芳基吡啶类Fe3+荧光探针的合成与分析应用

设计合成了两种新型的以2-苯基苯并噻唑为荧光团、N-(2-吡啶甲基)胺为识别基团的铁离子荧光分子探针2-(4-N-2-吡啶甲胺基)苯基-1,3-苯并噻唑(A1)和2-(4-N,N双2-吡啶甲胺基)苯基-1,3-苯并噻唑(A2),化合物结构用UV,IR,1HNMR和13CNMR进行了表征,并考察了探针的荧光特性.结果表明荧光分子探针A2在CH3 CH2OH/H-12O(1∶1,V/V)溶液中,能从常见的金属离子中以95％的荧光淬灭率选择性地识别铁离子,对Fe3+线性响应范围在0.15～1.3 μ mol/L之间,且检出限达10 nmol/L.     

Coordination-driven self-assembly of palladium(Ⅱ)-based metallacalixarenes as anion receptors using flexible pyridine-bridged diimidazole ligands

Two types of palladiu m(Ⅱ)-based metallacalixarenes[ML]²⁺and[ML₂]²⁺have been synthesized through coordination-driven self-assembly from a series of flexible pyridine-bridged diimidazole ligands[2,6-bis((1 H-imidazol-1-yl)methyl)pyridine(L¹),2,6-bis((1 H-benzo[d]imidazol-1-yl)methyl)pyridine(L²),2,6-bis((1 H-naphtho[2,3-d]imidazol-1-yl)methyl)pyridine(L³)],with palladium(II)-based building blocks[Pd(BF₄)₂(M¹-BF_4)and(tmeda)Pd(NO₃)₂(M²-NO₃)(tmeda=N,N,N',N'-tetramethyl-ethylenediamine)].All complexes were characterized by NMR spectroscopy(¹H NMR and¹³C NMR),mass spectrometry(CSIMS,ESI-HRMS)and elemental analysis.The single crystal X-ray diffraction analysis of[M¹L²_2](NO₃)₂,[M¹L³_2](NO₃)₂,[M¹L³_2](PF_6)_2 and[M~2 L³](NO₃)₂further confirmed the uniquely single bowl-shape and double bowl-shape structures.The anion binding properties within the metallacalixarenes as receptors were also investigated by NMR titration experiments in DMSO.     

含吡啶-2,6-二酰亚胺单元的大环化合物合成及性质

在硫酸催化作用下,用前体二醛1[1,3-二(2'-甲酰苯氧基)丙烷]和前体二胺2[N,N'-(2-胺基苯基)-2,6-二甲酰亚胺吡啶]合成了[1+1]席夫碱大环化合物3,进一步还原得到饱和大环4。 用¹H NMR、IR、元素分析和质谱等技术手段对大环3和4的组成进行了表征。 采用X射线衍射仪测定了大环3 和4的晶体结构。 用UV-Vis光谱仪对大环3和4与系列阴离子的作用分别进行了考察,结果表明,饱和大环4仅对F^-有明显的选择性作用,并测定了该配位反应的配位比和平衡常数,进一步考察了大环3和4对甲醇的吸附性能。     

铁、钴催化剂乙烯聚合原位紫外-可见光谱研究

利用乙烯常压聚合原位紫外 可见 (UV Vis)光谱技术 ,对 3个铁、钴络合物作为催化剂前体的催化剂体系进行了研究 .3个铁、钴络合物分别为 2 ,6 双 [1 (2 ,6 二甲基苯基亚胺 )乙基 ]吡啶二氯化铁 (a)、2 ,6 双 [1 (2 ,4,6 三甲基苯基亚胺 )乙基 ]吡啶二氯化铁 (b)和 2 ,6 双 [1 (2 ,6 二异丙基苯基亚胺 )乙基 ]吡啶二氯化钴(c) .实验结果表明 ,MAO对络合物催化剂前体的活化作用是一个快速过程 ;在聚合条件下分别观察到 5 6 0、6 30和 5 80nm的活性峰 ,考察了它们在聚合过程中的生长和在加入无水乙醇逐步使催化剂中毒时活性峰的消失规律 .对催化剂活性物种的结构和聚合机理进行了探讨     

