两个单核镍含氮配体配合物的合成、晶体结构及荧光性质(英文)

采用回流法在水溶剂中合成了2个含氮配体单核镍配合物[Ni(phen)2(H2O)2](1,6-nds)·2H2O(1)和[Ni(phen)3](1,6-nds)·10H2O(2)(1,6-nds=1,6-萘二磺酸根离子,phen=1,10-邻菲罗啉)。配合物1中,镍离子与2个1,10-邻菲罗啉和2个水分子配位,形成[Ni(phen)2(H2O)2]2+阳离子。2个没有配位的水分子通过氢键与[Ni(phen)2(H2O)2]2+和1,6-萘二磺酸根离子相互连接形成二维层状结构。配合物2中,镍离子与3个1,10-邻菲罗啉配位,形成[Ni(phen)3]2+阳离子。大量的氢键将自由的水分子和1,6-萘二磺酸根离子连接形成三维网状结构。2个配合物中1,6-萘二磺酸根离子均没有与镍离子配位,只是起到平衡电荷的作用。室温下,配合物显示了较大的荧光发射峰,其最大发射峰分别在443和438 nm。     

含有不同结构第二配体的铕(Ⅲ)三元有机配合物的合成与发光

合成了3种新的1, 10-菲罗啉的衍生物: 二吡啶[3, 2-f: 2', 3'-h]喹喔啉(DPQN), 咪唑并[5,6-f]邻菲罗啉(IP)和苯基咪唑并[5,6-f]邻菲罗啉(PIP), 以它们作为第二配体, 并以二苯甲酰甲烷(DBM)为第一配体, 合成了3种新的铕(Ⅲ)三元有机配合物.通过元素分析、红外光谱、1H-核磁共振光谱确定了它们的组成, 研究了3种配合物的热稳定性、成膜性能和光致发光性能(发光强度, 荧光量子效率和寿命),并初步从理论上探讨了含有不同结构的第二配体对铕(Ⅲ)配合物发光的影响, 为筛选有机电致发光新材料提供了认识基础.     

配合物生成反应速率常数与配体酸离解常数之间的直线自由能关系 V. 铜(II)-2,9-二甲基邻菲罗啉与α-氨基酸和N-苯基乙二胺生成三元配合物的动力学研究

应用温度跃迁装置和断流分光光度计分别研究了铜(II)-2,9-二甲基邻菲罗啉与α-氨基酸和N-苯基乙二胺在25℃、0.1mol·dm^-^3KNO3水溶液中的生成反应动力学。实验结果表明在铜(II)-2,9-二甲基邻菲罗啉-α-氨基酸三元配合物的生成速率常数与配体α-氨基酸的酸离解常数之间存在着如下的直线自由能关系: logkf=2.84+0.53pK2。根据Eigen机理讨论了铜(II)-2,9-二甲基邻菲罗啉-N-苯基乙二胺三元配合物的生成反应动力学。     

配合物生成反应速率常数与配体酸离解常数之间的直线自由能关系 V. 铜(II)-2,9-二甲基邻菲罗啉与α-氨基酸和N-苯基乙二胺生成三元配合物的动力学研究

应用温度跃迁装置和断流分光光度计分别研究了铜(II)-2,9-二甲基邻菲罗啉与α-氨基酸和N-苯基乙二胺在25℃、0.1mol·dm^-^3KNO3水溶液中的生成反应动力学。实验结果表明在铜(II)-2,9-二甲基邻菲罗啉-α-氨基酸三元配合物的生成速率常数与配体α-氨基酸的酸离解常数之间存在着如下的直线自由能关系: logkf=2.84+0.53pK2。根据Eigen机理讨论了铜(II)-2,9-二甲基邻菲罗啉-N-苯基乙二胺三元配合物的生成反应动力学。     

