A New Cadmium(Ⅱ) Coordination Polymer Constructed by 2-(2-Chloro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline and 1,2,3-Benzenecarboxylate: Synthesis, Structure and Luminescence

A new Cd（II） coordination polymer, namely, [Cd3（1,2,3-BTC）2（L）2]·2.25H2O （1, L = 2-（2-chloro-6-fluorophenyl）-1H-imidazo[4,5-A][1,10]phenanthroline and 1,2,3-BTC = 1,2,3-ben- zenetricarboxylate）, has been synthesized under hydrothermal conditions. The compound was characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group Pī with α = 11.650（2）, b = 12.240（2）, c = 19.760（4） A, α = 72.01（3）, β = 77.11（3）, γ = 83.48（3）°, V = 2609.4（9） A3, Z = 2, C56H31Cd3Cl2F2N8O14.25, Mr = 1489.99, Dc = 1.896 g/cm3, F（000） = 1466, μ（MoKa） = 1.401 mm^-1, R = 0.0401 and wR = 0.1104. Compound 1 shows a 1D chain structure, and the neigh- boring 1D chains of 1 are joined together by π···π interactions to result in a 2D supramolecular layer. In addition, the luminescent property of 1 has been studied in the solid state at room temperature.

Synthesis, Crystal Structure and Second-order Optical Nonlinearity of 6-Nitro-[1,10]phenanthroline-1-ium Nitrate, [HphenNO2]^+NO_3^-

The title compound [HphenNO2]+NO3- has been prepared and characterized by elemental analysis, electronic absorption spectroscopy, TG/DTA, IR, 1H and 13C NMR spectro- scopy. Single-crystal X-ray structure determination of the title compound was also carried out. It crystallizes in monoclinic, space group Cc with a = 13.861(3), b = 10.142(2), c = 8.7320(17) ? b = 103.70(3)? C12H8N4O5, Mr = 288.22, V = 1192.6(4) 3, Z = 4, Dc = 1.605 g/cm3 , F(000) = 592, (MoK) = 0.129 mm-1, R = 0.0439, wR = 0.1125 and GOF =1.114. In the crystal lattice, the molecules create a network structure through hydrogen bonds. The second order optical non- linearity was performed by quantum chemical method, showing the title compound has higher molecular hyper polarizability value (?= 24.66×10-30 esu).

Synthesis,Crystal Structure and DNA Interaction of a Chiral Platinum(Ⅱ)Complex with 2-(2,3-Dimethoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline

A new platinum（Ⅱ） complex of [Pt（chda）（2,3-dmopip）]Cl·H2O（1, chda = cyclohexan-ediamine, 2,3-dmopipH = 2-（2,3-dimethoxyphenyl）-1H-imidazo[4,5-f][1,10]phenanthroline） has been synthesized by hydrothermal methods and characterized by elemental analysis, IR, single-crystal X-ray diffraction, UV-vis and fluorescent spectrum. In complex 1, the platinum adopts a four-coordinated square planar geometry. The DNA-binding interaction has been investigated. The complex can bind to DNA by an intercalative mode, presenting high DNA-binding affinity.

Off-on-off luminescent switching of a dye containing imidazo[4,5-f][1,10]phenanthroline

A new acid-base fluorescent switch containing both imidazo[4,5-f][1,10]-phenanthroline and triphenylamine groups has been synthesized.Its fluorescence emissions and absorptions can be reversibiy changed through protonation/deprotonation of imidazole and amine moiety by controlling the intramolecular charge transfer（ICT） process,leading to off-on-off fluorescent molecular switching.

Highly regioselective synthesis of dicyano-8a,10,11-trihydropyrrolo[1,2-α][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.

