Highly regioselective synthesis of dicyano-8a,10,11-trihydropyrrolo[1,2-a][1,10]phenanthrolines via a domino-Knoevenagel-cyclization

1,10-Phenanthrolinium N-ylides,can react with malonitrile and aromatic aldehydes via a domino-Knoevenagel cyclization to afford a new class of trihydropyrrolo[1,2-a][l,10]phenanthroline derivatives as stable helical compounds in a simple,mild,and efficient protocol in excellent yields.     

Aza-bridged bis-1,10-phenanthroline acyclic derivatives: synthesis, structure, and regioselective alkylation

A family of acyclic aza-bridged bis-1,10-phenanthroline compounds has been synthesized in a convenient way. The resulting compounds 2 and 2·HCl were fully characterized and their solid state structures and NMR spectroscopic properties were investigated to assess how the structural units affect the alkylation reactions. The results reveal the transoid structure for 2. The broadening NMR peak in 2 is shown to be due to an unusual intramolecular CH?N hydrogen bond. This unique conformation offers an efficient and regioselective method to prepare the amino-substituted bis-2,2′-1,10-phenanthroline derivatives and 1,10-phenanthrolino-N-alkylated compounds.     

Infrared Spectroscopic Study on the Hofmann-dadn-type and the Td-dahxn-type clathrates

Infrared spectra of M(1,10-diaminodecane)Ni(CN)₄ · 1,5 G (M=Co, Ni or Cd; G=o-xylene, m-xylene, p-xylene) and Cd(l,6-diaminohexane)M(CN)₄ · C₆H₆ (M=Cd or Hg) clathrates are reported. The 1,10-diaminodecane and 1,6-diaminohexane molecules in the host permit the inclusion of bulky guest molecules. The spectral data of clathrates were compared with those of the corresponding host. The spectral features suggest that these compounds are similar in structure to other Hofmann-type and Hofmann-T_d type clathrates, respectively.     

Synthesis,Characterization, Antibacterial and Antifungal Activity of Yttrium(III) Complexes Including 1,10‐Phenanthroline

Two rare metal coordination complexes of yttrium(III) including 1,10‐phenanthroline, Y(phen)₂(NO₃)₃ and (phenH)₂[Y₂(pydc)₃(NO₃)₂·6H₂O] (phen=1,10‐phenanthroline, pydc=2,6‐pyridinedicarboxylate), and a proton transfer compound (phenH⁺)₂(pydc^2?) were synthesized and characterized by elemental analysis, molar conductance, infrared spectra (IR), nuclear magnetic resonance (NMR) and thermal analysis. The proposed structures of yttrium complexes were exhibited. The in vitro biological activities of the newly synthesized complexes have also been investigated against Bacillus coli, Staphylococcus aureus and Candida albicans. The results showed that yttrium(III) complexes including 1,10‐phenanthroline exhibited better antibacterial/antifungal activity than their ligands and corresponding compounds.     

Solvent-free synthesis of dibenzo[b,j][1,10]phenanthroline derivatives using Eaton’s reagent as catalyst

A new class of dibenzo[b,j][1,10]phenanthrolines has been prepared. The synthon acridones were achieved in very good yield by a one-pot reaction of 2-amino-5-chloro or 2′-chloro/flouro-substituted benzophenones with 1,2-cyclohexanedione in the presence of freshly prepared Eaton’s reagent (phosphorus pentoxide–methanesulfonic acid) without solvent, through Friedländer synthesis. Then these intermediates were reacted with 2-amino-3,5-dibromobenzaldehyde to afford 1,3-dibromo-10-chloro-8-aryl-6,7-dihydrodibenzo[b,j][1,10]phenanthroline. Also an one-pot reaction between 2?mol of 2-amino-5-chloro aryl benzophenones with 1?mol of 1,2-cyclohexanedione to get 3,10-dichloro-5,8-diaryl-6,7-dihydrodibenzo[b,j][1,10]phenanthroline has also been reported. The newly synthesized structures of the compounds were deduced by spectroscopic techniques.     

