基于苯基修饰策略的新型可溶液加工红光铱配合物的设计、合成及电致发光性能研究

利用向环金属配体的C-Ir键的对位进行苯基取代这一结构修饰策略,成功合成了两种新型铱（III）配合物（3PhNbt）₂Ir（acac）和（3OMePhNbt）₂Ir（acac）.相较其橙光发射的母体化合物（Nbt）₂Ir（acac）,两个目标化合物的抗结晶性、非晶态热稳定性及溶解性均有显著提高,其磷光发射带也发生了5~10 nm的红移.以（3PhNbt）₂Ir（acac）和（3OMePhNbt）₂Ir（acac）为发光客体材料所制备的单层溶液加工电致红光器件,其最大发光亮度分别为1830 cd·m^-2和6630 cd·m^-2,最大电流效率分别为2.4 cd·A^-1和8.7 cd·A^-1,CIE1931色坐标分别为（0.61,0.39）和（0.62,0.38）.相比之下,以母体化合物（Nbt）₂Ir（acac）为发光客体材料所制备的参比器件,其最大发光亮度则为1620 cd·m^-2,最大电流效率仅为1.5 cd·A^-1,CIE1931色坐标为（0.59,0.41）.上述研究结果表明：向C-Ir键对位进行苯基修饰可以在提高铱（III）配合物的可溶液加工性能的同时,获得更为红移的电致发光波长,是一种简单而有效的红光铱（III）配合物的分子设计策略.     

新型苯并咪唑-5,6-二羧酸锌配合物的合成及其性能研究

以ZnSO₄·7H₂O和苯并咪唑-5,6-二羧酸为原料，采用水热法合成了一种新型的锌配合物{\[Zn(H₂-bidc)₂(H₂O)₄]·(H₂O)₄}_n[1 (CCDC: 1007038), H₃-bidc=苯并咪唑-5,6-羧酸]，产率48%，其结构经IR,元素分析和X-射线单晶衍射表征。结果表明：1属正交晶系，Pnnm空间群，晶胞参数a=9.6451(19) ， b=19.459(4) ， c=6.6895(13) ，α=β=γ=90°， V=1255.5(4) ³， Dc=1.634 g·cm^-3， Z=8。采用FL和TGA研究了1的性能。结果表明：1具有一定的热稳定性，最大发射峰位于420 nm和416 nm， 1的荧光发射属于发射配体荧光。     

以3-乙酰基樟脑作为辅助配体的环金属铱配合物的合成及光电性能研究

以立体位阻3-乙酰基樟脑为辅助配体合成了系列新型的环金属铱配合物3-乙酰基樟脑-2-(2,4-二氟)苯基吡啶环金属铱配合物[(46dfppy)₂Ir(acam)], 3-乙酰基樟脑-2-苯基吡啶环金属铱配合物[(ppy)₂Ir(acam)], 3-乙酰基樟脑-2-苯并噻吩吡啶环金属铱配合物[(btp)₂Ir(acam)]. 将配合物的吸收光谱、光致发光光谱以及光致发光效率与辅助配体为乙酰丙酮(acac)的对应配合物进行了比较, 发现在配合物中引入具有大空间位阻的3-乙酰基樟脑使配合物的光致发光效率均有所提高. 并将(ppy)₂Ir(acam)用于有机电致发光器件, 电致发光光谱在516 nm 处有一最大强度峰, 驱动电压为12 V 时最大亮度为10930 cd/m², 最大亮度效率达到14.6 cd/A, 电压为10.7 V 时最大功率为4.23 lm/W, 亮度为698 cd/m².     

具有刺激响应型铜(Ι)配位聚合物的合成、结构及其荧光性质研究

以三(4-(吡啶-4-基)苯基)胺和Cu₄I₄(PPh₃)₄为原料,在水热条件下合成了一个新的Cu(Ι)配合物[Cu₂I₂(TPPA)₂]_n·4H₂O[1, TPPA=三(4-(吡啶-4-基)苯基)胺],其结构经IR、元素分析、X-射线单晶衍射表征。1属正交晶系,'P b c n'空间群,晶胞参数a=29.257(5) Å, b=12.621(2)Å, c=18.304(4) Å, α=90°, β=90°, γ=90°。固态荧光测试结果显示,在365 nm激发态下,配合物1在低温时具有多重发射峰,在CIE坐标下对其颜色做了一定的探究,可作为优良发光材料应用于LED上调节白光。      

