喹啉和吡啶取代三芳基三唑的两个铜配合物的合成与晶体结构（英文）

分别以3-(2-吡啶基)-4-(4-甲基苯基)-5-(2-喹啉基)-1,2,4-三氮唑(L~1)和3-(2-吡啶基)-4-(4-氟苯基)-5-(2-喹啉基)-1,2,4-三氮唑(L~2)作为配体,合成了2个新的单核铜配合物:trans-[Cu(L~1)_2(NO_3)(H_2O)]NO_3·H_2O(1)和trans-[Cu(L~2)_2(NO_3)(H_2O)]NO_3·H_2O(2),对其进行了红外、元素分析和单晶结构表征。2个配合物都属于三斜晶系,P1空间群。单晶结构表明,配合物1和2中的铜离子均处于一个扭曲的八面体配位环境[Cu N_4O_2],轴向上各有一个水分子和一个硝酸根配位。配体的吡啶氮原子和三氮唑的一个氮原子参与配位,而喹啉的氮原子不配位。配合物晶体中存在O-H…O、C-H…O、C-H…N氢键和C-H…π相互作用,从而连接单核配合物形成三维网络。     

呋喃取代三芳基三唑的单核铜配合物中共存两个不同的铜离子（英文）

分别以3-(2-吡啶基)-4-苯基-5-(2-呋喃基)-1,2,4-三氮唑(L~1)和3-(2-吡啶基)-4-(对氟苯基)-5-(2-呋喃基)-1,2,4-三氮唑(L~2)作为配体,合成了2个新的单核铜配合物:trans-[Cu(L~1)_2(NO_3)_2]_(0.5)[Cu(L~1)_2(H_2O)_2]_(0.5)(NO_3)(1)和trans-[Cu(L~2)_2(NO_3)_2]_(0.5)[Cu(L~2)_2(H_2O)_2]_(0.5)(NO_3)·2CH_3OH (2)。对它们进行了红外、元素分析、热重分析、单晶结构和粉末X射线衍射表征。2个配合物都属于三斜晶系,P1空间群。单晶结构表明,配合物1和2中均有2个不同的铜离子,且都处于一个扭曲的八面体[CuN_4O_2]配位环境,但在轴向上一个铜离子与2个水分子配位,另一个铜离子则与2个硝酸根配位。配体的吡啶氮原子和三氮唑的一个氮原子参与配位,而呋喃的氧原子不配位。配合物晶体中存在C—H…N、C—H…O、O—H…O氢键和C—H…π相互作用,从而连接单核配合物形成二维层状结构。     

铜配合物[CuL2(ClO4)2]的合成、晶体结构及热稳定性(L=3-对溴苯基-4-对甲苯基-5-(2-吡啶基)-1，2，4-三氮唑)

以3-对溴苯基-4-对甲苯基-5-(2-吡啶基)-1,2,4-三氮唑(L)作为配体,合成了1个铜配合物trans-[CuL2(ClO4)2],对其进行了红外、电喷雾质谱、热重分析和单晶结构表征,该配合物属于三斜晶系,空间群P1,a=0.829 29(15)nm,b=0.854 48(16)nm,c=1.502 7(3)nm,α=83.517(2)°,β=89.200(2)°,γ=73.064(2)°,V=1.011 9(3)nm3,Z=1,R1=0.041 2。单晶结构表明,铜离子处于1个扭曲的八面体配位环境中,2个高氯酸根离子呈反式配位,每个配体L通过三氮唑上的1个氮原子和吡啶氮原子参与配位。热重分析表明该配合物在310℃开始发生分解。     

不对称三芳基三氮唑的钴配合物中三氮唑-吡啶间二面角的反常变化

以3-对甲氧基苯基-4-对溴苯基-5-(2-吡啶基)-1,2,4-三氮唑(L)作为配体,合成了1个钴配合物[CoL2(H2O)2](ClO4)2.2C2H5OH,对其进行了红外、电喷雾质谱、热重分析和单晶结构表征,该配合物属于单斜晶系,空间群P21/n,a=0.876 3(5)nm,b=3.384 4(18)nm,c=0.920 3(5)nm,β=102.961(8)°,V=2.660(2)nm3,Z=2,R1=0.064 4。单晶结构表明,钴离子处于1个扭曲的八面体配位环境中,2个水分子呈反式配位,每个配体L通过三氮唑上的1个氮原子和吡啶氮原子参与配位。配体配位后三氮唑-吡啶间二面角反而变大。热重分析表明该配合物在345℃开始发生分解。     

