Synthesis and Properties of Novel Luminescent Compounds Containing Triphenylamine and Bipyridine Units

Blue luminescent compounds T1―T4 containing triphenylamine donors,bipyridine acceptors and olefinic linkers were synthesized and characterized by 1 H NMR,13 C NMR and high resolution mass spectrometry（HRMS）.Four compounds T1―T4 exhibit excellent solubility in common solvents and good film forming properties.Quantum chemical calculations show that compounds T1―T4 have asymmetric linear structures and the proper highest occupied molecular orbital（HOMO） levels.The UV-Vis absorption and fluorescence emission spectra of the four compounds in dilute chloroform solutions and on the solid films were measured.It reveals that compounds T1―T4 exhibit similar spectral behavior,suggesting that these compounds can form amorphous state in solid films.The calculated absorption and emission spectra of compounds T1―T4 are in good agreement with experimentally determined ones.Compounds T1―T4 have absolute fluorescence quantum yield above 17% in dilute chloroform solutions.Four compounds possess high glass-transition temperature（T g） exceeding 97 ℃ and the maximum T g is 155.28 ℃ for compound T3.Cyclic voltammetry measurements show that these compounds have proper HOMO levels in a range of-5.01―-5.13 eV for hole injection.The properties of compounds T1―T4 indicate that these compounds are candidates for the application in organic light-emitting devices（OLEDs） as hole-transporting materials（HTMs）.

Crystal Structures,Luminescent Properties and Hirshfeld Surface Analyses of Zn(Ⅱ)and Cd(Ⅱ)Compounds Based on 1-(2-Carboxyl-phenyl)-3-(pyridin-2-yl)pyrazole

Two compounds,[Zn2（Hcppp）2（cppp）2（H2O）2]·2 NO3·6 H2O（1） and [Cd（Hcppp）2Cl2]· 3H2O（2）（Hcppp = 1-（2-carboxyl-phenyl）-3-（pyridin-2-yl）pyrazole）,are synthesized and characterized by IR,TGA and X-ray single-crystal/powder diffraction.Compound 1 crystallizes in monoclinic system,space group P21/c with a = 9.894（2）,b = 15.856（3）,c = 20.430（4） A,β = 101.70（3）°,V = 3138.5（11） A3,Z = 2,Mr = 1457.94,Dc = 1.543 g/cm^3,F（000） = 1504,R = 0.0278 and wR = 0.0749 for 6157 observed reflections（I 〉 2σ（I））.Compound 2 crystallizes in triclinic system,space group P1 with a = 9.1424（4）,b = 11.6427（5）,c = 16.1345（7） A,α = 102.6430（10）°,β = 95.4530（10）°,γ = 104.0060（10）°,V = 1605.94（12） A3,Z = 2,Mr = 767.88,Dc = 1.588 g/cm^3,F（000） = 776,R = 0.0307 and wR = 0.0764 for 6275 observed reflections（I 〉 2σ（I））.Compound 1 exhibits a binuclear structure while compound 2 shows a mononuclear structure.In compound 1,two cppp-ligands display the μ2-kN,N′：k O and two Hcppp ligands show the μ1-kN,N′ coordination modes.However,two Hcppp ligands connect one Cd（Ⅱ） cation and exhibit the μ1-kN,N′ binding mode in compound 2.The compounds are both studied using Hirshfeld surface analyses and 2D fingerprint plots.The luminescent properties are also discussed.

A Zn(Ⅱ) Coordination Polymer with 4-Connected bbf Topology： Synthesis, Crystal Structure and Luminescent Property

A new Zn（Ⅱ） compound, namely {Zn（BTA）（pdc）0.5}n（1, HBTA = 1,2,3-benzotriazole, H2pdc = terephthalic acid）, has been hydrothermally synthesized and characterized by elemental analysis, infrared analysis, powder X-ray diffraction analysis and single-crystal X-ray structural analysis. The crystal structure is of monoclinic system, space group P21/c with a = 10.751（3）, b = 9.792（3）, c = 9.292（3）A, β = 95.391（4）°, V = 973.9（5） A^3, C10H6N3O2 Zn, Mr = 265.57, Z = 4, Dc = 1.811 g/cm3, F（000） = 532, μ = 2.506 mm-1, R = 0.0221 and w R = 0.0605 for 2075 observed reflections（I 〉 2s（I））. Single-crystal X-ray structural analysis reveals that compound 1 features a three-dimensional（3D） framework with 4-connected bbf topology. Moreover, the thermogravimetric（TG） analysis and photoluminescent property of 1 were also discussed.

Hydrothermal Synthesis, Crystal Structure and Luminescent Property of a Cd(Ⅱ) Compound with(4,6)-Connected Topology

A new Cd（Ⅱ） coordination polymer, namely {Cd_2（L）（biimpy）（H_2O）}_n（1, H4 L = 3-（3？,5？-dicarboxylphenoxy）phthalic acid, biimpy = 2,6-bis（1-imdazoly）pyridine）, has been successfully synthesized via the hydrothermal reactions of Cd（Ⅱ） ions, H_4L and biimpy. The crystal structure is of triclinic, space group P1 with a = 7.7874（5）, b = 9.9716（5）, c = 18.5278（6） ？, α = 91.327（4）, β = 96.689（4）, γ = 111.896（5）o, V = 1322.39（12） ？~3, C_（27）H_（17）Cd_2N_5O_（10）, M_r = 796.26, Z = 2,D_c = 2.000 g/cm^3, F（000） = 780, μ = 1.679 mm^（-1）, R = 0.0345 and wR = 0.0767 for 3890 observed reflections（I 〉 2s（I））. Single-crystal X-ray structural analysis reveals that compound 1 features a three-dimensional（3D） framework based on two different dinuclear [Cd_2（COO）_2] building subunits, and topological analysis shows that it can be simplified into a binodal（4,6）-connected topological network with the point symbol of {3.4~2.5~2.6}{3~2.4~2.5~2.6~4.7~4.8}. Moreover, the thermal stability and luminescent property of compound 1 were also studied.

