-diazahexane 1a and of tnalH₂ or 1,7-bis(2-pyridyl) -2,6-bis(2-hydroxy-3-formyl-5-methylbenzyl)-2,6-diazaheptane, 1b are described     

两个带呋喃悬臂不对称大环双核铜配合物的合成、结构及性质(英文)

合成并表征了2个不对称大环双核铜配合物[Cu2(L1)Cl2]·CH3CN(1)和[Cu2(L2)Br2]·CH3CN·H2O(2)。配合物与CT-DNA的作用通过紫外-可见光谱,粘度实验,圆二色谱和凝胶电泳实验进行了研究。紫外-可见光谱的结果表明配合物与DNA的结合常数分别为6.2×105和7.2×105,圆二色谱的实验表明配合物能与DNA较好的结合,粘度实验表明配合物与DNA的结合为非典型的插入模式,凝胶电泳实验显示配合物通过氧化机理对DNA有较强的切割活性。     

两个带呋喃悬臂不对称大环双核铜配合物的合成、结构及性质

合成并表征了2个不对称大环双核铜配合物[Cu₂（L¹）Cl₂]·CH₃CN（1）和[Cu₂（L²）Br₂]·CH₃CN·H₂O（2）。配合物与CT-DNA的作用通过紫外-可见光谱,粘度实验,圆二色谱和凝胶电泳实验进行了研究。紫外-可见光谱的结果表明配合物与DNA的结合常数分别为6.2×10⁵和7.2×10⁵,圆二色谱的实验表明配合物能与DNA较好的结合,粘度实验表明配合物与DNA的结合为非典型的插入模式,凝胶电泳实验显示配合物通过氧化机理对DNA有较强的切割活性。     

The synthesis and structural analysis of cis -β-{(1,6-di(2′-pyridyl)(2,5-dibenzyl-2,5-diazahexane O(1,2-diazahexane))(1,2-benzoquinone diimine))ruthenium(II)} and related complexes

Several isomers are possible when N₄-tetradentate ligands coordinate to form metal complexes. Here we report the synthesis and structural analysis of cis-β-{[1,6-di(2′-pyridyl)(2,5-dibenzyl-2,5-diazahexane)(1,2-benzoquinone diimine)]ruthenium(II)} formed exclusively from the β-precusor, β-{[1,6-di(2′-pyridyl)(2,5-dibenzyl-2,5-diazahexane) (dimethylsulfoxide)chloride] ruthenium(II)} hexaflourophosphate. Ruthenium(II) complexes synthesised from 1,6-di(2′-pyridyl)-2,5-dibenzyl-2,5-diazahexane, produce only two isomers which can be separated by recrystallisation into α- and β-[Ru(picenbz₂)(dmso)Cl]PF₆ (where picenbz₂ is 1,6-di(2′-pyridyl)-2,5-dibenzyl-2,5-diazahexane). The distinctively different proton NMR spectra of the isomers are an especially convenient feature with which to assess separation. Isomeric structure of the precursor, α or β, is conserved upon coordination of a bidentate ligand, such as benzene-1,2-diamine, 4,5-dimethyl-benzene-1,2-diamine, naphthalene-2,3-diamine, 2,2′-bipyridine, 1,10-phenanthroline or dipyrido[3,2-d:2′3′-f] quinoxaline, to produce complexes of the type α- or β-[Ru(picenbz₂)(bidentate)](PF₆)₂. The synthesis, separation and characterisation of the α- and β-precursors and the α- and β-[Ru(picenbz₂)(bidentate)](PF₆)₂ complexes are reported. Moreover, the crystal structures have been determined for β-[Ru(picenbz₂)(dmso)Cl]PF₆.0.5H₂O (C₃₀H₃₇N₄O_1.5F₆PSClRu); it is triclinic, space group P 1, a?=?9.987, b?=?12.883, c?=?14.287?Å, α?=?72.11, β?=?78.65, γ?=?88.39° and Z?=?2 and β-[Ru(picenbz₂)(bqdi)](PF₆)₂, (C₃₄H₃₈N₆F₁₂P₂Ru) which is triclinic, space group P 1, with a?=?10.129, b?=?10.338, c?=?19.587?Å, α?=?104.42, β?=?93.36, γ?=?92.00° and Z?=?2. The structures were determined at room temperature and refined by least-squares methods to R?=?0.044 for 5109 and R?=?0.075 for 3057 non-zero diffractometer data, respectively, for the dmso and bqdi species above.     