Synthesis, Structure and Photoluminescence of a New Cd(Ⅱ) Coordination Polymer Based on 4-(Carboxymethoxy)-benzoic Acid and 1,10-Phenanthroline Derivative

A new ID coordination polymer, [Cda（L1）2（L2）2].H2O （1, H2L1 = 4-（carboxy- methoxy）benzoic acid and L2 = 2-（4-fluorophenyl）-I H-imidazo[4,5-f][1,10]phenanthroline）, has been hydrothermally synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 9.985（5）, b = 10.768（5）, c = 12.512（5） A, a = 68.959（5）, β = 80.354（5）, γ = 79.663（5）°, V= 1227.4（10） A3, Z = 1, C56H36Cd2F2N8O11, Mr = 1259.73, Dc = 1.704 g/cm3, F（000） = 630, μ（MoKa） = 0.949 mm-1, R = 0.0261 and wR = 0.0655. The L1 anions link the neighboring Cd（II） atoms to form a 1D double chain structure. The L2 ligands are alternately located on both sides of the double chains. More interestingly, the lateral L2 ligands from adjacent double chains are paired to furnish strong π-π interactions, yielding a 2D supramolecular layer. N-H...O, O-H...N and O-H...O hydrogen bonds further stabilize the structure of 1. The luminescent property of 1 was studied in solid state at room temperature.

A New Cadmium(Ⅱ) Dimer Constructed by 1,10-Phenanthroline Derivative and Chlorine Anions: Syntheses, Crystal Structure and Photoluminescence

In this work, a new Cd（Ⅱ） dimeric compound, [Cd（Cl）2（L）（H2O）]2 （1, L = 2-（4- fluorophenyl）-lH-imidazo[4,5-f][1,10]phenanthroline）, has been achieved under hydrothermal conditions. The structure of compound 1 was determined by single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic, space group P21/c with a = 8.944（2）, b = 18.781（5）, c = 10.904（3） A, β = 91.392（4）°, V = 1831.2（8） A^3, Z = 2, C3sH26Cd2F2C14Cl4N8O2, Mr = 1031.27, Dc = 1.870 g/cm3, F（000） = 1016, μ（MoKα） = 1.513 mm^-1, R = 0.0532 and wR = 0.1407. Each Cd（ll） atom is in an octahedral coordination sphere, completed by two nitrogen atoms from one L ligand, two chlorine anions, and one water oxygen atom. Two chlorine anions bridge two Cd（Ⅱ） atoms to give a dimer [Cd（Cl）2（L）（H2O）]2. Adjacent dimers are stacked by one type of π…π interactions among L ligands to generate a 1D supramolecular chain. Further, the 1D supramolecular chains are stacked by another type of π…π interactions among L ligands to give a 2D supramolecular layer. Finally, the luminescent property of 1 has been studied in solid state at room temperature.

Diastereoselective Synthesis of 1,10-Dihydropyrrolo [ 1,2-a] [1,10]phenanthroline Derivatives via 1,3-Dipolar Cycloaddition Reaction

The functionalized 1,10-dihydropyrrolo[1,2-a][1,10]phenanthroline derivatives were synthesized in good yields and with high diastereoselectivity by 1,3-dipolar cycloaddition reactions of N-phenacylphenanthrolinium bromides or N-ethoxycarbonylmethylene phenanthrolinium bromide with various nitrostyrenes in acetonitrile at room temperature in the presence of triethvlamine,

Synthesis,luminescent properties,and theoretical study of novel Sm^(3+) and Dy^(3+) complexes containing β-diketone and 1,10-phenanthroline

Two new ternary complexes of 1-（2-thienyl）-3-（p-phenylethynylphenyl）-1,3-propanedione（HTPP） and 1,10-phenanthroline（phen） with Sm^3＋ and Dy^3＋ were synthesized.The composition of the ternary complexes was characterized as Sm（TPP）3phen and Dy（TPP）3phen,respectively,by infrared（IR） spectra,chemical analysis,elemental analysis,and thermodynamic analysis.At room temperature,under UV light excitation,the Sm^3＋ and Dy^3＋ complexes exhibit characteristic emissions of the central ions.It is found that the fluorescence intensity of Sm（TPP）3phen is stronger than that of Dy（TPP）3phen.In order to explain this phenomenon,an accurate quantum chemistry calculation was carried out,and the result is in good agreement with the experiment data.

