吡啶-2,6-二甲酸氢锂的合成、结构及热化学性质

以甲醇和水的混合溶液为溶剂, 合成了吡啶-2,6-二甲酸氢锂Li(HDPC)(H₂O)(s), 利用X射线单晶衍射法表征了其晶体结构. 用精密自动绝热热量计测量了其在78～378 K温区的低温热容. 通过最小二乘法拟合得到摩尔热容随折合温度变化的多项式方程, 利用此方程计算出了化合物的舒平热容和各种热力学函数. 设计合理的热化学循环, 利用等温环境溶解-反应热量计分别测定所设计热化学反应的反应物和产物在选定溶剂中的溶解焓, 通过计算得到反应焓为-(46.83 ±0.16) kJ/mol. 利用Hess定律计算出吡啶-2,6-二甲酸氢锂的标准摩尔生成焓为-(747.90 ±1.46) kJ/mol. 利用紫外-可见光谱仪对反应物和产物溶液的测量证实所设计热化学循环的可靠性.     

吡啶-2,6-二甲酸氢钾的合成、结构表征及热化学性质

合成了吡啶-2,6-二甲酸氢钾(KHDPC). 利用X射线单晶衍射仪确定了化合物的晶体结构. 用精密自动绝热热量计测量了其在78~360 K温度区间的低温热容. 利用最小二乘法对配合物的实验热容进行拟合, 得到热容随温度变化的多项式方程. 利用此方程计算出温度区间内的舒平热容值及相对于298.15 K时的热力学函数值. 利用Hess定律设计合理的热化学循环, 在等温环境下利用溶解-反应热量计分别测定所设计热化学反应的反应物和产物在所选溶剂中的溶解焓并计算出反应的反应焓. 最后, 计算出该化合物的标准摩尔生成焓为-(1052.69±1.52) kJ/mol.     

Synthesis, Structure, Luminescence and Theoretical Investigations on a New Tin Complex with (2,3-f)-pyrazino(1,10)phenanthroline-2,3-dicarboxylic Acid

A new tin complex Sn(CH3 HPPDA)Cl4 (1) was prepared from SnCl4·5H2O with (2,3-f)-pyrazino(1,10)phenanthroline-2,3-dicarboxylic acid (H2PPDA) by solvothermal reaction in methanol, and characterized by single-crystal X-ray diffraction analysis, optical absorption spectrum and photoluminescence. Compound 1 crystallizes in a monoclinic centrosymmetric space group of P21/c with a = 12.418(2), b = 11.9467(12), c = 15.845(3), β= 107.948(7)°, V = 2236.2(6)3 , Z = 4, Mr = 594.78, Dc = 1.767 g/cm3 , μ= 1.651 mm-1 , F(000) = 1160, S = 1.023 and T = 293(2) K. The final R = 0.0847 and wR = 0.2431 for 3144 observed reflections with Ⅰ > 2σ(Ⅰ). The discrete mononuclear Sn(CH 3 HPPDA)Cl 4 complex is connected into a supramolecular network of 1 by intramolecular and intermolecular C-H···Cl and intermolecular C-H···O hydrogen bonding interactions. Compound 1 displays fluorescence with a lifetime value of about 7.58 ns in the visible region under visible-light excitation, and the origin of the luminescent emission is primarily assigned to the combination of intraligand charge-transfer of CH3 HPPDA and Cl--to-CH 3 HPPDA charge-transfer mechanism which is probed by the density of states (DOS) calculations.     

Hydrothermal Synthesis and Crystal Structure of a Heterometallic Cu/Cd Complex with H2dipic （Pyridine-2,6-dicarboxylic Acid）

1 INTRODUCTION In recent years the chemistry of coordination poly- mers has been very prosperous, affording diverse architectures[1]. The creation of these compounds with tunable properties and functions has been applied in many fields, such as molecular recogni- tion, adsorption and separation processes, catalysis, ion exchange and molecular magnet[2～4]. The advan- tage of these metal-organic compounds allows a wide choice in various parameters, including diverse electronic properties an…     

Synthesis,Crystal Structure and Properties of the Cobalt(Ⅱ) Complex of Methyl-5-norbornene-2,3-dicarboxylic Acid