一个不对称三芳基三氮唑锰配合物的合成、晶体结构和性质研究

以3-对甲氧苯基-4-对氯苯基-5-(2-吡啶基)-1,2,4-三氮唑(L)为配体,合成了1个单核锰配合物trans-[MnL2(NCS)2],对其进行了红外、电喷雾质谱、热重和单晶结构表征,该配合物属于单斜晶系,空间群为P21/c,a=1.458 5(3)nm,b=0.915 00(18)nm,c=1.616 3(3)nm,β=101.70(3)°,V=2.112 2(7)nm3,Z=2,R1=0.058 5。单晶结构表明,锰离子处于1个扭曲的八面体配位环境中,2个硫氰根离子呈反式配位,每个配体L通过三氮唑上1个氮原子和吡啶上1个氮原子参与配位。热重分析表明该配合物在260℃开始发生分解。变温磁化率显示该配合物为顺磁性(1.8～300 K)。     

新型噻吩并嘧啶酮类衍生物的合成及其抑菌活性

以1,2,4-三氮唑为起始原料,经取代、Gewald反应、Wittig反应和成环反应合成了7个新型的含氟噻吩并嘧啶酮类衍生物——2-二烷氨基-3-对氟苯基-5-甲基-6-(1H-1,2,4-三唑-1-基)-噻吩并[2,3-d]嘧啶-4(3H)-酮(6a~6g),其结构经1H NMR,MS和元素分析表征。抑菌活性测试结果表明:6对棉花枯萎菌、水稻纹枯菌、黄瓜灰霉菌、小麦赤霉菌、苹果轮纹及棉花炭疽具有较好的抑制作用,其中2-二异丁氨基-3-对氟苯基-5-甲基-6-(1H-1,2,4-三唑-1-基)-噻吩并[2,3-d]嘧啶-4(3H)-酮(6f)的抑菌活性最好,在用药量为5×10-5g·L-1时,对棉花枯萎菌的抑制率为85%。     

一些含三氮杂茂偶氮染料O,N供体的Zr(Ⅱ)配合物的合成、表征和抗微生物活性(英文)

合成了9种3-(2-羟基萘基-1-偶氮)-1,2,4-三氮唑(HL1),3-(2,4-二羟苯基-1-偶氮)-1,2,4-三氮唑(HL2),3-(2-羟基-3-羧基萘基-1-偶氮)-1,2,4-三氮唑(HL3),3-(2-羟基-5-溴苯基-1-偶氮)-1,2,4-三氮唑(HL4)和3-(2-羟基-5-甲基苯基-1-偶氮)-1,2,4-1,2,4-三氮唑(HL5)的Zr(Ⅱ)配合物并用元素分析,摩尔电导,磁矩,IR,UV-Vis,1H-NMR以及热分析(TGA和DTA)对其进行了表征。结果表明HL1-HL5以二齿一元配体方式通过偶氮的氮原子和羟基基团的氧原子与Zr(Ⅱ)离子配位生成单核配合物。用4种革兰氏阴性菌,即大肠杆菌(Escherichia coli),粘质沙雷氏菌(Serratia marcescens),阴沟肠杆菌(Enterobacter cloacae)和普通变形杆菌(Proteus vulgaris),以及2种真菌,即白色念珠菌(Candida albicans)和黑曲霉菌(Aspergillus niger)对配体及其配合物的生物学活性进行了研究。最小抑菌浓度(MICs)用纸上杯碟琼脂扩散法测定,结果表明在大多数情况下,金属化的配合物的抗微生物活性与自由配体相比有所增强。     

基于3-甲基-4-对溴苯基-5-(2-吡啶基)-1，2，4-三氮唑的锰配合物的合成和晶体结构

以3-甲基-4-对溴苯基-5-(2-吡啶基)-1,2,4-三氮唑作为配体(L),合成了1个新的锰配合物[MnL2(NCS)2],对其进行了红外、电喷雾质谱和单晶结构表征,该配合物属于单斜晶系,空间群P21/n,a=1.6480(2)nm,b=0.90707(13)nm,c=2.1919(3)nm,β=97.454(2)°,V=3.248 8(8)nm3,Z=4,R1=0.043 9。单晶结构表明,锰离子处于1个扭曲的八面体配位环境中,2个硫氰根离子呈顺式配位,每个配体L通过三氮唑上1个氮原子和吡啶上1个氮原子参与配位。     