Hydrothermal Syntheses and Crystal Structures of Three Lanthanide(Ⅲ)Complexes Based on Carboxyl Derivatives of 1,10-Phenanthroline

Three lanthanide（III） complexes [Ln（4-NCP）（1,4-BDC）]n·xn H2O（Ln = Pr（1）, Sm（2）, Nd（3）. 4-HNCP = 2-（4-carboxyphenyl）imidazo（4,5-f）（1,10）phenanthroline, 1,4-H2 BDC = benzene-1,4-dicarboxylic acid） have been hydrothermally synthesized and characterized via elemental analysis, infrared spectrometry and single-crystal X-ray diffraction. Structural analyses revealed that complexes 1~3 possess similar porous three-dimensional frameworks with the point symbol {4^（12）·6~3}. Meanwhile, complexes 1~3 exhibit excellent thermal stabilities and complex 2 exhibits characteristic luminescent property.

Fluorescence of complexes of EuⅢwith aromatic carboxylic acid-1,10-phenanthroline

The 1,10 phenan throline aromatic carboxylic acid(benzoic acid and o phthalic acid) binary and ternary complexes of europium were synthesized.The fluorescence and FT IR spectroscopy,elemental analysis,UV spectroscopic studies on these complexes were also performed.These complexes can emit strong red fluorescence of Eu? excited by UV light.At the same excited wavelength,the fluorescence spectra of the complexes were also studied.The results indicated that the fluorescence intensities of ternary complexes are stronger than that of binary complexes.The reason is that phenanthroline has higher electron density and higher orbit scope in the conjugated system and consequently an easier energy transfer to the europium ion,which makes the fluorescence intensity of ternary complexes be stronger than that of binary complexes.

Crystal Structure of cis-Dichlorobis-(1,10-phenanthroline) Manganese(Ⅱ)

MnCl2 (C12,H8N2)2, Mr= 486. 26, monoclinic, P21,/c, a= 9. 461 (5),b= 15. 20(1), c= 14. 514(2) A, β=98. 82(3)°, V=2062(2) A3, Z=4, Dc= 1. 57g/cm3. λ(MoKα) = 0. 71073 A, μ(MoKα) = 0. 895 mm-l, F (000) = 988, T= 296K. Final R= 0. 043, Rw= 0. 053 for 2569 observed reflections. The Mn atom is co-ordinated by two Cl anions and four N of two phenanthroline (phen) molecules, forming a distorted octahedron. Two Mn--Cl bond lengths are 2. 437(2) and 2. 449(2) A,respectively. The Mn--N bond lengths vary from 2. 290(3) to 2. 367 (4) A。 The dihedral angle between two phen best planes is 90. 4°.

Syntheses of Novel 5-Alkylamido-1,10-phenanthrolines

Amino-1,10-phenanthroline and three types of new 5-substituted 1,10-phenanthroline derivatives by different alkyl amides, phen-NHCOR[phen=1,10-phenanthroline; R=CHCH 2; (CH 2) nBr, n=1,3—5; (CH 2) nCH 3, n=9—14], were synthesized. They were characterized by means of elemental analyses, infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and mass spectroscopy. These new compounds are important ligands or the active materials of ruthenium(Ⅱ) electrochemiluminescent(ECL) sensors.