基于3,5-吡啶二羧酸和双咪唑配体构筑的锌(Ⅱ)配位聚合物的合成、晶体结构及其荧光性质

以1,3-双咪唑丙烷,3,5-吡啶二羧酸和Zn(NO₃)₂·6H₂O为原料,在水热条件下合成了一个新的Zn(Ⅱ)配合物{［Zn(bbi)(3,5-pdc)］·2H₂O}_n(1, bbi=1,3-二咪唑丙烷,3,5-pdc=3,5-吡啶二羧酸), 其结构和热性能经IR, 元素分析,Ｘ-射线单晶衍射和TGA表征。1属三斜晶系,P-1空间群,晶胞参数a=9.070 8(5) , b=10.213 1(8), c=11.266 7(7), α=82.138(6)°,β=89.368(5)°, γ=75.419(6)°。室温固态荧光测试结果显示,在330 nm激发态下,1在424 nm具有强烈的荧光发射峰。     

铬酸根桥联Cu(Ⅱ)/Ni(Ⅱ)链状配位聚合物的合成及性质

设计合成了2个一维链状铬酸根桥连的配位聚合物(NH₄)₂[Cu(NH₃)₂(CrO₄)₂](1)和(NH₄)₂·[Ni(NH₃)₂(CrO₄)₂](2), 并对其进行了X射线单晶结构分析、 热重-差热分析和多种磁学测试. 晶体结构分析表明, 2个配合物的晶体均属于三斜晶系, 空间群均为P1. 配合物1的晶胞参数为: a=0.59090(12)nm, b=0.6929(3) nm, c=0.73740(15) nm, α=107.03(4)°, β=92.79(3)°, γ=112.44(2)°; 配合物2的晶胞参数为: a=0.56987(7)nm, b=0.69972(9) nm, c=0.73335(8)nm, α=104.929(3)°, β=96.121(3)°, γ=112.325(4)°. 热重分析结果表明, 配合物1和2均在150 ℃左右开始分解, 生成H₂Cr₂CuO₅和H₂Cr₂NiO₅, 在410 ℃以上继续分解, 脱水得到相应的氧化物. 配合物的变温磁化率测试结果表明, 相邻Cu(Ⅱ)离子(配合物1)或Ni(Ⅱ)离子(配合物2)之间存在较弱的反铁磁相互作用; 低温变场和交流磁化率测试结果表明, 2个配合物均为反铁磁体.     

一种新型有机离子晶体的合成与热致变色性能研究

以4,4'-（蒽-9,10-二基）二苯甲酸和NaOH为原料,通过酸碱中和反应合成了一种新型的有机离子晶体[Na⁺(L^-)]·7H₂O（1, L=4,4'-（蒽-9,10-二基）二苯甲酸,CCDC: 1993840),其结构经IR,元素分析和X-射线单晶衍射表征。1属P-1空间群的三斜晶系,晶胞参数a=6.8552(5)Å, b=7.1529(5)Å, c=16.1933(12), α=77.314(6)°, β=86.573(6)°, γ=82.295(5)°。室温固态荧光测试结果表明：在380 nm激发态下,配合物1在456 nm处具有很强的发射峰,荧光量子产率为39.4%;加热后,发射峰从蓝光红移至绿光,晶体颜色从绿色透明晶体变成淡黄色不透明固体,具有热致变色行为。      

新型离子型配合物的合成、晶体结构及性质

利用水热法合成了4-(N,N′-双(4-羧基苄基)氨基)苯磺酸（H₃L）的两个离子型配合物：[Mn(phen)₂(H₂O)₂]?(HL)?(H₂O)₄（1）和[Zn(phen)₂(H₂O)₂]?(HL)?(H₂O)₆（2, phen =邻菲罗啉）,其结构经FL、 IR、元素分析、X-射线单晶衍射、 X-射线粉末衍射和TG表征。结果表明：化合物1属于单斜晶体,P2₁/c空间群,晶胞参数a=11.997(1) Å, b=22.978(1) Å, c=18.093(1) Å, β=92.749(3)°, V=4981.8(3) ų, Z=4。化合物2属于单斜晶体,P2₁/c空间群,晶胞参数a=11.861(1) Å, b=22.816(1) Å, c=18.251(1) Å, β=92.832(5)°, V=4932.8(5) ų,Z=4。化合物2有较好的荧光性质;初始分解温度为80 ℃。      