新型1,2,4-三唑三氮烯衍生物的合成及其生物活性

以对氨基苯甲酸为原料,经多步反应合成了16个未见文献报道的1,2,4-三唑三氮烯衍生物.利用~1H NMR~,(13)C NMR和HRMS对标题化合的结构进行了表征.衍生物的细胞毒活性测试结果表明,2-[4-(3,3-二甲基三氮烯-1-基)苯基]-3-氨基-4-S-(4-氯基苄基)-1,2,4-三唑(6g)、2-[4-(3,3-二甲基三氮烯-1-基)苯基]-3-氨基-4-S-(2,4-二氯基苄基)-1,2,4-三唑(6h)、2-[4-(3,3-甲基苯甲基三氮烯-1-基)苯基]-3-氨基-4-S-苄基-1,2,4-三唑(6i)、2-[4-(3,3-甲基苯甲基三氮烯-1-基)苯基]-3-氨基-4-S-(4-甲基苄基)-1,2,4-三唑(6j)、2-[4-(3,3-甲基苯甲基三氮烯-1-基)苯基]-3-氨基-4-S-(4-甲氧基苄基)-1,2,4-三唑(6l)、2-[4-(3,3-甲基苯甲基三氮烯-1-基)苯基]-3-氨基-4-S-(2,4-二氯基苄基)-1,2,4-三唑(6p)对膀胱癌细胞具有较好的抑制作用,其IC50值分别为23.883,5.512,8.731,8.077,5.590和12.195μmol/L,化合物6h,6i,6j,6l对前列腺癌细胞具有较好的抑制作用,其IC50值分别为13.690,21.908,10.772和4.827μmol/L.     

1，4，7-三氮环壬烷衍生物铜、锌配合物切割DNA及催化对硝基苯磷酸单酯水解

系统研究了1,4,7-三(2-羟基丙基)-1,4,7-三氮环壬烷(L1)和1,2-双[N,N′-二(2-羟基丙基)-1,4,7-三氮杂环壬基]乙烷(L2)铜配合物([CuL1](ClO4)(NO3)和[Cu2L2](ClO4)4])以及锌配合物([ZnL1](ClO4)2)与CT-DNA的相互作用以及核酸酶活性和催化磷酸酯水解功能。两个铜配合物对DNA切割具有浓度、时间和pH依赖性。荧光和CD光谱实验表明[Cu2L2](ClO4)4能插入DNA双螺旋中。配位饱和的[ZnL1](ClO4)2和[Cu2L2](ClO4)4能催化对硝基苯磷酸单酯水解生成对硝基苯,[ZnL1](ClO4)2和[Cu2L2](ClO4)4催化磷酸单酯水解的表观一级反应速率常数分别为2.8×10-5min-1和5.9×10-6min-1。     

Synthesis and some first-row transition-metal complexes of the 1,2,4-triazole-based Bis(terdentate) ligands TsPMAT and PMAT