配合物的稳定性与配体酸碱强度之间的直线自由能关系 Ⅺ.铜(Ⅱ)—5—取代邻菲罗啉—α—氨基酸三元体系

在25.0±0.1C和0.1mol·dm~(-3)KNO_3存在下,用pH法测定了邻菲罗啉、5-硝基邻菲罗啉、5-氯邻菲罗啉、5-甲基邻菲罗啉为第一配体;脯氨酸、α-氨基异丁酸、异亮氨酸、缬氨酸、甘氨酸、丝氨酸为第二配体与铜(Ⅱ)形成三元配合物的稳定常数,结果表明三元配合物的稳定性与第一配体和第二配体的酸碱强度之间均存在直线自由能关系,应用反馈π键存在的程度讨论了配合物稳定性的变化趋势。     

新型共晶配合物[Co(1,10-phen)2(AcO)]·H2SDA·11H2O的合成、晶体结构及性质

采用溶剂热法,以4,4′-二苯乙烯二羧酸,1,10-邻菲罗啉和乙酸钴为原料,构筑了一个新型共晶钴配合物[Co(1,10-phen)₂(AcO)]·H₂SDA·11H₂O（CCDC: 1983364, 1,10-phen=1,10-邻菲罗啉,H₂SDA=4,4′-二苯乙烯二羧酸）,其结构和性质经FL, IR,元素分析,TGA和X-射线单晶衍射表征。结果表明：配合物属三斜晶系,P_ī空间群。配合物是由一个单核钴配合物以及一个H₂SDA 分子构成的共晶配合物,其中单核钴配合物中的Co(II)分别与乙酸根中的两个氧原子以及两个1,10-邻菲罗啉配体中的4个氮原子配位,形成了一个六配位的CoN₄O₂八面体构型。共晶化合物分子间通过O-H…O氢键形成二维结构,再经π…π堆积作用形成三维空间构型。配合物在低浓度条件下表现出荧光性质,并存在荧光浓度自猝灭效应。     

对—苯二甲酸邻菲罗啉铕镧配合物的红外光谱及荧光光谱研究

用对-苯二甲酸铵和邻菲罗啉与氯化铕和氯化镧在乙醇-水溶液中反应,合成了对-苯二甲酸邻菲罗啉铕镧异核稀土配合物,测定了配合物的C,H,N和稀土元素的含量、红外光谱、紫外光谱及荧光光谱,确定了配合物的组成。结果表明,羧基氧和邻菲罗啉氮原子均与稀土离子配位,桥联配体对-苯二甲酸根可有效的传送能量,不发光的镧离子对铕离子的发光有明显的增强作用。     

配合物的稳定性与配体酸碱强度之间的直线自由能关系 Ⅺ.铜(Ⅱ)-5-取代邻菲罗啉-α-氨基酸三元体系

在25.0±0.1C和0.1mol·dm^-3KNO₃存在下,用pH法测定了邻菲罗啉、5-硝基邻菲罗啉、5-氯邻菲罗啉、5-甲基邻菲罗啉为第一配体;脯氨酸、α-氨基异丁酸、异亮氨酸、缬氨酸、甘氨酸、丝氨酸为第二配体与铜(Ⅱ)形成三元配合物的稳定常数,结果表明三元配合物的稳定性与第一配体和第二配体的酸碱强度之间均存在直线自由能关系,应用反馈π键存在的程度讨论了配合物稳定性的变化趋势。     

钐、铕-2,4-二氯苯氧乙酸的二元、三元配合物的合成及荧光性能

以2,4-二氯苯氧乙酸为第一配体、1,10-菲罗啉为第二配体,合成了钐、铕的二元、三元配合物。通过元素分析、EDTA络合滴定及热重分析,确定了配合物的通式为RE(DCP)3.H2O,RE(DCP)3phen(RE=Sm,Eu;DCP=2,4-二氯苯氧乙酸根;phen=邻菲罗啉);测定了配合物红外光谱、紫外光谱、荧光光谱;研究了配合物的热稳定性。结果表明,三元配合物较二元配合物稳定;Eu(DCP)3.H2O和Eu(DCP)3phen具有荧光性能。     