A new cobalt complex Co(C10H8N2)(H2O)3[C9H11O2(COO)] with methy-5-norbornene-2,3-dicarboxylic anhydride acid(MNA) and 2,2'-bipyridine as ligands has been synthesized in the mixed solvents of ethanol and water. It crystallizes in monoclinic, space group P21/c with a = 13.0430(13), b = 21.014(2), c = 7.5151(7) ?, β = 102.319(2)o, V = 2012.4(3) ?3, Dc = 1.529 g/cm3, Z = 4, F(000) = 964, GOOF = 1.051, the final R = 0.0457 and wR = 0.0974. The crystal structure shows that the cobalt ion is coordinated with four oxygen atoms from one MNA molecule and three water molecules together with two nitrogen atoms from the 2,2'-bipyridine molecule, forming a distorted octahedral coordination geometry. The thermal stability and electrochemical properties have studied in this paper.     

4-羟基吡啶-2，6-二羧酸配体构筑的环状四核镉配合物的水热合成、晶体结构及性质研究

在水热条件下合成了一个金属镉配合物[Cd4(cam)4(phen)4]·4H2O(H2cam=4-羟基吡啶-2,6-二羧酸,phen=1,10-邻菲咯啉),并用元素分析、红外光谱、X-射线单晶衍射、热重分析和荧光分析对其进行了表征。晶体结构表明:该配合物属于单斜晶系,P21/c空间群,晶胞参数为:a=1.42161(10)nm,b=1.94642(13)nm,c=1.43966(10)nm,β=115.3850(10)°。每个CdⅡ离子七配位呈变形五角双锥几何构型,两对CdII离子与4个(cam)2-离子相连形成了环状四核结构。相邻的四核单元通过氢键的识别作用形成二维超分子网;氢键和π…π堆积作用进一步将其扩展为三维超分子结构。     

以吡啶-2,5-二羧酸或噻吩-2,5-二羧酸为配体的过渡金属配合物的合成、晶体结构及性质

以吡啶-2,5-二羧酸(2,5-pyridinedicarboxylic acid,H_2L_1)、噻吩-2,5-二羧酸(Thiophene 2,5-dicarboxylic acid,H_2L_2)为主要配体,4,4′-联吡啶(4,4′-bipy)、菲咯啉(phen)为辅助配体,采用溶剂热法成功合成了3个过渡金属配合物:[Co_2(L_1)_2(bipy)(H_2O)_6]·bipy·H_2O (1)、[Cu(L_2)_2(bipy)_2]n(2)、[Ni_2(L_2)(phen)_2(H_2O)_4](3),并利用X射线单晶衍射法、红外光谱(IR)、荧光光谱(FL)和热重分析(TG/DTG)等测试手段对其进行了表征。单晶结构分析表明:配合物1、配合物2为P1空间群,配合物3为P2/n空间群;配合物1和配合物3为零维双核小分子结构,配合物2为二维层状结构。     

Synthesis, Structural Characterization and Luminescence of Lanthanide Coordination Polymers with Pyridine-2,5-dicarboxylic Acid

The complexes of formulas [Ln₂(pydc)₂(Hpydc)₂(H₂O)₄]·2H₂O [Ln=Ce ( 1 ), Pr ( 2 ), H₂pydc=pyridine‐2,5‐di‐carboxylic acid] have been hydrothermally synthesized and characterized by elemental analysis, IR, TG and single‐crystal X‐ray diffraction. The structure analyses for 1 and 2 indicate that one‐dimensional metal helical chains are linked through carboxylate groups, and the helical chains are connected with the bridging pydc^2? anion, forming two‐dimensional layered polymeric structures. The luminescent properties of complexes were also discussed.     