Synthesis of a New Dicompartment Multifunctional Groups Ligand

Phenol‐based acyclic ligand 1,6‐bis(2‐chlorobenzyl)‐2,5‐bis(2‐hydroxy‐3‐formyl‐5‐methylbenzyl)‐2,5‐diazahexane, LH₂ and its dilithium form Li₂L possessing two dissimilar compartments having multifunctional groups were prepared through a Mannich reaction. To synthesize this ligand first, diamine compound 1,6‐bis(2‐chlorobenzyl)‐2,5‐diazahexane was prepared and then in a one‐step procedure an equivalent of diamine and two equivalents of 4‐methyl‐2‐formylphenol in the presence of an excess amount para‐formaldehyde were reacted. All characterization data for the new compounds including diimine, diamine, LH₂ and Li₂L are reported.     

Synthesis of 4-norpyridoxine (3-hydroxy-5-hydroxymethyl-2-methylpyridine)

3-Hydroxy-5-hydroxymethyl-2-methylpyridine (4-norpyridoxine) has been synthesized by the heterodiene condensation of 4-methyl-5-propoxyoxazole and 5-ethoxy-2,5-dihydrofuran-2-one through the stage of 3-hydroxy-2-methylpyridine-5-carbaldehyde with reduction of the latter by NaBH₄. One of the isomeric adducts has been isolated, and its stereochemistry has been established by PMR spectroscopy.     

Five- and six-coordinated transition-metal mixed-anion compounds containing the sterically constrained pyrazole-containing ligand 1,6-bis(3′,5′-dimethylpyrazol-1′-yl)-2,5-dimethyl-2,5-diazahexane

The dimethylpyrazole derivative of N,N′-dimethylethylenediamine, viz. 1,6-bis(3′,5′-dimethylpyrazol-l′-yl)-2,5-diazahexane (debd), forms coordination compounds with the transition-metal ions Co(II), Ni(II), Cu(II) and Zn(II) in the presence of a halide and a perchlorate anion of stoichiometry [M(debd)X(H₂O)_nClO₄ (n = 0 or 1). The ligand is always tetradentate. With cobalt and nickel six-coordinate compounds are formed. With copper and zinc five-coordinate compounds are formed. The compounds have been characterized by spectroscopic and magnetic methods (IR, ligand field, ESR and NMR).     

Synthesis of some imidazole- and pyrazole- derived chelating agents

Procedures involving condensation of o-phenylenediamines with carboxylic acids, and reaction of bifunctional alkyl halides with bifunctional nucleophiles are described. Syntheses are reported of 2,6-bis-(2-benzimidazyl)-pyridine, 1,3-bis(2-benzimidazyl)-2-thiapropane, 1,7-bis(2-benzimidazyl)-2,6-dithiaheptane, 2-hydroxymethyl-5,6-dimethylbenzimidazole, 2-chloromethyl-5,6-dimethylbenzimidazole hydrochloride, 1,7-bis(5,6-dimethyl-2-benzimidazyl)-2,6-dithiaheptane, 3,6-bis(1-pyrazolyl)pyridazine, 2-(2-hydroxy-3-methyl–phenyl)benzimidazole, 2-(2-hydroxyphenyl)benzimidazole, 5-(2-hydroxphenyl)-3-methyl-1-phenylpyrazole, 3(5)-(2-hydroxyphenyl)-5(3)-methylpyrazole, 3(5)-(2-hydroxyphenyl)-5(3)-phenylpyrazole, and 1,3-bis((5-methylpyridyl)imino)isoindoline.     