Crystal Structures and Luminescent Properties of Three Coordination Polymers Based on 2,5-Furandicarboxylic Acid Ligand and 1,10-Phenanthroline

Three new coordination polymers,namely [Zn（FDA）（phen）（H2O）·H2O]n（1）,[Cd（HFDA）（phen）2（NO3）]（2） and [Cd（FDA）（phen）]n（3）（H2FDA = 2,5-furandicarboxylic acid,phen = 1,10-phenanthroline） have been synthesized by the solvothermal method and characterized by elemental analysis,IR,powder X-ray diffraction,thermogravimetric analysis and X-ray single-crystal diffraction analysis.For 1,the neighboring Zn^2＋ ions are bridged by FDA2-as linkers to form one-dimensional（1D） chains,and phen ligands are as the terminal ligands.Furthermore,the 1D chains are packed into a three-dimensional（3D） supramolecular structure through hydrogen bonds and π-π interactions.For 2,the H2FDA ligand is partial deprotonation,which is a rare phenomenon among other coordination polymers based on H2FDA.Under the synergetic effect of phen ligands and the partial deprotonation of H2FDA,the structure of 2 is discrete.For 3,the Cd^2＋ ions are linked by two carboxylates of FDA^2-ligand to give rise to 1 D zig-zag chains,and phen ligands chelate the Cd^2＋ ions like 1.In addition,solid-state luminescent spectra of three coordination polymers were also studied at room temperature.

PREPARATION AND MAGNETIC PROPERTIES OF POLYMERIC COMPLEXES CONTAINING 1,10-PHENANTHROLINE

A series of polymeric complexes were prepared from Fe^2＋, Co^2＋ or Ni^2＋ and poly（Schiff base） （DAPcIPA）, which was obtained by polycondensation of 5,6-diamino-1,10-phenanthroline （DAP） with isophthalaldehyde （IPA）. The structures of the polymer and the polymeric complexes were characterized by IR, 1^H-NMR and elemental analysis. The magnetic behavior of these complexes was measured as a function of magnetic field strength （0-3.98 ~ 106 A/m） at 5 K and as a function of temperature （5-300 K） at a magnetic field strength of 2.39 × 10^6 A/re. Experimental results show that DAPcIPA-Ni^2＋, DAPcIPA-Co^2＋ are soft ferromagnets while DAPcIPA-Fe^2＋ exhibits features of an antiferromagnet.

Luminescent Properties of Bi-Rare Earth Complexes with m-methylbenzoic Acid and 1,10-phenanthroline

The bi rare earth complexes EuTb( m MBA) 6(phen) 2·2H 2O, TbY( m MBA) 6(phen) 2·2H 2O were synthesized by the reaction of RECl 3 with m methylbenzoic acid and 1,10 phenanthroline in ethanol solution, where m MBA=m methylbenzoate and phen=1,10 phenanthroline. The luminescence properties of the title complexes were studied in comparison with the corresponding complexes Eu 2( m MBA) 6(phen) 2·2H 2O and Tb 2( m MBA) 6(phen) 2·2H 2O respectively. The results indicate that the emission intensity from europium ion can be greatly enhanced by the terbium ion, while the emission from terbium ion was strongly quenched by europium ion in EuTb( m MBA) 6(phen) 2·2H 2O; the emission intensity from terbium ion can be greatly enhanced by yttrium ion in TbY( m MBA) 6(phen) 2·2H 2O. The mechanism about the results was discussed.