2-Aminopyrrolines: new chiral amidinate ligands with a rigid well-defined molecular structure and their coordination to Ti(IV)

The use of an amino-oxazolinate (NN(ox) = kappa2-2,6-dimethylphenylamido-4(S)-isopropyloxazoline) as a chiral analogue to amidinate ligands in the chemistry of titanium was found to lead to undesired side reactions. The reaction of 2,6-dimethylphenylamido-4(S)-isopropyloxazoline with [Ti(NMe2)4] afforded the bis(amidinato) complex [Ti(NN(ox))2(NMe2)2] (2) which was thermally converted to the ring-opened decomposition products [Ti(NN(ox)){kappa3-N(2,6-C6H3Me2)C(NMe2)NC(iPr)CH2O}(NMe2)] (3) and [Ti{kappa3-N(2,6-C6H3Me2)C(NMe2)-NC(iPr)CH2O}2] (4). The NMR spectra of 4 recorded at low temperature displayed two sets of resonances corresponding to two symmetric isomers in a 2:5 ratio, the probable geometries of which were established by ONIOM (QM/MM) simulations. To suppress ring opening of the oxazolines, their oxygen atom was formally replaced by a CH2 group in the synthesis of a series of amino-pyrroline protioligands 2-RN(H)(5-C4H5NR') (HN(R)N(R')). Their reaction with [Ti(NMe2)4] gave the thermally stable complexes [Ti(N(R)N(R'))2(NMe2)2], of which three derivatives were characterized by X-ray diffraction. They are stereochemically dynamic and undergo reversible ligand rearrangements in solution, for which the activation parameters were determined by variable-temperature (1)H NMR spectroscopy.     

Photomagnetic properties of iron(II) spin crossover complexes of 2,6-dipyrazolylpyridine and 2,6-dipyrazolylpyrazine ligands

The photomagnetic properties of the following iron(II) complexes have been investigated: [Fe(L1)2][BF4]2, [Fe(L2)2][BF4]2, [Fe(L2)2][ClO4]2, [Fe(L3)2][BF4]2, [Fe(L3)2][ClO4]2 and [Fe(L4)2][ClO4]2 (L1 = 2,6-di{pyrazol-1-yl}pyridine; L2 = 2,6-di{pyrazol-1-yl}pyrazine; L3 = 2,6-di{pyrazol-1-yl}-4-{hydroxymethyl}pyridine; and L4 = 2,6-di{4-methylpyrazol-1-yl}pyridine). Compounds display a complete thermal spin transition centred between 200-300 K, and undergo the light-induced excited spin state trapping (LIESST) effect at low temperatures. The T(LIESST) relaxation temperature of the photoinduced high-spin state for each compound has been determined. The presence of sigmoidal kinetics in the HS --> LS relaxation process, and the observation of LITH hysteresis loops under constant irradiation, demonstrate the cooperative nature of the spin transitions undergone by these materials. All the compounds in this study follow a previously proposed linear relation between T(LIESST) and their thermal spin-transition temperatures T(1/2): T(LIESST) = T(0)- 0.3T(1/2). T(0) for these compounds is identical to that found previously for another family of iron(II) complexes of a related tridentate ligand, the first time such a comparison has been made. Crystallographic characterisation of the high- and low-spin forms, the light-induced high-spin state, and the low-spin complex [Fe(L4)2][BF4]2, are described.     

One-pot synthesis of [1+1] and 62-membered [2+2] Schiff base macrocycles

New [1+1] and 62-membered [2+2] Schiff base macrocycles containing a 2,6-diamidopyridine subunit have been synthesized by condensation reaction of the precursors pyridine-2,6-dicarboxamide and 1,10-bis(20-formylphenyloxy)decane in the presence of phosphoric acid via a one-pot process. The cyclocondensed products were effectively isolated by gel column chromatography and characterized by ~1H NMR, FTIR, mass spectrometry and X-ray analysis. The two macrocycles have a twisted structure, and not an open ‘circular' conformation in the solid state.     