[2.2](2,5)Pyrazinophanes: Synthesis and Molecular Structure

The pseudoortho (4a) and the pseudogeminal [2.2](2,5)pyrazinophane (_4b) have been synthesized via 1,6-Hofmann elimination of [(5-methyl-2-pyrazinyl)methyl]trimethylammonium hydroxide (2b) and dimerization of the generated 2,5-dihydro-2,5-bis(methylene)pyrazine (3). The molecular structures of both isomers, 4a and 4b were determined by X-ray analysis.     

New glucose esters from the fresh leaves of Jacaranda mimosaefolia

From the fresh leaves of Jacaranda mimosaefolia were isolated Phytoquinoids 1-4 established as beta-D-glucopyranose 2-benzeneacetatel,6-bis(1-hydroxy-4-oxo-2,5-cyclohexadiene-1-acetate), for which the name Jacaranoside is proposed; beta-D-glucopyranose 2-(4-hydroxybenzeneacetate) 1,6-bis(1-hydroxy-4-oxo-2,5-cyclohexadiene-1-acetate), for which the name Jacarandol is proposed; beta-D-glucopyranose 2-benzeneacetate 1-(1-hydroxy-4-oxo-2,5-cyclohexadiene-1-acetate) and beta-D-glucopyranose 1,6-bis (1-hydroxy-4-oxo-2,5-cyclohexadiene-1-acetate) respectively.     

Construction of metal-organic frameworks through coordination and hydrogen bonding interactions: Syntheses, structures and photoluminescent properties of metal complexes with macrocyclic ligand

A macrocyclic ligand L with two diethylenetriamine units linked by two rigid biphenylene spacers was used as building block for construction of metal-organic frameworks. A silver(I) complex with macrocyclic and open-chain mix-type ligands [Ag₂(L)(L′)](ClO₄)₂ (1) [L′=1,6-bis(4-imidazol-1′-ylmethylphenyl)-2,5-diazahexane] was obtained by reaction of L and L′ together with AgClO₄·H₂O. It is interesting that the open-chain tetradentate ligand L′ only served as a bidentate ligand to bridge the Ag₂L units into an infinite one-dimensional (1D) cationic chain. Neutral 1D chain coordination polymer [Cu₂(L)(μ-SO₄)₂]·3H₂O·3MeOH (2) is formed by sulfate bridges between the neighboring Cu₂L units. When L reacted with nickel(II) sulfate instead of copper(II) sulfate, a monomacrocycle molecular complex [Ni₂(L)(H₂O)₄(SO₄)₂] (3) was obtained in which the sulfate anion acts as monodentate ligands rather than as bridges. When Cd(II) salts were used for the reactions with L, another two neutral 1D coordination polymers, [Cd₂(L)(μ-Cl)₂Cl₂]·2H₂O (4) and [Cd₂(L)(μ-Br)₂Br₂] (5), with the same structure were isolated. All the synthesized complexes exhibit three-dimensional framework structures linked by various hydrogen bonds. The photoluminescent properties of the synthesized complexes were studied in the solid state at room temperature, and the Ag(I) and Cd(II) complexes were found to show strong blue luminescence.     

Synthesis,structures, optical and electrochemical properties,and complexation of 2,5-bis(pyrrol-2-yl)phospholes

2,5-Bis(pyrrol-2-yl)phosphole derivatives were prepared using the reaction of titanacycles, generated in situ from a Ti^II reagent and pyrrole-capped 1,6-heptadiynes, with dichloro(phenyl)phosphine. The 2,5-bis(pyrrol-2-yl)phosphole derivatives were found to possess narrower optical HOMO–LUMO gaps and less positive oxidation potentials than those of previously reported 2,5-diarylphosphole analogs. This demonstrates that the intrinsic nature of the electron excessive pyrrole subunits as well as the effective π-conjugation over the coplanar heterole rings. The σ³-P type 2,5-bis(5-phenylpyrrol-2-yl)phosphole underwent complexation with AuCl(SMe₂) and PtCl₂ to yield the respective AuCl–monophosphine and PtCl₂–bisphosphine complexes. In the square planar Pt^II complex, the pyrrolic NH protons were found to form intramolecular hydrogen bonds with the chlorine atoms that gave rise to symmetrically split, parallel π-chromophores linked by two Pt–P bonds. Density functional theory calculations on a Pt^II model complex suggested that this cooperative interaction induces a significant split of the original LUMOs of the symmetrical π-conjugated ligands.     