基于乳酸衍生物的螺旋手性配位聚合物的合成与荧光性质

在水热条件下,半刚性的乳酸衍生物(R)-(1-羧基乙氧基)苯甲酸[(R)-H₂CBA]和(S)-(1-羧基乙氧基)苯甲酸[(S)-H₂CBA]分别与辅助配体1,1'-(2,5-二甲基-1,4-亚苯基)双(1H-咪唑), 1,4-PBM和Zn(Ⅱ)反应,合成了一对包含螺旋链的三维超分子手性配位聚合物[Zn₂((R)-CBA)₂(1,4-PBM)₂]_n(1-D,CCDC:2010329)和[Zn₂((S)-CBA)₂ (1,4-PBM)₂]_n(1-L, CCDC:2010330),其结构和性能经IR, XRD, TGA和FL表征。结果表明：1-D结晶于单斜的P2₁手性空间群,晶胞参数a=8.9753(5)Å, b=18.2446(8)Å, c=15.1201(12)Å,β=90.935(6)°,V=2475.7(3)ų, Dc=1.373g·cm^-3, Z=2, Flack parameter=0.022(6); 作为对映体,1-L也结晶于单斜的P2₁手性空间群,晶胞参数a=9.0090(6)Å, b=18.2280(8)Å, c=15.1227(10)Å,β=90.935(6)°, V=2483.1(3) ų, Dc=1.369 g·cm^-3, Z=2,Flack parameter=0.060(7)。 1-D和1-L的初始分解温度为317℃;1-D在440 nm处有强发射峰。      

一种双吡啶双酰胺配体修饰的Keggin型硅钼酸盐基配合物的合成、结构与催化性能

水热反应条件下制备了一个基于半刚性双吡啶双酰胺配体3-bpcd(N,N'-双(3-吡啶)环己烷-1,4-双甲酰胺)和Keggin型多金属氧酸盐的银配合物{[Ag₂(3-bpcd)₃][Ag(3-bpcd)(SiMo₁₂O₄₀)]₂(3-H₂bpcd)₂}·7H₂O,并通过红外光谱、元素分析和X射线单晶衍射等技术手段确定了其晶体结构。结构分析表明该配合物属于三斜晶系,P-1空间群,晶胞参数a=1.3597(5) nm,b=1.4949(5) nm,c=2.5249(10) nm,α=88.998(6)°,β=88.856(7)°,γ=67.458(6)°,V=4.739(3) nm³,M_r=6471.02,D_c=2.261 g/cm³,Z=1,S=0.955,F(000)=3124,R₁=0.0768,wR₂=0.1936。 配合物是由一维[Ag(3-bpcd)(SiMo₁₂O₄₀)]₂^6-链、双金属[Ag₂(3-bpcd)₃]²⁺结构单元、2个未配位的质子化有机配体3-H₂bpcd和7个结晶水共同组成的复杂结构,多种结构单元间通过氢键作用形成三维超分子网络结构。 标题配合物修饰的碳糊电极对NO₂^-有好的电催化还原活性,此配合物作为催化剂对罗丹明B的降解有显著的催化效果。 CCDC:1401875     

Synthesis of a highly phosphorescent emitting iridium(III) complex and its application in OLEDs

A rigid ligand benzo[de]benzo[4,5]imidazo[2,1-α]isoquinolin-7-one (biio) was designed and conveniently synthesized, and the corresponding bis-cyclometalated iridium complex (biio)₂Ir(acac) (acac = acetylacetone) was prepared. The light emitting and electrochemical properties of this complex were studied. The complex has the characters of simply synthetic procedure and strong phosphorescence. The electroluminescent device using this complex as dopant was fabricated. The device had the structure of ITO/NPB (40 nm)/Ir complex:CBP (7%, 30 nm)/BCP (15 nm)/Alq₃ (30 nm)/LiF (1 nm)/Al (100 nm). The maximum emission of the device was at 496 nm. The maximum brightness of the device can reach 79640 cd m⁻² with an external quantum efficiency of 12.1% and a maximum current efficiency of 31.7 cd A⁻¹.     

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。     

一种新型红色三线态喹喔啉铱(Ⅲ)配合物的合成及发光性质

利用2,3-二苯基喹喔啉和水合三氯化铱(IrCl₃?H₂O)反应, 合成了一种新型喹喔啉铱的配合物[Ir(DPQ)₂(acac)], 通过元素分析, ¹H NMR和HRMS对配合物结构进行了表征, 结果显示得到的是目标化合物. 利用紫外光谱和荧光光谱对配合物的吸收光谱和光致发光光谱进行了研究. 利用该材料作为磷光材料制备了结构为[ITO/NPB(30 nm)/NPB∶7% Ir(DPQ)₂(acac)(25 nm)/PBD (10 nm)/Alq₃ (30 nm)/Mg∶Ag (10∶1)(120 nm)/Ag(10 nm)] 的电致发光器件, 研究了其电致发光光谱. 结果表明, 配合物[Ir(DPQ)₂(acac)]在476和625 nm处存在单重态¹MLCT(金属到配体的电荷跃迁)和三重态³MLCT的吸收峰; 发光光谱结果显示, 在660 nm处有较强的金属配合物三重态的磷光发射; 电致发光光谱显示, 该器件的启动电压是4.25 V, 器件的最大亮度为4910 cd/m², 外量子效率为5.14%, 器件的流明效率为1.12 lm/W, 是一种新型红色磷光材料.     