2-[4-(2,6-二氟苯基)噻唑-2-基]-3-羟基丙烯腈衍生物的合成及生物活性

为了寻找生物活性良好的噻唑基丙烯腈类化合物, 利用2-[4-(2,6-二氟苯基)噻唑-2-基]乙腈(3)分别与取代氯甲酸酯4和取代苯基异氰酸酯6在碱存在下反应, 合成了8个2-[4-(2,6-二氟苯基)噻唑-2-基]-3-羟基-3-烃氧基丙烯腈化合物5和7个2-[4-(2,6-二氟苯基)噻唑-2-基]-3-羟基-3-取代苯胺基丙烯腈化合物7, 均为首次报道的丙烯腈类化合物. 化合物结构经1H NMR, IR, MS和元素分析表征. 初步生物活性测定结果表明, 在试验浓度下, 目标化合物均具有一定的杀虫和抑菌活性, 其中化合物5f和5h在100 mg/L浓度下对炭疽病菌的抑制率达95%; 化合物5g和7d在250 mg/L浓度下对棉红蜘蛛的致死率达85%.     

Synthesis and electrochemical properties of 2,6-bis（6-aryl-[1,2,4]- triazolo[3,4-b][1,3,4]-thiadiazole-3-yl）pyridines

By the condensation of 2,6-bis（4-amino-5-mercapto-[1,2,4]-triazoles-2）pyridine with aromatic acid in the presence of phosphorus oxychloride. Compounds of 2,6-bis（6-aryl-[1,2,4]-triazolo[3,4-b][1,3,4]-thiadiazole-3-yl）pyridines were synthesized. Their structures were confirmed by IR, ^1H NMR spectroscopies and elemental analysis. Their electrochemical behavior and cyclic voltammogram also were be studied. The results showed that they have high ionization potentials and good affinity.     

新型吡啶双亚胺铁催化乙烯聚合反应

合成与表征了一种新型吡啶双亚胺铁烯烃聚合催化剂2,6-二[1-(4-羟基-2,6-二甲基苯胺)乙基]吡啶氯化铁（1a）。结果表明,在亚胺环的对位引入羟基,可同时提高催化剂的活性和聚合物的分子量。在改性甲基铝氧烷(MMAO)的活化下,该催化剂引发乙烯聚合的活性（以单位时间（h）mol Fe引发乙烯聚合的PE质量（g）来表征）可达到6.78×10⁶ g/（mol•h）,明显高于已知催化剂2,6-二[1-(2,6-二甲基苯胺)乙基]吡啶氯化铁（1b）,且能得到更高分子量的聚乙烯。     

Fluxional behavior of methyl-substituted tricarbonyl(tropone)iron complexes and their different reactivity

The compositions of regioisomeric mixtures of tricarbonyliron complexes of 2-methyltropone (1a,b), 3-methyltropone (2a,b) and 2,6-dimethyltropone (3a,b) are studied and compared with the results of ab initio computations. The structures, frontier orbitals, and population analysis are evaluated by means of density functional theory. The thermodynamic and kinetic parameters of regioisomerizations are determined using dynamic ¹H NMR technique. The influence of methyl-substituent(s) on the equilibrium ratio of regioisomers resulting from the haptotropic rearrangement is discussed. Significant differences in the reactivity of C-protonized methyl- and dimethyl-substituted tricarbonyl(tropone)iron complexes 4–6 in nucleophilic additions and corresponding O-trimethylsilylated complexes 7–9 in [3+2] cycloadditions are explained in terms of electronic and steric effects of the methyl group(s). Various hydroazulenone cycloadducts of tricarbonyl(η⁴-2,6-dimethyltropone)iron 3a,b have been prepared by stereoselective [3+2] cycloaddition with Fp-reagents 12–14 and characterized. Formerly proposed mechanism of [3+2] cycloaddition was approved.     