Synthesis and Structure of a New Gadolinium Porous Complex Assembled from 2,3-Pyrazinedicarboxylic Acid and Ammonia

A new gadolinium porous complex,(NH_4)_2[Gd2(pzdc)4(H_2O)2], was synthesized through hydrothermal reaction of 2,3-pyrazinedicarboxylic acid and Gd(NO3)3·6 H_2O with the pH value adjusted by ammonia. It was characterized by elemental analysis, FT-IR, TGA and further by single-crystal X-ray crystallography. It crystallizes in monoclinic, space group P21/c with a = 14.249(7), b = 15.889(8), c = 12.846(7) ?, β = 95.724(10)°, V = 2894(3) ?3, Z = 4, Dc = 2.385 g/cm3, μ(Mo Ka) = 4.65 mm–1 and F(000) = 1976. 1976 reflections were measured and 6446 independent reflections(Rint = 0.0985) were used in further refinement. The complex exhibits a 3D framework constructed from the [Gd2(pzdc)4(H_2O)2]2-building blocks. It is scarce that the NH4+ cations are located in the channels and balance the charge of anion framework. Furthermore, the ion exchange property of this complex has also been studied. The NH4+ cations can be replaced by Na+ cations, which is an uncommon phenomenon for gadolinium-containing porous complex.     

吡啶-2,6-二甲酸配位聚合物的研究进展

概述了以吡啶-2,6-二甲酸为配体的配位聚合物的研究进展.按照同多核和异多核配位聚合物进行分类,并介绍了它们的合成技巧、结构特点以及突出性能等.     

Synthesis,Crystal Structure and Photoluminescence of a TADF Cuprous Complex

A cuprous mononuclear copper complex [Cu(adpypz)CH3CNPPh3]BF4·CH2Cl2(1, adpypz = 9,9-dimethyl-10-(6-(3-phenyl-1H-pyrazol-1-yl)pyridin-2-yl)-9,10-dihydroacridine) was synthesized and characterized by Elemental Analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic, space group P1 with a = 11.3388(4), b = 13.4569(4), c = 16.2561(6) ?, α = 97.154(3), β = 92.187(3), γ = 114.119(4)°, V = 2235.38(13) ?3, Z = 2, Mr = 967.12, Dc = 1.437 g/cm~3, F(000) = 996, μ = 2.62 mm~(–1), GOOF = 1.031, the final R = 0.0417, and w R = 0.1024 for 8043 observed reflections with I 2σ(I). The Cu(I) atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. In the solid state, the complex exhibits bluish-green photoluminescence with emission peaks λmax = 492 nm(1), lifetimes 235 μs and quantum yields(ф = 0.279) at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that the complex displays thermally activated delayed fluorescence(TADF) at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ILCT excited states.     

Synthesis,Crystal Structure and Photoluminescence of a TADF Cuprous Complex

A four-coordinate mononuclear cuprous complex oCBP-Cu-Pym(1, oCBP =1,2-bis(diphenylphosphine)-nido-carborane, Pym = 2-methyl-6-(1 H-pyrazol-1-yl)pyridine) was synthe-sized and characterized by elemental analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in monoclinic space group C2/c with a = 28.4182(8), b =16.2994(4), c = 22.2708(5) ?, β = 127.219(2)°, V = 8214.8(3) ?3, Z = 8, Mr = 766.92, ρcalc = 1.24 g/cm3, F(000) = 3160, μ = 2.30 mm–1, GOOF = 1.063, the final R = 0.0700 and wR = 0.1903 for7158 observed reflections with I 2σ(I). The Cu(I) ion adopts a highly distorted tetrahedral geometry defined by two nitrogen and two phosphorous atoms. Under UV 365 nm at room temperature, this complex exhibits green emission with maximum emission peak at 516 nm,lifetime 32.4 μs and quantum yield(ф = 0.461) in the solid state. Photophysical investigation suggests that the emission of complex 1 at room temperature was attributed to TADF, which is strongly supported by theoretic calculation.     

Synthesis,Crystal Structure and Photoluminescence of a Dinulear Copper Complex

A binuclear cuprous complex [Cu(μ-I)(NPPh)]2(1,NPPh = 1-(2-(diphenylphosphanyl)phenyl)-3-phenyl-4,5-dihydro-1 H-pyrazole) was synthesized and characterized by elemental analysis,NMR and X-ray single-crystal structure analysis.It crystallizes in triclinic space group P2_1/n with a = 10.7520(3),b = 18.1860(5),c = 11.8487(3) ?,β = 91.864(2),V = 2315.61(11) ?~3,Z = 4,Mr = 594.87,Dc = 1.706 g/cm~3,F(000) = 1176.0,μ = 12.582 mm~(–1),GOOF = 1.048,the final R = 0.0289 and wR = 0.0670 for 3787 observed reflections with I 2σ(I).The Cu atoms in the complex are four-coordinated and adopt distorted tetrahedral coordination geometry.In the solid state,the complex exhibits greenish yellow photoluminescence with a peak maximum of 533 nm,a decay time of 34 μs,and a photoluminescence quantum yield of 63.6% at room temperature,respectively.     