Synthesis and Structure of Catena-[Bis(2-Methylimidazole)(μ-Phthalato)cobaltate(II)]

A new coordination compound [Co(Pht)(2-MeIm)₂] (I), where Pht^2–is the deprotonated radical of o-phthalic acid (H₂Pht) and 2-MeIm is 2-methylimidazole, was synthesized. Its structure was established using X-ray diffraction analysis. The crystal is orthorhombic: space group Pca2₁, a= 15.350(3), b= 7.957(2), c= 13.997(3) Å, (calcd.) = 1.505 g/cm³, and Z= 4. The tetrahedral coordination of the Co(II) atom includes two N atoms of two 2-methylimidazole molecules and two oxygen atoms of two carboxyl groups from different acid radicals. The Co–N distances are equal to 2.022(2) and 2.031(2) Å, while the Co–O distances are 1.972(2) and 2.000(2) Å. The carboxyl groups of the Pht^2–radical and the aromatic nucleus form angles of 47.2° and 35.9°, whereas the angle formed by the carboxyl groups themselves is 50.3°. Compound Iis a polymer, which is confirmed by the 1,6-bridging function of the o-phthalic acid radical. The Co···Co distance in a chain is equal to 7.367 Å. Separate chains are united in the crystal into a framework via N–H···O hydrogen bonds.     

Phase relations in the CaOIrO2Ir system in air

The equilibrium phase relations for the CaOIrO₂Ir system were determined in air using the quenching technique. The system contains three stable compounds 4CaO·IrO₂, 2CaO·IrO₂, and CaO·IrO₂; they dissociate to an oxide phase, Ir metal, and oxygen at 1240, 1170, and 1135°C, respectively. A metastable form of CaO·IrO₂ occurs at temperatures between 900 and 1100°C. Indexed X-ray diffraction powder patterns of all compounds are given.     

Hydrothermal synthesis and structural characterization of two organically templated zincophosphites with three-dimensional frameworks, (C6H14N2)·[Zn3(HPO3)4] and (C4H12N2)·[Zn3(HPO3)4]

Two organically templated zincophosphites, (C₆H₁₄N₂)·[Zn₃(HPO₃)₄] and (C₄H₁₄N₂)·[Zn₃(HPO₃)₄] have been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction. (C₆H₁₄N₂)·[Zn₃(HPO₃)₄] crystallizes in the triclinic space group , with cell parameters, a=9.363(4) Å, b=10.051(4) Å, c=10.051(4) Å, α=85.777(13)°, β=82.091(9)°, and γ=79.783(9)°. (C₄H₁₄N₂)·[Zn₃(HPO₃)₄] crystallizes in the monoclinic space group P2₁/c, with cell parameters, a=9.9512(3) Å, b=10.1508(3) Å, c=17.8105(5) Å, and β=95.6510(10)°. Although the two structures are different, they have the same anionic framework compositions of [Zn₃(HPO₃)₄]²⁻. Their frameworks are built up from strictly alternating ZnO₄ tetrahedra and HPO₃ pseudo pyramids by sharing vertexes. There exist channels with an eight-membered ring window along the a- and c-axis. Powder X-ray diffraction, IR spectroscopy, ³¹P MAS solid-state NMR, thermogravimetric and differential thermal analyses were also carried out.     

Synthesis and crystal structure determination of Cl-substituted iridium(III) acetylacetonate