钯(Ⅱ)-芳香氮碱-氨基酸三元配合物中的电子效应和芳环堆积作用

用pH-电位滴定法测定了Pd(L)(Aa)+三元配合物及相应的二元配合物,在25±O.5℃,30%的乙醇水溶液(体积分数),I=0.1(KNO3)条件下的稳定常数及表征常数.其中L=邻菲罗啉(phen)、苯并咪唑邻菲罗啉(PIP)、邻菲罗啉-5,6-二酮(dophen)、2,9-二甲基邻菲罗啉(dmphen)和联吡啶3,3′-二羧酸(BDA);Aa为甘氨酸(gly)、苯丙氨酸(phe)、酪氨酸(tyr)、S-苄基-半胱氨酸(bcys)、谷氨酰胺(glu)和γ-谷氨酰-α-萘胺(gnapa).从配合物配体间的电子效应和芳环堆积等观点对配合物的附加稳定性进行了讨论,并计算了电子效应和芳环堆积效应各自对三元配合物附加稳定性的贡献.     

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,~1H-NMR and elemental analysis.The magnetic behavior of these complexes was measured as a function of magnetic field strength(0-3.98×10~6 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/m.Experimental results show that DAPcIPA-Ni~(2 ),DAPcIPA-Co~(2 ) are soft ferromagnets while DAPcIPA-Fe~(2 ) exhibits features of an antiferromagnet.     

PREPARATION AND MAGNETIC PROPERTIES OF POLY(SCHIFF BASE) COMPLEXES CONTAINING PHENANTHROLINE UNITS

Two poly(Schiff base)s (PDBT and PDPE) were synthesized by polycondensation of 1,10-phenanthroline-5,6- dione (PD) with 2,2′-diamino-4,4′-bithiazole (DABT) and 4,4′-diaminodiphenyl ether (DAPE),respectively.The structures of the polymers were determined by FTIR and element analysis.The metal (Fe~(2+),Ni~(2+)) complexes were prepared from the polymers with FeSO_4 or NiSO_4,and the metal contents of the complexes were measured by complexometric titration.The magnetic behaviors of the complexes were examine...     

Synthesis and magnetic properties of novel containing 1,10-phenanthroline polymeric complexes

The polymer (DAPcTPA) was synthesized by polycondensation of 5,6-diamine-1,10-phenanthroline (DAP) with terephthaldehyde (TPA). Three polymeric complexes were first prepared from polymer (DAPcTPA) and NiSO₄, CoCl₂ or FeSO₄, respectively. The structures of polymer and complexes were characterized by IR, ¹H NMR spectra and elemental analysis. The magnetic behavior of these complexes was measured as a function of magnetic field strength (0-50 kOe) at 5 K and as a function of temperature (5-300 K) at a magnetic field strength of 30 kOe. The results show that DAPcTPA-Ni²⁺ and DAPcTPA-Co²⁺ are soft ferromagnets, while DAPcTPA-Fe²⁺ exhibits features of an antiferromagnet.     

PREPARATION AND MAGNETIC PROPERTIES OF POLY(SCHIFF BASE) COMPLEXES CONTAINING PHENANTHROLINE UNITS

 Two poly(Schiff base)s (PDBT and PDPE) were synthesized by polycondensation of 1,10-phenanthroline-5,6-dione (PD) with 2,2′-diamino-4,4′-bithiazole (DABT) and 4,4′-diaminodiphenyl ether (DAPE), respectively. The structures of the polymers were determined by FTIR and element analysis. The metal (Fe²⁺, Ni²⁺) complexes were prepared from the polymers with FeSO₄ or NiSO₄, and the metal contents of the complexes were measured by complexometric titration. The magnetic behaviors of the complexes were examined as a function of magnetic field strength at 4 K and as a function of temperature (4-300 K) at a magnetic field strength of 2.4 ×106 A/m. The results show that the relative saturation magnetization of the PDBT complexes is higher than that of the corresponding PDPE complexes, and PDBT-Ni²⁺ and PDPE-Ni²⁺ are soft ferromagnets, while PDBT-Fe²⁺ and PDPE-Fe²⁺ exhibit the features of antiferromagnet.     