以2，2′-联嘧啶为副配体的铱配合物的合成、晶体结构和发光性质研究

利用环金属配体2-(4',6'-二氟苯基)吡啶(dfppy)和副配体2,2'-联嘧啶(bpm)合成了一个铱配合物[Ir(dfppy)z(bpm)]Cl,通过1H NMR,质谱,元素分析及红外光谱对其进行了表征,并且测定了其晶体结构.同时利用得到的中间配合物[Ir(dfppy):(bpm)] [Ir(dfppy)2(Cl)2]n晶体结构讨论了配合物形成过程.对配合物[Ir(dfppy)2(bpm)]Cl的紫外可见吸收光谱和发光光谱的研究表明,其常温发射位于609 nm处,初步推测该磷光发射可能来自金属到配体的电荷转移(MLCT)跃迁和配体自身,π→π*跃迁(LC)的混合.     

Synthesis,Structure Characterization and Photoluminescence of a Novel Complex with（6,4,4）-Network [Ce_2（2,5-pydc）_3（H_2O）_2]（2,5-pydc = Pyridine-2,5-dicarboxylic Acid）

A new three-dimensional supramolecular [Ce2(2,5-pydc)3(H2O)2](1) has been hydrothermally synthesized at 180 ℃ and characterized by single-crystal X-ray diffraction.X-ray crystal analyses reveal that the compound belongs to the monoclinic system,space group P21/c,C21H13Ce2N3O14,a = 6.561(1),b = 17.986(5),c = 9.411(3) ,β = 95.558(5)° and Z = 2.In the structure of 1,each Ce(1) center is surrounded by 2,5-pydc ligands,forming the 6-connected node,and the 2,5-pydc ligand coordinates to the Ce(Ⅲ) in two different coordination modes.In mode 1,the four oxygen atoms of two carboxyl groups connect neighboring Ce(Ⅲ) ions,giving 4-connected(4-c) second building unit(SBU-1).Furthermore,the structure is extended into a 2-D layer from SBU-1 by sharing Ce(1) atoms.In mode 2,the ligand coordinates to the Ce(Ⅲ) ion from the adjacent chain with the 4-connected(4-c) second building unit(SBU-2),generating a 1-D ladder from SBU-2 by sharing Ce(1) atoms.Finally,the structure is extended into a 6,4,4-c network.Its photoluminescence property was also investigated.     

新型铱配合物的合成及电致发光性质研究

合成了一种新型橙红色磷光材料铱的配合物(npp)₂Ir(acac)(npp=2-(1-萘基)-4-苯基吡啶，acac=乙酰丙酮)，通过 ¹H NMR、MS、元素分析对其结构进行了表征。以铱配合物(npp)₂Ir(acac)作为发光体，制备了结构为ITO/Ir(5%)：PVK(60 nm)/F-TBB(15 nm)/Alq₃(15 nm)/LiF(1 nm)/Al(150 nm)的电致发光器件，研究了其电致发光性质。结果表明器件的最大发射波长在599 nm，最大发光亮度为3 841 cd·m^-2，最大电流效率达3.9 cd·A^-1。     

铕和镧与吡啶－2，6－二甲酸配合物的NMR研究

合成了稀土铕、镧与吡啶－２，６二甲酸形成的二元配合物及铕与邻菲罗啉和吡啶－２，６二甲酸形成的三元配合物。经元素分析确定该配合物的组成分别为二元：Ｎａ３［Ｅｕ（ＤＰＣ）３］·２Ｈ２Ｏ，Ｎａ３［Ｌａ（ＤＰＣ）３］·２Ｈ２Ｏ；三元：ＮａＥｕ（ＤＰＣ）２·ｐｈｅｎ·４Ｈ２Ｏ。用核磁共振研究了配体与稀土的配位方式，讨论了诱导效应、屏蔽效应及稀土离子的顺磁性对配合物化学位移和ＮＭＲ谱图的影响。ＮＭＲ研究表明，三种配合物具有相似的对称结构和相同的化学位移变化规律。吡啶－２，６二甲酸中的羧酸以单齿配位（整个分子为三齿配位），二元配合物中，铕和镧的配位数均为９，三元配合物中，铕的配位数最低为８。     