Two New Sesquiterpenoids from the Rhizomes of Curcuma xanthorrhiza

Zedoardiol ( 1 ), a new furanoguaiane sesquiterpenoid, and 3,4‐dihydroxybisabola‐1,10‐diene ( 2 ), a new naturally occurring bisabolane sesquiterpenoid, together with six known compounds, were isolated from Curcuma xanthorrhiza Roxb . Their structures were determined on the basis of comprehensive spectroscopic analyses, mainly 1D‐ and 2D‐NMR, MS, IR and X‐ray single‐crystal diffraction. Herein, the isolation and structure elucidation of the compounds are described.     

Terminal group effects on the fluorescence spectra of Eu(III) nitrate complexes with a family of amide-based 1,10-phenanthroline derivatives

Four ligands 1,10-phenanthroline-5,6-bis(N,N-dibenzyl-1′-oxopropylamide) (L^a) 1,10-phenanthroline-5,6-bis(N-methyl-N-benzyl-1′-oxopropylamide) (L^b) 1,10-phenanthroline-5,6-bis(N-benzyl-1′-oxopropylamide) (L^c) and 1,10-phenanthroline-5,6-bis(N,N-diethyl-1′-oxopropylamide) (L^d), and their lanthanide(III) (La and Eu) complexes were synthesized. The complexes were characterized by elemental analysis, IR, fluorescence spectroscopy and conductivity. The lanthanide atoms are coordinated by O atoms from C=O, Ar–O –C and N atoms from phen With the difference of the ligands, the fluorescent intensities of the Eu(III) complexes vary regularly in the THF solution. Some factors that influence the fluorescent intensity were discussed.     

Displacement reactions of 2-chloro- and 2,9-dichloro-1,10-phenanthroline: synthesis of a sulfur-bridged bis-1,10-phenanthroline macrocycle and a 2,2′-amino-substituted-bis-1,10-phenanthroline

The synthesis and structural assignments of 9-chloro-1,1-phenanthroline-2(1H)-thione and 1,10-dihydro-1,10-phenanthroline-2,9-dithione have been accomplished. The sulfur-bridged bis-1,10-phenanthroline macrocycle was readily prepared by heating the thione or equimolar amounts of the dithione and 2,9-dichloro-1,10-phenanthroline in diphenyl ether. Displacements of 2-chloro- or 2,9-dichloro-1,10-phenanthroline with N,N-dimethylethylenediamine afforded the corresponding amine and diamino analogues. An amino-substituted-2,2′-bis-1,10-phenanthroline has been prepared.     

Thermal lens spectrometry as a tool for determination of stability constants of complex compounds

The potential of thermal lens spectrometry in the determination of stability constants of complex compounds was explored using copper(I) and iron(II) complexes with 1,10-phenanthroline and 2,9-dimethyl-1,10-phenanthroline as examples. Thermal lens spectrometry offers advantages over conventional spectrophotometry in the determination of stability constants both in aqueous and nonaqueous media. The overall and stepwise stability constants of iron(II) tris(1,10-phenanthrolinate), copper(I) bis(2,9-dimethyl-1,10-phenanthrolinate), and copper(I) bis(1,10-phenanthrolinate) were determined at levels as low as 10⁻⁸–10⁻⁶ mol L⁻¹.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 123–133, January, 2005.     

Dinuclear Complexes of Copper(I) with Crown Ether‐containing N‐Thiophosphorylated Bis‐thioureas and 2,2′‐Bipyridine or 1,10‐Phenanthroline: Synthesis,Characterization, and Picrate Extraction Properties

Reaction of O,O′‐diisopropylthiophosphoric acid isothiocyanate (iPrO)₂P(S)NCS with 1,10‐diaza‐18‐crown‐6, 1,7‐diaza‐18‐crown‐6, or 1,7‐diaza‐15‐crown‐5 leads to the N‐thiophosphorylated bis‐thioureas N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 ( H₂L^I ), N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐18‐crown‐6 ( H₂L^II ) and N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐15‐crown‐5 ( H₂L^III ). Reaction of the potassium salts of H₂L^I–III with a mixture of CuI and 2,2′‐bipyridine ( bpy ) or 1,10‐phenanthroline ( phen ) in aqueous EtOH/CH₂Cl₂ leads to the dinuclear complexes [Cu₂(bpy)₂L^I–III] and [Cu₂(phen)₂L^I–III] . The structures of these compounds were investigated by ¹H, ³¹P{¹H} NMR spectroscopy, and elemental analysis. The crystal structures of H₂L^I and [Cu₂(phen)₂L^I] were determined by single‐crystal X‐ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(=CMe₂)CH₂P(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(S)NHP(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 towards the picrate salts LiPic, NaPic, KPic. and NH₄Pic were also studied.     