The synthesis of 5-carboxamido-4-hydroxy-3-(β-D-ribofuranosyl)-thiophene derivatives,analogues of pyrazofurin

Methyl 5-carboxamido-4-hydroxy-3(β-D-ribofuranosyl)-2-thiophene carboxylate $\text{2}$a and the corresponding 2,5-thiophene dicarboxamide $\text{2}$b, two new analogues of the antiviral compound pyrazofurin, were synthesized. A base mediated condensation method with dimethyl thiodiacetate and methyl 2(2,3,5,-tri-O-$\text{t}$-butyldimethylsilyl-β-D-ribofuranosyl)-2-oxoacetate $\text{5}$ was used. The structure of these compounds and their intermediates was determined spectroscopically.     

Synthesis,crystal structure,and fluorescence properties of several schiff-base compounds

Two new Schiff-base compounds, 1,6-bis(4-dimethylaminobenzyl)-2,5-diaza-1,5-hexadiene (bdh), 1,4-bis(4-dimethylaminobenzyl)-2,3-diaza-1,3-butadiene (bdb), and a silver complex of the latter ([Ag₂(bdb)₃(NO₃)₂]·H₂O, 1) have been synthesized and characterized. The crystal structure of complex 1 was determined. 1 is a dinuclear complex, with the silver ions lying in coordination tetrahedra formed by two nitrogen atoms from the bdb ligands and two oxygen atoms from the nitrate anions. The fluorescence properties of bdh and bdb were studied; the fluorescence of bdb was quenched by the addition of silver ions, indicating that it is a potential fluorescent reagent for the analysis of silver.     

Synthesis and crystal structure of copper complex of 7,16-bis(2-hydroxy-5-methyl-3-nitrobenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane

A lariat crown ether compound 7,16-bis(2-hydroxy-5-methylbenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane has been prepared via one-pot Mannich reaction. A copper(II) complex with the ligand 7,16-bis(2-hydroxy-5-methyl-3-nitrobenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane was unexpectedly synthesized and characterized by elemental analysis, IR and UV spectra. The crystal structure of the complex has been determined by X-ray diffraction. Both crystal structure analysis and spectroscopy study indicated that the side-arm phenols of lariat crown ether are nitrated while complexing with Cu(NO₃)₂. Structure shows that the copper(II) ion is coordinated to two nitrogen and four oxygen atoms, two from the crown ether and other two from the deprotonated phenolate groups. The coordination polyhedron is a distorted octahedron.     

P-stereogenic wide bite angle diphosphine ligands

Two modular synthetic approaches for the preparation of novel wide bite angle diphosphine ligands containing stereogenic P-atoms have been developed, leading to compounds (S,S)-2,2′-bis(methylphenylphosphino)diphenyl ether (L1) and (S,S)-2,2′-bis(ferrocenylphenylphosphino)diphenyl ether (L2) in very good diastereomeric ratios. Both protocols involve diphenyl ether as backbone and (2R_P,4S_C,5R_C)-(+)-3,4-dimethyl-2,5-diphenyl-1,3,2-oxazaphospholidine borane (R_P)-5 as initial auxiliary to induce chirality at phosphorus. The absolute configuration of intermediates (S,S)-9-(BH₃)₂ and (R,R)-10-(BH₃)₂ as well as the ligands (S,S)-L1-BH3 and (S,S)-L2 was determined by X-ray crystallographic analysis.     