γ-Halogen-substituted iridium(III) acetylacetonates of general formula Ir(acacX)₃,where acacX = CH₃ -CO-CX-CO- CH₃,X =Br, I, were synthesized. The compounds are characterized by melting points and chemical analysis data for C, H, Br, and I. An X-ray diffraction analysis was performed for iridium(III) acetylacetonate and its y-substituted analogs, crystal data were obtained, and crystal structures were determined. The crystals are monoclinic;the structures are molecular. Crystal data: Ir(acac)3 _- IrO₆C₁₅H₂₁,a = 13.900(2), b = 16.440(3), c = 7.494(2) ?, γ =98.63(2)‡, V= 1693.2 ?³,space group P2₁/b,Z = 4, d_calc =1.92 g/cm³,sin θ/λ_max = 0.703, F_hkl = 2841, R = 0.044. Ir(acacBr)_3- IrBr₃O₆C₁₅H₁₈,a = 12.794(2), b = 15.753(2), c = 9.990(2) ? Β = 105.76(2)‡, V= 1937.6 ?³,space group P2₁/n,Z =4, d_calc =2.49 g/cm³, sinθ/λ_max = 0.702, F_hkl = 1748, R = 0.048. Ir(acacI)3- M₃O₆C₁₅H₁₈,a = 12.855(2), b = 10.136(2), c =16.338(3)?, Β = 104.6(2)‡, V=2059.8?³,space group P2₁/n, Z =4, d_calc = 2.79g/cm³, θ_max =25‡, F_hkl = 2817, R =0.032. The Ir..Ir distances were estimated to be > 7.49 ? for Ir(acac)3 and > 8.10 ? for Ir(acacBr)3 and Ir(acacl)₃.If the estimate is limited to 10 ?, the intermolecular coordination number (ICN) in the structures is 10. Translated fromZhurnal Struktumoi Khimii, Vol. 40, No. 2, pp. 331–339, March–April, 1999     

Preparation, characterization and crystal structure of Na4[Mn(NCS)6]·13H2O

Na₄[Mn(NCS)₆] · 13H₂O was prepared and characterized by chemical analysis, magnetic susceptibility, thermal dehydration reactions, and single crystal X-ray structure analysis. The crystals are triclinic with a=9.310(1)Å, b=9.367(1)Å, c=9.730(2)Å, = 89.89(1)°,=75.33(1)°, =70.72(1)°, space group P¯I.Z=1. The structure is built up from Na(H₂O)₅ S, Na(H₂O)₆, and Mn(NCS)₆, octahedra. All water molecules are coordinated to Na⁺ -ions in terminal as well as bridging fashion. They form O-H···O as well as O-H···S hydrogen bonds.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Palladium Clusters Pd4(SEt)4(OAc)4and Pd6(SEt)12: Structure and Properties

Palladium clusters Pd₄(SEt)₄(OAc)₄(I) and Pd₆(SEt)₁₂(II) were synthesized and studied. Their structure was determined by X-ray diffraction analysis. For I, a= 9.774(2) Å, b= 10.821(2) Å, c= 13.061(3) Å, = 92.88(3)°, V= 1379.6(5) ų, (calcd.) = 2.182 g/cm³, space group P2₁/n, Z= 4, N _ref= 1558, and R= 0.031; for II, a= 10.581(1) Å, b= 10.584(2) Å, c= 11.478(2) Å, = 101.62(1)°, = 104.95(1)°, = 106.74(1)°, V= 1135.2(4) ų, (calcd) = 2.007 g/cm³, space group P1, Z= 1, N _ref= 2828, and R= 0.022. In cluster I, four Pd atoms form a planar cycle. The neighboring palladium atoms are bound by two acetate or by two mercaptide bridges, the Pd···Pd distances being 3.036–3.195 Å. In cluster II, Pd atoms form a planar six-membered cycle with Pd···Pd distances of 3.083–3.127 Å. The neighboring palladium atoms are bound by two mercaptide bridges. The formation of analogous clusters in solution was confirmed by IR spectroscopy.     

Crystal Structure of Hexafluosilicates of Protonated Thiosemicarbazide and 2,5-Diamino-1,3,4-thiadiazole Produced in the Reaction of Thiosemicarbazide with Fluosilicic Acid

The structure of the crystal complex (L¹H)₂(L²H)(SiF₆)_1.5(L¹is thiosemicarbazide, L²is 2,5-diamino-1,3,4-thiadiazole) was studied by X-ray diffraction analysis. The complex was prepared by reacting an aqueous solution of L¹with 45% fluosilicic acid. The crystals are monoclinic: a= 16.080(3) Å, b= 5.4860(8) Å, c= 20.079(4) Å, = 91.46(1)°, Z= 4, space group P2/n, R= 0.0427. The components of the ionic structure of the complex are L¹H⁺and L²H⁺cations and SiF^2– ₆anions combined by a system of H bonds of the NH···S and NH···F types, the -nitrogen atom of the hydrazine fragment and the endocyclic nitrogen atom of the heterocycle being the protonation centers in L¹H⁺and L²H⁺, respectively. The bond lengths in the SiF^2– ₆anions range within 1.621(6)–1.691(2) Å.