Two [2]pseudorotaxane-like complexes and their corresponding [2]rotaxanes stabilized via interactions on opposite ends of the same macrocycle

A multiple-use macrocycle recognizes dibenzylammonium ions and 2,6-lutidine derivatives, each in a [2]pseudorotaxane-like manner, through interactions with its diethylene glycol (hydrogen bonding) and 2,6-pyridinedicarboxamide (Pd²⁺ chelation) spacers, respectively. We characterized these complexes in the solid state (X-ray crystallography) and in solution (¹H NMR spectroscopy). The synthesis of two corresponding [2]rotaxanes confirmed that these recognition systems possess [2]pseudorotaxane geometries in solution.     

Double N-H bond activation of N,N'-bis-substituted hydrazines with stable N-heterocyclic silylene

The reaction of N-heterocyclic silylene (NHSi) L [L = CH{(C[double bond, length as m-dash]CH(2))(CMe)(2,6-iPr(2)C(6)H(3)N)(2)}Si] with benzoylhydrazine, 1,2-dicarbethoxyhydrazine, 1,2-diacetylhydrazine and 1,2-bis(tert-butoxycarbonyl)hydrazine in 1 : 1 molar ratio resulted in compounds 1-4 with an almost quantitative yield and five coordinate silicon atoms. Compounds 1-4 were formed by double N-H bond activation by deliberate selection of N,N'-bis-substituted hydrazine compounds bearing the -C(O)NHNH- unit. Compounds 1-4 were characterized by NMR spectroscopy, EI-MS and elemental analysis. The molecular structures of compounds 1-3 were unambiguously established by single crystal X-ray structural analysis.     

NCN pincer palladium complexes: their preparation via a ligand introduction route and their catalytic properties

A wide range of NCN pincer palladium complexes, [4-tert-butyl-2,6-bis(N-alkylimino)phenyl]chloropalladium (alkyl = n-butyl, benzyl, cyclohexyl, tert-butyl, adamantyl, phenyl, 4-methoxyphenyl), were readily prepared from trans-(4-tert-butyl-2,6-diformylphenyl)chlorobis(triphenylphosphine)palladium via dehydrative introduction of the corresponding alkylimino ligand groups (ligand introduction route) in excellent yields (71-98%). NMR studies on this route for forming pincer complexes revealed the intermediacy of [4-tert-butyl-2,6-bis(N-alkylimino)phenyl]chlorobis(triphenylphosphine)palladium which is in equilibrium with the corresponding NCN pincer complexes via coordination/dissociation of the intramolecular imino groups and triphenylphosphine ligands. A series of chiral NCN pincer complexes bearing pyrroloimidazolone units as the trans-chelating donor groups, [4-tert-butyl-2,6-bis{(3R,7aS)-2-phenylhexahydro-1H-pyrrolo[1,2-c]imidazol-1-on-3-yl}phenyl]chloropalladium, were also prepared from the same precursor via condensation with proline anilides in high yields. The catalytic properties of the NCN imino and the NCN pyrroloimidazolone pincer palladium complexes were examined in the Heck reaction and the asymmetric Michael reaction to demonstrate their high catalytic activity and high enantioselectivity.     

Photochromism of polymorphic 4,4'-methylenebis(N-salicylidene-2,6-diisopropylaniline) crystals

4,4[prime or minute]-Methylenebis(N-salicylidene-2,6-dialkylaniline) derivatives were prepared and their structures were determined by (1)H NMR, IR, DSC and X-ray crystallographic analyses. The 2,6-diisopropylaniline derivative yielded definite polymorphic crystals: the space groups of the crystals were C2/c and P2(1)/n, respectively. It was found that both polymorphs were similarly photochromic but the thermal stability of the photochrome was different due to the variance of the shape of molecule and cavity in each crystal.     