Metallkomplexe von Farbstoffen. VIII Übergangsmetallkomplexe des Curcumins und seiner Derivate

Metal Complexes of Dyes. IX. Transition Metal Complexes of Curcumin and Derivatives The bidentate monoanions of curcumin[CU, (1, 7-bis(4-hydroxy-3-methoxyphenyl)-hepta-1,6-diene-3,5-dione)], diacetylcurcumin[DACU, (1,7-bis(4-acetyl-3-methoxyphenyl)-hepta-1,6-diene-3,5-dione)], dihydroxycurcumin[DHCU, (1,7-bis(4-hydroxiphenyl)-hepta-1,6-diene-3,5-dione)], dimethylcurcumin [DMCU, (1,7-bis(3,4-dimethoxyphenyl)-hepta-1, 6-diene-3,5-dione)] and trimethylcurcumin[TMCU, (1,7-bis(3,4-dimethoxyphenyl)-4-methylhepta-1,6-diene-3,5-dione)] form with chloro bridged complexes [(R₃P)MCl₂]₂ (M?Pd, Pt; R?phenyl, n-butyl, ethyl, tolyl), [η⁵-C₅Me₅)MCl₂]₂ (M?Rh, Ir), [(η⁶-p-cymene)RuCl₂]₂, [(η³-C₃H₅)PdCl]₂, di-μ-chlorobis[N-(diphenylmethylene)-glycinethylester-(C,N)]-dipalladium(II) and with [(η⁵-C₅Me₅)Co(CO)I₂] monochelate dye complexes. The structure of [(η⁶-p-cymene)(Cl)Ru(DMCU)] was determined by X-ray diffraction. The dichelates (DMCU)₂M with M?Cu, Ni, (CU)₂Pd and the trichelate (CU)₃Fe were obtained. Cationic bipyridine copper(II) complexes with CU, DHCU, and DMCU were sythesized by treating the dye ligands with copper(II) acetate, 2,2′-bipyridine and ammoniumtetrafluoroborate. In comparison to the free 1.3-diketones the dye complexes show a bathochromic shift in the UV/VIS spectra.     

Synthesis of Macrocyclic Pyrimidine Derivatives

A reaction was studied of previously unknown 1,3-bis(2-hydroxy-3-chloropropyl)uracil, 1,3-bis(2- hydroxy-3-chloropropyl)-6-methyluracil, and 1,3-bis(2-hydroxy-3-chloropropyl)-5-fluorouracil with 1,3-bis[3-(3-methyl-2H-5-pyrazolon-1-yl)-2-hydroxypropyl]-6-methyluracil.     

多二茂铁基二氮杂己烷及其过渡金属配合物的合成

乙二胺与二茂铁甲醛或双二茂铁甲基氟硼酸盐反应，合成了１，６－二（二茂铁基）－２，５－二氮杂己烷和１，１，６，６－四（二茂铁基）－２，５－二氮己烷，它们与过渡金属（Ｆｅ＾２＋，Ｃｏ＾２＋，Ｎｉ＾２＋，Ｃｕ＾２＋，Ｚｎ＾２＋）盐在乙醇或乙醇－二氯甲烷中反应，是１４种过渡金属配合物，对这些化合物进行了表征，二种配体及其铜配合物用作复合固体推进剂的燃速调节剂时，基本不迁移，而燃速催化效率均超过辛基二茂铁。     

All-polymer solar cells with perylenediimide polymer acceptors

Four polymers based on perylenediimide co-polymerized with thiophene, bithiophene, selenophone and thieno[3,2-b]thiophene were investigated as the acceptor materials in all-polymer solar cells. Two different donor polymers, poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b′]dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene)-2-carboxylate-2,6-diyl](PTB7-Th) and poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3′′′-di(2-dodecyltetradecyl)-2,2′;5′,2″;5″,2′′′-quaterthiophen-5,5′′′-diyl)](Pff BT4T-2DT), with suitably complementary absorption spectra and energy levels were applied and examined. Among all different donor-acceptor pairs studied here, the combination of PTB7-Th:poly[N,N′-bis(1-hexylheptyl)-3,4,9,10-perylenediimide-1,6/1,7-diyl-alt-2,5-thiophene](PDI-Th) exhibited the best power conversion efficiency(PCE) of 5.13%, with open-circuit voltage(V_(oc)) = 0.79 V, short-circuit current density(J_(sc)) = 12.35 mA·cm~(-2) and fill-factor(FF) = 0.52. The polymer of PDI-Th acceptor used here had a regio-irregular backbone, conveniently prepared from a mixture of 1,6- and 1,7-dibromo-PDI. It is also noteworthy that neither additive nor posttreatment is required for obtaining such a cell performance.