Syntheses,Crystal Structures and Luminescent Properties of Three New Gallium Complexes Containing Pyridine-2,6-dicarboxylic Acid

Three new gallium complexes formulated as [Ga(PDA)₂][Ga(H₂O)(PDA)(phen)]·4H₂O(1), [Ga(PDA)₂]· (H₂IN)·2H₂O(2) and [Ga(OH)(PDA)(H₂O)]₂(3)(H₂PDA=pyridine-2,6-dicarboxylic acid; phen=1,10-phenanthroline; HIN=isonicotinic acid) have been synthesized under hydrothermal conditions. In the mixed-ligand system of complex 1, PDA^2? and phen are connected to the central Ga³⁺ cation as tri- and bi-dentate ligands, respectively. In complex 2, each Ga³⁺ cation is six-coordinated by two PDA^2? anions octahedrally. Complex 3 shows a binuclear structure, with the bond distance of Ga1-Ga2 being 0.30061(3) nm. The 3D supramolecular structures of the three complexes are constructed via hydrogen bonds and aromatic π-π packing interactions. All the three complexes exhibit intense blue emission at room temperature in the solid state, which are attributed to π^*-π transition centered on the ligands.     

2,3-吡啶二酸钙配合物的合成及其晶体结构与荧光性质

2,3-吡啶二酸( H2pdc)与CaCO3反应制得配合物[Ca2pdc2 (H2O)8] (1),其结构经IR,元素分析及X-射线单晶衍射表征.1属三斜晶系,空间群P-1,晶胞参数a=7.880 8(2)(A),b=10.163 5(3)(A),c=13.7457(4)(A),α=80.427(2)°,β=87.855(2)°,γ=88.563(2)°,V=1 084.69(5)(A)3,Mr=554.50,Dc=1.698 g·cm-3,F(000) =288,μ=0.611 mm-1,Z=2,R=0.029 6,wR=0.085 0.1为之字形一维链结构,Ca(Ⅱ)中心采取七配位扭曲的五角双锥几何构型,配体pdc2 -作为μ2-桥连结2个Ca(Ⅱ)形成一维链,通过O -H----O氢键将一维链连结在一起形成二维层,进一步通过O -H----O氢键将二维层结合在一起形成三维结构.研究了1的荧光性能,结果表明,在326 nm激发波长激发下,1的最大发射峰位于402 nm.     

Synthesis,Crystal Structure and Photoluminescence of a Blue-emitting Dinulear Copper Complex

A binuclear cuprous complex [Cu(μ-I)(NP)]_2·CH_2Cl_2(1, NP = 1-(2-(diphenylphosphino)phenyl)-3,5-dimethylpyrazole) was synthesized and characterized by elemental analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic space group P1 with a = 9.2838(6), b = 12.2672(7), c = 12.4033(7) ?, α = 114.941(6), β = 108.707(5), γ = 91.717(5)o, V = 1190.51(12) ?~3, Z = 1, M_r = 1178.58, D_c = 1.644 g/cm~3, F(000) = 582, μ = 13.232 mm~(-1), GOOF = 1.016, the final R = 0.0384 and wR = 0.1015 for 4145 observed reflections with I 2σ(I). The Cu atoms in the complex are four-coordinated and adopt a distorted tetrahedral coordination geometry. In the solid state, the complex exhibits blue photoluminescence with a peak maximum of 468 nm, a decay time of 9 μs, and a photoluminescence quantum yield of 16.8% at room temperature, respectively. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that the complex displays thermally activated delayed fluorescence(TADF) at room temperature. The results of experimental and DFT calculations suggest that the excited states in the solid state are of(M+X+L)LCT character.