Studies on the synthesis and magnetic property of binuclear oxovanadium(IV) complexes bridged by chloranilato group

Six novel oxovanadium(IV) binuclear complexes have been synthesized and characterized, namely, [(VO)₂(CA)L₂]SO₄ [L denotes 5-methyl-1,10-phenanthroline (Me-phen); 2,9-dimethyl-1,10-phenanthroline (Me₂-phen); 5-chloro-1,10-phenanthroline (Cl-phen); diaminoethane (en); 1,3-diaminopropane (pn) and 1,2-diaminopropane (ap) respectively.], where CA represents the dianion of chloranilic acid. Based on elemental analyses, molar conductivity and room temperature magnetic moment measurements, IR and electronic spectral studies, it is proposed that there complexes have CA-bridged structures and consist of two vanadium(IV) ions in a square-pyramidal environment. The complexes [(VO)₂(CA)(Me-phen)₂]SO₄ (1) and [(VO)₂(CA)(Me₂-phen)₂]SO₄ (2) were characterized by variable temperature magnetic susceptibility measurements (4～300 K) and the observed data were fitted to the modified Bleaney-Bowers equation by the least-squares method, giving the exchange integral J=-15.8 cm^?1 for 1 and J=-10.6 cm^?l for 2. This result indicates that there is a weak antiferromagnetic spin-exchange interaction between the two VO²⁺ ions within each molecule.     

4－硝基邻苯二甲酸根桥联双核钴(Ⅱ)配合物的合成、磁性及抗癌活性

研究桥联多核配合物的磁性不仅有助于了解桥联多核配合物在生物体内所起的各种生物功能,而且可为分子铁磁体的设计和合成提供信息.某些过渡金属配合物已显示了体外抗艾滋病和抗癌活性,有关桥联多核配合物在这方面的研究甚少.     

Synthesis and magnetic properties of complexes of a conjugated hyperbranched polymer containing bithiazole rings

A novel conjugated hyperbranched polymer containing bithiazole rings（PBTADB） was synthesized by polycondensation of 1,3,5-benzenetricarboxaldehyde and 2,2’-diamino-4,4’-bithiazole（DABT）.The structure of the hyperbranched polymer was confirmed by FT-IR and ¹H-NMR.PBTADB dissolved in organic polar solvents such as DMSO and NMP.Bithiazole rings were introduced to provide bidentate N-donor sites for binding metal ions.The metal complexes were prepared by chelation of the polymer with Co²⁺ and Sm³⁺.The magnetic behavior of coordination compounds was measured as a function of magnetic field strength（0-4.8×10⁶ A/m） at 5 K and as a function of temperature（5-300 K） at magnetic field strength of 2.4×10⁶ A/m.The magnetic hysteresis loops of PBTADB-Sm³⁺and PBTADB-Co²⁺showed the typical ’S’ shape at 5 K with the Curie-Weiss temperature T_θ=96 K and 41 K respectively.The results show that they exhibit properties of soft ferromagnetic materials.     

对苯二甲酸根桥联的双核铬(Ⅲ)配合物的合成与磁性

以对苯二甲酸根(TPHA)为桥联配体.分别端接4.4＇-二甲基-2.2＇-联吡啶(Me 2bpy),2.9-二甲基-1.10-邻菲哕啉(Me2phen)和5-氯-1,10-邻菲哕啉(Cl-phen).合成了3种新的双核铬(Ⅲ)配合物[Cr2-(TPHA)(Me2bpy)4](NO3)4(1),[Cr2(TPHA)(Me2phen)4](NO3)4(2)和[Cr 2(TPHA)(Clphen)4](N)3)4(3).经元素分析、摩尔电导和磁性测定以及红外光谱和电子光谱等手段,推定这些配合物具有TPHA桥联双核铬(Ⅲ)结构,其中,每个铬(Ⅲ)离子处于畸变八面体配位环境.测定了配合物(1)的变温磁化率(4～300 K),其数值用最小二乘法和从自旋Hamiltonian算符(H=-2JS^1S^2)导出的磁方程拟合,求得交换积分为-2.98 cm-1,结果表明双核配合物中金属离子间存在弱的反铁磁自旋交换作用.     