Three Unusual New Sesquiterpenes from Alpinia oxyphylla

Two new norcadinene sesquiterpenes oxyphyllones C and D ( 1 and 2 , resp.), and one new 1,10‐secoguaiane sesquiterpene, (+)‐mandassidion ( 3 ), together with two known compounds, oxyphyllenodiol B ( 4 ) and (1R,2R)‐p‐menth‐3‐ene‐1,2‐diol ( 5 ), were isolated from the fruits of Alpinia oxyphylla. Their structures were determined on the basis of spectroscopic analysis, including 2D‐NMR spectroscopic techniques. Compounds 1, 2 , and 3 exhibited no cytotoxicity against three cancer cell lines.     

Crystallographic report: Cis‐[Zn(3,5‐dinitrobenzoato)2(1,10‐phenanthroline)2]·CH3CH2OH

Cis‐[Zn(3,5‐dinitrobenzoato)₂(1,10‐phenanthroline)₂]·CH₃CH₂OH features unidentate and cis‐disposed 3,5‐dinitrobenzoate ligands and chelating 1,10‐phenanthroline ligands so that a distorted octahedral N₄O₂ coordination geometry results. Copyright © 2005 John Wiley & Sons, Ltd.     

选择性响应Cu~(2+)、Ag~+及阴离子的菲咯啉-水杨醛荧光探针

在乙酸酐中用2,9-二甲基-1,10-菲咯啉与水杨醛缩合反应得到2,2′-(1E,1′E)-2,2′-(1,10-菲咯啉-2,9-二基)双(乙烯-2,1-二基)双(2,1-亚苯基)二乙酸酯(探针1);再将其进一步水解得到2,2′-(1E,1′E)-2,2′-(1,10-菲咯啉-2,9-二基)双(乙烯-2,1-二基)二苯酚(探针2)。经1H NMR、13C NMR、IR、MS表征,探针化合物为大共轭结构,发光性能良好。两种探针分别表现出对Cu2+、Ag+不同的荧光猝灭作用,探针2还能识别阴离子F-和AcO-,具有双功能离子检测性能。光谱滴定、等温滴定量热及质谱等测定了配合物组成、作用常数及热力学参数,探针与金属离子的配合为放热反应,作用比为2∶1。     

Synthesis,characterization, and crystal structure of a copper(II) complex of 1,10-phenanthroline and succinate

A mixed ligand complex of Cu(II) with 1,10-phenanthroline and succinate has been synthesized from the reaction of hydrated copper nitrate, succinate, and 1,10-phenanthroline. The nature of bonding and the structure of the complex were characterized by elemental analyses, infrared spectrum, TGA/DTA, and X-ray diffraction. The crystal crystallizes in triclinic space group P 1. The complex is polymeric and the geometry around each copper varies from square planar to distorted square pyramidal or octahedral. Each copper coordinates two oxygens of succinate and two nitrogens of 1,10-phenanthroline. The thermal decomposition of the complex has also been studied by TGA and DTA under inert atmosphere.     

选择性响应Cu2+、Ag+及阴离子的菲咯啉-水杨醛荧光探针

在乙酸酐中用2,9-二甲基-1,10-菲咯啉与水杨醛缩合反应得到2,2’-（1E,1’E）-2,2’-（1,10-菲咯啉-2,9-二基）双（乙烯-2,1-二基）双（2,1-亚苯基）二乙酸酯（探针1）;再将其进一步水解得到2,2’-（1E,1’E）-2,2’-（1,10-菲咯啉-2,9-二基）双（乙烯-2,1-二基）二苯酚（探针2）。经¹H NMR、¹³C NMR、IR、MS表征,探针化合物为大共轭结构,发光性能良好。两种探针分别表现出对Cu²⁺、Ag⁺不同的荧光猝灭作用,探针2还能识别阴离子F^-和AcO^-,具有双功能离子检测性能。光谱滴定、等温滴定量热及质谱等测定了配合物组成、作用常数及热力学参数,探针与金属离子的配合为放热反应,作用比为2：1。     

Synthesis of chelating tertiary phosphine oxides via palladium-catalysed C–P bond formation

Bis(diphenylphosphine oxides) and bis(tert-butyl(phenyl)phosphine oxides) of 1,10-phenanthroline, 2,2′-bipyridine and pyridine were synthesised in good yields via the Pd(OAc)₂/dppf mediated cross-coupling reactions between 6,6′-dichloro-2,2′-bipyridine, 2,9-dichloro-1,10-phenanthroline, or 2,6-dichloropyridine and the corresponding secondary phosphine oxides. These compounds represent potential tetradentate chelating ligands for ions of f-block elements.     