白细胞介素10工程化修饰人脐带间充质干细胞优效治疗炎症性肠病

背景:间充质干细胞来源广泛、易体外增殖,并可分泌一系列免疫调节因子抑制炎症、促进组织修复再生,广泛应用于各种疾病治疗研究。但是对于多种疾病,间充质干细胞的治疗效果有限。针对疾病特定发病机制或者干预靶点进行工程化修饰间充质干细胞是未来细胞治疗的重要发展方向。目的:白细胞介素10是一种典型的抗炎细胞因子,有助于调节免疫反应并诱导巨噬细胞向抗炎表型极化,该研究探讨白细胞介素10基因工程化修饰人脐带间充质干细胞对炎症性肠病的治疗效果。方法:通过电转染建立稳定过表达人白细胞介素10基因的人脐带间充质干细胞,并基于细胞治疗产品标准筛选出临床级细胞。给予C57BL/6J小鼠自由饮用5%葡聚糖硫酸钠盐水溶液建立急性结肠炎模型,分别在造模前1 d(尾静脉途径)与造模后第4天(腹腔途径)注射空质粒转染的人脐带间充质干细胞或过表达人白细胞介素10基因的人脐带间充质干细胞(1×10~6个/只)。在造模后第6天取结肠组织进行苏木精-伊红染色评估组织学变化,免疫荧光染色检测增殖细胞核抗原与CD31的表达。结果与结论:构建的稳定过表达白细胞介素10的工程化人脐带间充质干细胞,满足临床级人脐带间充质干细胞质量标准;人脐带间充质干细胞对小鼠急性结肠炎具有修复效果,过表达白细胞介素10基因的人脐带间充质干细胞的治疗效果更加优效,更显著地抑制急性结肠炎小鼠的体质量下降(P<0.05)、结肠缩短(P<0.05)以及结肠组织损伤(P<0.05);过表达白细胞介素10基因人脐带间充质干细胞组结肠组织切片中增殖细胞核抗原阳性细胞与CD31阳性细胞显著多于人脐带间充质干细胞组,表明过表达白细胞介素10基因的人脐带间充质干细胞可能通过显著促进肠组织细胞增殖和血管再生进而促进结肠组织修复。

Photophysical Properties of Rare Earth Complexes with 3,4-Furandicarboxylic Acid and 1,10-Phenanthroline

Synthesis, IR spectra, UV vis spectra and photophysical properties of Gd 3+ , Eu 3+ , Tb 3+ complexes with 3,4 furandicarboxylic acid and 1,10 phenanthroline are reported. Intramolecular energy transfer process for these complexes is discussed in detail. It is found that the intramolecular energy transfer efficiency depends on the relative positions between the resonance energy levels of the central rare earth ions and the lowest triplet state energies of ligands.

RUTHENIUM COORDINATION COMPOUBNDS WITH POLYPYRIDINES Ⅳ SYNTHESIS AND CHARACTERIZATION OF （2－PHENYL）IMIDAZO［f］ 1， 10－PHENANTHROLINE AND THEIR Ru（Ⅱ） COORDINATION COMPOUNDS

Two new polypyridine ligands. imidazo[f] 1, 10-phenanthroline(IP)and 2-phenyl-imidazo[f]1,10-phenanthroline (PIF) and their Ru (Ⅱ)mixedtype coordination compounds together with 2,2'-bipyridine(bpy)and1, 10-phenanthroline(phen)are synthesised and charaeterized by elementalanalyses meltion points ,electronic absorption,IR,emission spectra and eyclic voltammetry.

Synthesis and Properties of Eu(Ⅲ) Complexes with Aromatic Carboxylic Acid, Dibenzoylmethane and 1, 10-phenanthroline

In order to obtain an excellent luminescent material, herein four complexes of Eu(Ⅲ) were synthesized with dibenzoylmethane (DBM), benzoic acid (BA) and phenylacetic acid (PLA) as the anion ligands, and 1, 10-phenanthroline (phen) as the neutral ligand. The complexes Eu(DBM)3phen (1), Eu(DBM)(BA)2phen (2), Eu(DBM)(PLA)2phen (3) and Eu(DBM)2(PLA)phen (4) were characterized by elemental analysis, IR and TG-DTG. In these complexes, the Eu(Ⅲ) ions are bonded to the oxygen atoms of carboxylate (or dibenzoylmethane), and the nitrogen atoms of phen. The TG-DTG analysis indicated that these complexes are thermally stable. Their excitation and luminescence spectra revealed that the complexes emitted the characteristic luminescence of Eu(Ⅲ): 579 nm (5D0→7F0), 589 nm (5D0→7F1), 610 nm (5D0→7F2). The emission peak at ca. 610 nm was the most intensive. The order of their fluorescence intensity was: Eu(DBM)2(PLA)phen (4)>Eu(DBM)(PLA)2phen (3)>Eu(DBM)3phen (1)>Eu(DBM)(BA)2phen (2).