Photophysical, spectroscopic, and computational studies of a series of Re(I) tricarbonyl complexes containing 2,6-dimethylphenylisocyanide and 5- and 6-derivatized phenanthroline ligands

The ligand 2,6-dimethylphenylisocyanide (CNx) forms six complexes of the formula [Re(CO)3(CNx)(L)]+, where L = 1,10-phenanthroline (1), 5-chloro-1,10-phenanthroline (2), 5-nitro-1,10-phenanthroline (3), 5-methyl-1,10-phenanthroline (4), 5,6-dimethyl-1,10-phenanthroline (5), and 1,10-phenanthrolinopyrrole (6). The lowest-energy absorption peaks of the complexes red-shift in the order 1 < 2 < 3 < 4 < 5 < 6. The time-dependent density functional theory (TDDFT) and conductor-like polarizable continuum model (CPCM) computed singlet excited states in ethanol deviate by 1000 cm(-1) or less from the experimental UV-vis peaks. The complexes undergo reversible reductions and irreversible oxidations. The electronic energy gap increases in the order 3 < 2 < 1 < 4 < 5 < 6, which is the order of increasing electron-donating power of the phen substituents. The reduction potentials linearly correlate with the B3LYP calculated LUMO energies for 1-6. The complexes emit at room temperature and at 77 K except 3, which emits only at 77 K. The calculated (3)MLLCT energies are within 1100 cm(-1) from the experimental emission energies at 77 K. The 77 K emission curve-fitting analysis results agree with the computational assignment of the emitting state as 3MLLCT for 1-5 and 3LC for 6. The experimental 77 K emission energies and the calculated 3MLLCT state energies increase in the order 6 < 5, 3 < 2 < 4, 1. The 77 K emission lifetimes increase upon addition of substituents from 65 micros for 1 to 171 micros for 2, to 230 micros for 4 and 5, and to 322 micros for 3. The emission quantum yields at room temperature in solution are 0.77, 0.78, 0.83, 0.56, and 0.11 for complexes 1, 2, 4, 5, and 6, respectively.     

Potentiometric Studies on Complexation of Cu(II) Ion with Methyl/Nitro-Substituted 1,10-Phenanthrolines and Selected Amino Acids

Protonation constants of methyl/nitro substituted 1,10-phenanthrolines {(m/n-sphen): 4-methyl-phenanthroline (4-mphen), 5-methyl-1,10-phenanthroline (5-mphen), 4,7-dimethyl-1,10-phenanthroline (dmphen), 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) and 5-nitro-1,10-phenanthroline (5-nphen)] and the amino acids (aa) l-tyrosine (tyr) and glycine (gly), and their corresponding binary and ternary stability constants with Cu(II), were determined in aqueous 0.1 mol·L^?1 KCl ionic media at 298.15 K. The protonation constants of the ligands and the stability constants of the binary and ternary complexes of Cu(II) with the ligands were calculated from the potentiometric data using the “BEST” software package. The species distribution diagrams were obtained using the “SPE” software package under the experimental conditions described. The order of stability of the ternary complexes in terms of the primary ligands is [Cu(tmphen)(aa)]⁺ > [Cu(dmphen)(aa)]⁺ > [Cu(4-mphen)(aa)]⁺ > [Cu(5-mphen)(aa)]⁺ > [Cu(5-nphen)(aa)]⁺. The stability constants of the ternary complexes decrease in the following order: [Cu(m/n-sphen)(gly)]⁺ > [Cu(m/n-sphen)(tyr)]⁺, which is identical to the sequence found for the binary complexes of Cu(II) with gly and tyr.