The employment of a strategy based on nucleophilic substitution, rather than Schiff base condensation, for the preparation of 1,2,4-triazole-based ligands has been investigated and has led to the synthesis of two new ligands, 4-amino-3,5-bis{[N-(2-pyridylmethyl)-N-(4-toluenesulfonyl)amino]methyl}-4H-1,2,4-triazole (TsPMAT, 14) and 4-amino-3,5-bis{[(2-pyridylmethyl)amino]methyl}-4H-1,2,4-triazole (PMAT, 15). These are the first examples of bis(terdentate) ligands incorporating the 1,2,4-triazole unit. TsPMAT (14) forms a dinuclear 2:2 complex with Co(BF4)2.6 H2O even when reacted in a metal-to-ligand molar ratio of 2:1. Similarly, the reaction of PMAT (15) with Mn(ClO4)2.6H2O or M(BF4)2.6 H2O (M=Fe, Co, Ni, Zn) in a ligand-to-metal molar ratio of 1:1 has afforded a series of complexes with the general formula [M(II) (2)(PMAT)2]X4. The metal centres in these complexes of TsPMAT (14) and PMAT (15) are encapsulated by two ligand molecules and doubly bridged by the N2 units of the 1,2,4-triazole moieties, which gives rise to N6 coordination spheres that are strongly distorted from octahedral, as evidenced by the X-ray crystal structure analyses of [Co(II) (2)(TsPMAT)(2)](BF(4))(4)6 MeCN (246 MeCN) and [Fe(II) 2(PMAT)2](BF4)4DMF (27DMF). Studies of the magnetic properties of [Co(II) 2(TsPMAT)2](BF4)4.4 H2O (244 H2O), [Mn(II) 2(PMAT)2](ClO4)4 (26), and [Co(II) 2(PMAT)2](BF4)4 (28) have revealed weak antiferromagnetic coupling (J=-3.3, -0.16, and -2.4 cm(-1), respectively) between the two metal centres in these complexes.     

Synthesis, crystal structure, and characterization of new tetranuclear Ag(I) complexes with triazole bridges

The self-assembly of Ag(I) ions with 3,5-dimethyl-4-amino-1,2,4-triazole (L1) and 4-salicylideneamino-1,2,4-triazole (L2) gave two novel complexes, [Ag4(mu2-L1)6][Ag4(mu2-L1)6(CH3CN)2](ClO4)8.2H2O (1) and [Ag4(mu2-L2)6(CH3CN)2](AsF6)4.2H2O (2), both of which contain tetranuclearic clusters constructed via Ag(I) ions and six N1,N2-bridged triazoles with a Ag4N12 core. When 4-(6-amino-2-pyridyl)-1,2,4-triazole (L3) was employed, {[Ag4(mu2-L3)4(mu3-L3)2](CF3SO3)4.H2O}n (3), {[Ag4(mu2-L3)4(mu3-L3)2](ClO4)4}n (4), and {[Ag4(mu2-L3)2(mu3-L3)4](PF6)4.CH3CN.0.75H2O}n (5) were isolated. 3 and 4 are 1D polymers, while 5 is a 2D polymer. 1D and 2D coordination polymers are constructed via the self-assembly of Ag4N12 cores as secondary building units (SBUs). The connection of these SBUs can be represented as a ladderlike structure for 1D polymers and a 4.8(2) net for 2D polymers. Electrospray ionization mass spectrometry measurements and NMR (1H and 13C) studies demonstrate that the tetranuclear SBU retains its integrity and the coordination polymers decompose into the tetranuclear Ag4N12 core in solution. 2 exhibits blue emission in the solid state and green emission in solution at ambient temperature. Strong blue fluorescence for complexes 3-5 in the solid state can be assigned to the intraligand fluorescent emission.     

High and low spin mononuclear and dinuclear iron(II) complexes of 4-amino and 4-pyrrolyl-3,5-di(2-pyridyl)-4H-1,2,4-triazoles

The first dinuclear iron(II) complexes of any 4-substituted 3,5-di(2-pyridyl)-4H-1,2,4-triazole ligands, [Fe(II)2(adpt)2(H2O)1.5(CH3CN)2.5](BF4)4 and [Fe(II)2(pldpt)2(H2O)2(CH3CN)2](BF4)4, are presented [where adpt is 4-amino-3,5-di(2-pyridyl)-4H-1,2,4-triazole and pldpt is 4-pyrrolyl-3,5-di(2-pyridyl)-4H-1,2,4-triazole]. Both dinuclear complexes feature doubly triazole bridged iron(II) centers that are found to be [high spin-high spin] at all temperatures, 4-300 K, and to exhibit weak antiferromagnetic coupling. In the analogous monometallic complexes, [Fe(II)(Rdpt)2(X)2](n+), the spin state of the iron(II) center was controlled by appropriate selection of the axial ligands X. Specifically, both of the chloride complexes, [Fe(II)(adpt)2(Cl)2] x 2 MeOH and [Fe(II)(pldpt)2(Cl)2] x 2 MeOH x H2O, were found to be high spin whereas the pyridine adduct [Fe(II)(adpt)2(py)2](BF4)2 was low spin. Attempts to prepare [Fe(II)(pldpt)2(py)2](BF4)2 and the dinuclear analogues [Fe(II)2(Rdpt)2(py)4](BF4)4 failed, illustrating the significant challenges faced in attempts to develop control over the nature of the product obtained from reactions of iron(II) and these bis-bidentate ligands.     