Synthesis,Crystal Structure and Photoluminescent Property of a Novel Dy^(3+) Coordination Compound Containing Rare(H_2O)_(22) Clusters

A novel Dy^（3＋） coordination compound,（H_2pipz）（H_3O）[Dy（pydc）_3]·11H_2O（1,pipz = piperazine and H_2pydc = pyridine-2,6-dicarboxylic acid）,has been hydrothermally synthesized and characterized by X-ray single-crystal diffraction,elemental analysis. It is interesting that the packing structure of compound 1 contains 22-core water clusters. Compound 1 is extended into a threedimensional supramolecular structure via O···H···O hydrogen bonding interactions. Furthermore,the luminescent property of compound 1 was also investigated.

A Novel Zn(Ⅱ)Complex with 4-Connected umc Topology:Synthesis,Crystal Structure and Luminescent Property

A novel complex, [Zn（L）]2·H2O（1, H2 L = 4-aminophthalic acid）, has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in monoclinic, space group C2/c with a = 12.4267（6）, b = 7.7482（3）, c = 18.6983（8） A, β = 110.437（3）°, V = 1687.04（13） A3, Z = 4, C16H12N2O9Zn2, Mr = 507.06, Dc = 1.996 g/cm3, μ = 2.903 mm-1, S = 0.989, F（000） = 1016, the final R = 0.0304 and w R = 0.0720 for 12618 observed reflections（I 〉 2σ（I））. Single-crystal X-ray structural analysis reveals that compound 1 features a three-dimensional（3D） framework with 4-connected umc topology. Moreover, the thermogravimetric（TG） analysis and photoluminescent property of 1 were also discussed.

Two Three-dimensional Terbium-1,4-benzenedicarboxylate Coordination Polymers：Syntheses,Structures,and Luminescence

Two coordination polymers with 1,4-benzenedicarboxylic acid（H2BDC） ligand, namely, [Tb3（BDC）（4.5）（H2O）（DMF）2]n （1） and [Tb2（BDC）3（H2O）2（DMF）2]n（2）, have been synthesized and characterized. Both compounds crystallize in the triclinic system, space group P1. For compound 1, a = 10.8528（5）, b = 12.2516（5）, c = 16.9031（7） A, α = 104.462（1）, β = 93.659（1）, γ = 101.404（1）°, V = 2118.1（2） A^3, Z = 2, C（42）H（34）N2O（21）Tb3, Mr = 1379.47, Dc = 2.163 g/cm^3, μ = 5.045 mm^-1, F（000） = 1326, the final R = 0.0212 and wR = 0.0570 for 8592 observed reflections with I 〉 2σ（I）. For compound 2, a = 8.547（1）, b = 10.170（1）, c = 11.192（1）A？, α = 65.531（1）, β = 71.886（1）, γ = 78.796（1）°, V = 839.2（2） A^3, Z = 1, C（30）H（30）N2O（16）Tb2, Mr = 992.40, Dc = 1.964 g/cm^3, μ = 4.257 mm^-1, F（000） = 482, the final R = 0.0220 and wR = 0.0649 for 3626 observed reflections with I 〉 2σ（I）. The compounds exhibit different structural topologies depending on the nature of templating agents in the reactions though the templating agents are not incorporated in the final solids. Compound 1 exhibits a three-dimensional（3D） framework based on the rod-shaped terbium-carboxylate building blocks constructed from linear trinuclear Tb3 units. Compound 2 has a 3D framework containing two interpenetrating pcu topological networks based on the 6-connected dinuclear Tb2 secondary building units. Photoluminescence studies show both compounds exhibit typical Tb（Ⅲ） luminescence emissions. An efficient ligand-to-Tb（Ⅲ） energy transfer is observed in the emission spectra for both compounds.

Synthesis,Crystal Structure and Photophysical Property of 4-(9-Oxoacridin-10(9H)-yl)Benzonitrile

A purely organic compound, 4-（9-oxoacridin-10（9 H）-yl） benzonitrile（1）, was synthesized and characterized by NMR, UV-Vis, high resolution mass spectrum, and X-ray single-crystal structure analysis. It crystallizes in monoclinic system, space group P21/c with a = 9.7420（2）, b = 10.4967（2）, c = 14.3896（3）A°, β = 104.755（2）°, V = 1422.94（5）, Z = 4, Mr = 296.32, Dc = 1.383 g/cm^3, F（000） = 616, μ = 0.690 mm^–1, GOOF = 1.035, the final R = 0.0370 and w R = 0.1010 for 2649 observed reflections with I 〉 2σ（I）. Compound 1 in tolune exhibits deep blue luminescence with maximum emission peaks at 403 and 419 nm, lifetimes of 3.8 ns and quantum yields of ф = 0.46 at room temperature. The experimental and computational results show that the emission of the compound originates from the acridinone moiety and has π-π＊ character.