Crystallographic report: {[Zn(O2CC6H4NO2‐m)(1,10‐phenanthroline)2] O2CC6H4NO2‐m}·2H2O·HO2CC6H4NO2‐m

The structure of {[Zn(O₂CC₆H₄NO₂‐m)(1,10‐phenanthroline)₂]O₂CC₆H₄NO₂‐m}·2H₂O·HO₂CC₆H₄NO₂‐m features chelating m‐nitrobenzoate and 1,10‐phenanthroline ligands so that a distorted octahedron N₄O₂ coordination geometry results. Copyright © 2005 John Wiley & Sons, Ltd.     

以1，4-二硝基苯甲酸及邻菲啰啉为配位的镧系金属配位聚合物的合成、结构及性质研究

以1,4-二硝基苯甲酸（HL）和1,10-邻菲罗啉（phen）为配体,通过水热法与镧系金属盐合成了7个一维链状配位聚合物,其分子式为[Ce₂L₆（phen）₂]_n（1）和[LnL₃phen]_n（Ln=Sm,2;Eu,3;Gd,4;Tb,5;Dy,6;Er,7）。由X-射线单晶衍射测定了化合物晶体结构,通过磁性以及荧光测试表征了部分化合物的磁性和荧光性质。     

Synthesis,structures and properties of ternary rare earth complexes with fluorobenzoic acid and 1,10-phenanthroline

Three dimeric rare-earth complexes [Eu(p-FBA)₃(phen)(H₂O)]₂ (1), [Tb(p-FBA)₃phen]₂ (2), and [Tb(o-FBA)₃phen]₂ (3) (where p-FBA = p-fluorobenzoate, o-FBA = o-fluorobenzoate, phen = 1,10-phenanthroline) were synthesized and structurally characterized. All are neutral dimeric molecules. Complex 1 crystallizes in triclinic system, space group P 1. Each Eu(III) ion is eight-coordinate with one 1,10-phenanthroline, one monodentate carboxylate, one water and four bridging carboxylates. Complex 2 crystallizes in triclinic system, space group P 1. Each Tb(III) is also eight-coordinate with one 1,10-phenanthroline molecule, one bidentate chelating carboxylate and four bridging carboxylates. Complex 3 crystallizes in the monoclinic system, space group P2₁/c and consists of two crystallographically different binuclear molecules. Tb(III) ions are eight-coordinate with one 1,10-phenanthroline, one bidentate chelating carboxylate and four bridging carboxylates in both of them. Complex 1 shows bright red luminescence, 2 and 3 show green luminescence under UV light at room temperature. Thermal analysis indicates that are all quite stable to heat.     

MOLECULAR RECOGNITION OF AN ORGANIC MOLECULE BY BIS(TETRAFLUOROBORATE)ZINC(II). SYNTHESIS AND CRYSTAL STRUCTURE OF {[Zn(phen)3](BF4)2}2·MNA·(H2O)1.5

Abstract

The 2:1 adduct {[Zn(phen)₃](BF₄)₂}₂·MNA·(H₂O)_1.5 (1) (where phen = 1,10-phenanthroline and MNA = 2-methyl-4-nitrobenzenamine) was prepared by self-assembly and characterized by X-ray crystallography. The central zinc atom in two non-equivalent [Zn(phen)₃]²⁺ cations exhibits distorted octahedral geometry with Zn-N bond distances of 2.151(6)-2.194(6) Å and 2.136(6)-2.210(6) Å, respectively. The 2-methyl-4-nitrobenzenamine molecule is connected with bis(tetrafluoroborate)tris(1,10-phenanthroline)zinc(II) through a hydrogen bond (N13-H13a…F23? 3.044 Å, ?1 - x, 1 - y, - z). High shape specificity was observed in the recognition process.