Two novel heterometallic chains featuring Mn(II) and Na(I) ions in trigonal-prismatic geometries alternately linked to octahedral Mn(IV) ions: synthesis, structures, and magnetic behavior

Two new one-dimensional heterometallic complexes, [Mn(3)Na(L)(4)(CH(3)CO(2))(MeOH)(2)](ClO(4))(2)·3H(2)O (1), [Mn(3)Na(L)(4)(CH(3)CH(2)CO(2))(MeOH)(2)](ClO(4))(2)·2MeOH·H(2)O (2) [LH(2) = 2-methyl-2-(2-pyridyl)propane-1,3-diol], have been synthesized and characterized by X-ray crystallography. Both complexes feature Mn(II) and Na(I) ions in trigonal-prismatic geometries that are linked to octahedral Mn(IV) ions by alkoxy bridges. Variable-temperature direct- and alternating-current magnetic susceptibility data indicated a spin ground state of S = 11/2 for both complexes. Density functional theory calculations performed on 1 supported this conclusion.     

Tuning the selectivity/specificity of fluorescent metal ion sensors based on N2S2 pyridine-containing macrocyclic ligands by changing the fluorogenic subunit: spectrofluorimetric and metal ion binding studies

Two new fluorescent chemosensors for metal ions have been synthesized and characterized, and their photophysical properties have been explored; they are the macrocycles 5-(2-quinolinylmethyl)-2,8-dithia-5-aza-2,6-pyridinophane (L5) and 5-(5-chloro-8-hydroxyquinolinylmethyl)-2,8-dithia-5-aza-2,6-pyridinophane (L6). Both systems have a pyridyl-thioether-containing 12-membered macrocycle as a binding site. The coordination properties of these two ligands toward CuII, ZnII, CdII, HgII, and PbII have been studied in MeCN/H2O (1:1 v/v) and MeCN solutions and in the solid state. The stoichiometry of the species formed at 25 degrees C have been determined from absorption, fluorescence, and potentiometric titrations. The complexes [CuL5](ClO4)(2).1/2MeCN, [ZnL5(H2O)](ClO4)2, [HgL5(MeCN)](ClO4)2, [PbL5(ClO4)2], [Cu3(5-Cl-8-HDQH-1)(L6H-1)2](ClO4)(3).7.5H2O (HDQ=hydroxyquinoline), and [Cu(L6)2](BF4)(2).2MeNO2 have also been characterized by X-ray crystallography. A specific CHEF-type response of L5 and L6 to the presence of ZnII and CdII, respectively, has been observed at about pH 7.0 in MeCN/H2O (1:1 v/v) solutions.     

Ag(I)/V(V) Heterobimetallic Frameworks Generated from Novel-Type {Ag(2)(VO(2)F(2))(2)(triazole)(4)} Secondary Building Blocks: A New Aspect in the Design of SVOF Hybrids

A series of new silver(I)-containing MOFs [Ag(2)(tr(2)ad)(2)](ClO(4))(2) (1), [Ag(2)(VO(2)F(2))(2)(tr(2)ad)(2)]·H(2)O (2), [Ag(2)(VO(2)F(2))(2)(tr(2)eth)(2)(H(2)O)(2)] (3), and [Ag(2)(VO(2)F(2))(2)(tr(2)cy)(2)]·4H(2)O (4) supported by 4-substituted bifunctional 1,2,4-triazole ligands (tr(2)ad = 1,3-bis(1,2,4-triazol-4-yl)adamantane, tr(2)eth = 1,2-bis(1,2,4-triazol-4-yl)ethane, tr(2)cy = trans-1,4-bis(1,2,4-triazol-4-yl)cyclohexane) were hydrothermally synthesized and structurally characterized. In these complexes, the triazole heterocycle as an N(1),N(2)-bridge links either two adjacent Ag-Ag or Ag-V centers at short distances forming polynuclear clusters. The crystal structure of compound 1 is based on cationic {Ag(2)(tr)(4)}(2+) fragments connected in a 2D rhombohedral grid network with (4,4) topology. The neighboring layers are tightly packed into a 3D array by means of argentophilic interactions (Ag···Ag 3.28 ?). Bridging between different metal atoms through the triazole groups assists formation of heterobimetallic Ag(I)/V(V) secondary building blocks in a linear V-Ag-Ag-V sequence that is observed in complexes 2-4. These unprecedented tetranuclear {Ag(2)(VO(2)F(2))(2)(tr)(4)} units (the intermetal Ag-Ag and Ag-V distances are 4.24-4.36 and 3.74-3.81 ?, respectively), in which vanadium(V) oxofluoride units possess distorted trigonal bipyramidal environment {VO(2)F(2)N}ˉ, are incorporated into 1D ribbon (2) or 2D square nets (3, 4) using bitopic μ(4)-triazole ligands. The valence bond calculation for vanadium atoms shows +V oxidation state in the corresponding compounds. Thermal stability and photoluminescence properties were studied for all reported coordination polymers.     

In situ solvothermal generation of 1,2,4-triazolates and related compounds from organonitrile and hydrazine hydrate: a mechanism study

The facile and effective one-pot solvothermal syntheses of 3,5-disubstituted 1,2,4-triazole and its derivatives (substituted group = alkyl, aryl, and pyridyl) through cyclocondensations of organonitriles and hydrazine hydrate in the absence/presence of metal salts have been established. By control of the solvothermal conditions and/or the addition of counteranions, different intermediates and final products were derived from various organonitriles, in which an intermediate N,N'-bis(picolinamide)azine (H4bpa) has been successfully trapped in its neutral manganese(II) complexes. A systematical study shows that, after the initial formation of 2-pyridylamidrazone from 2-cyanopyridine and hydrazine, two reaction paths are involved in the formation of 1,2,4-triazoles: via the formation of 3,6-bis(2-pyridyl)-1,2-dihydro-1,2,4,5-tetrazine and H4bpa as intermediates. The tetrazine and H4bpa paths are preferred in the absence and presence of metal ions, respectively. In the presence of metal ions, metal ion binding can stabilize the tautomers, enhance the nucleophilic reactivity of the imino C atom, and inhibit the tautomerization of H4bpa, hence leading to the formation of 1,2,4-triazolates or H4bpa in complexed forms. The in situ cyclocondensation reactions of 2-pyridylamidrazone and carboxylate into asymmetric 3,5-disubstituted 1,2,4-triazolates under solvothermal conditions have also been observed for the first time. Crystal structures of the crystalline metal complexes have been obtained, including dinuclear [Mn2(bpt)2Cl2(H2O)2] (1) and [Mn2(bpt)2(SCN)2(H2O)2] (3; Hbpt = 3,5-bis(2-pyridyl)-4H-1,2,4-triazole), tetranuclear [Mn4(H3bpa)2(mpt)4(N3)2].2H2O (5; Hmpt = 3-methyl-5-(2-pyridyl)-1H-1,2,4-triazole), [Mn4(H3bpa)2(pt)4(N3)2].2C2H5OH (6; Hpt = 5-(2-pyridyl)-1H-1,2,4-triazole), and [Mn4(H3bpa)4(SCN)4].2C2H5OH (7), as well as helical [Cu(bpt)] (2). Among them, 7 is the first example of a neutral tetranuclear [2 x 2] grid manganese(II) complex. Both 5 and 7 exhibit antiferromagnetic interactions.     

Syntheses,crystal structures,and spectral characterization of an asymmetrically substituted 1,2,4-triazole and its iron(II) complex

One new asymmetrically substituted 1,2,4-triazole, 4-amino-3-(p-bromophenyl)-5-(2-pyridyl)-1,2,4-triazole (L), and its iron(II) complex, trans-[FeL₂(NCS)₂] (1), have been synthesized and characterized by elemental analyses, FT-IR, ¹H NMR, ESI mass spectra, and single-crystal X-ray crystallography. Crystallographic studies revealed that 1 contains a distorted octahedral [FeN₆] core with two trans NCS^?. Each L adopts a chelating bidentate coordination via N of pyridyl and one N of the triazole ring. Magnetic susceptibility measurements indicated that 1 remained in a high-spin state between 1.8 and 300?K.