In vitro microbial studies of new pyrazolyl quinazolin-4(3H) ones

A series of new 2-[2-(2,6-dichlorophenyl)amino]phenyl methyl-3-[(5-substituted phenyl)-1,5-dihydro-1H-pyrazol-3-yl-amino]-6-iodoquinazolin-4(3H) ones (6a–m) have been synthesized by the reaction of 2-[2-(2,6-dichlorophenyl)amino]phenyl methyl-3-substituted phenyl acryl amido-6-iodoquinazolin-4(3H) ones with hydrazine hydrate in the presence of glacial acetic acid. The chalcone (5a–m) have been prepared by the condensation of 2-[2-(2,6-dichlorophenyl)amino]phenyl methyl-3-acetamido-6-iodoquinazolin-4(3H) one with different substituted aromatic aldehyde. The compound 1 on treatment with 5-iodoanthranilic acid in pyridine undergoes cyclisation gave 2-[2-(2,6-dichlorophenyl)amino]phenyl methyl-6-iodo-3,1-benzoxazin-4(3H) one (2). Treatment on benzoxazine with hydrazine hydrate gave 3-amino-2-[2-(2,6-dichlorophenyl)amino]phenyl methyl-6,8-dibromo quinazolin-4(3H) one (3) followed by acetylation synthesized 2-[2-(2,6-dichlorophenyl)amino]phenyl methyl-3-acetamido-6,8-dibromoquinazolin-4(3H)-one (4). The structure of synthesized compounds has been elucidated by IR, ¹H NMR, ¹³C NMR and elemental analysis. The products were screened for antibacterial and antifungal activity. Among the series containing some of the compounds showed promising results against standard drugs.     

Structural diversity in iron(II) complexes of 2,6-di(pyrazol-1-yl)pyridine and 2,6-di(3-methylpyrazol-1-yl)pyridine

The syntheses, magnetochemistry and crystallography of [Fe(L1)2]I0.5[I3]1.5 (1), [Fe(L1)2][Co(C2B9H11)2]2 (2) and [Fe(L2)2][SbF6]2 (3) (L1 = 2,6-di(pyrazol-1-yl)pyridine; L2 = 2,6-di(3-methylpyrazol-1-yl)pyridine) are described. Compounds 1 and 3 are high-spin between 5-300 K. For 1, this reflects a novel variation of an angular Jahn-Teller distortion at the iron centre, which traps the molecule in its high-spin state. No such distortion is present in 3; rather, the high-spin nature of this compound may reflect ligand conformational strain caused by an intermolecular steric contact in the crystal lattice. Compound 2 exhibits a gradual high --> low spin transition upon cooling with T(1/2) = 318 +/- 3 K, that is only 50% complete. This reflects the presence of two distinct, equally populated iron environments in the solid. One of these unique iron centres adopts the same angular structural distortion shown by 1 and so is trapped in its high-spin state, while the other, which undergoes the spin-crossover, has a more regular coordination geometry. In contrast with 3, the solvated salts [Fe(L2)2][BF4]2 x 4 CH3CN and [Fe(L2)2][ClO4]2 x (CH3)2CO both undergo gradual thermal spin-transitions centred at 175 +/- 3 K.     

Aluminum complexes incorporating bidentate amido phosphine ligands

A series of aluminum complexes supported by o-phenylene-derived amido phosphine ligands, N-(2-diphenylphosphinophenyl)-2,6-dimethylanilide ([Me-NP]-) and N-(2-diphenylphosphinophenyl)-2,6-diisopropylanilide ([iPr-NP]-), have been prepared. The reactions of trialkylaluminum with H[Me-NP] and H[iPr-NP], respectively, in refluxing toluene produced the corresponding dialkyl complexes [Me-NP]AlR(2) and [iPr-NP]AlR(2) (R = Me, Et). Deprotonation of H[Me-NP] with n-BuLi in THF at -35 degrees C followed by addition of AlCl(3) in toluene at -35 degrees C afforded [Me-NP]AlCl(2), which was subsequently reacted with 2 equiv of trimethylsilylmethyllithium in toluene to give [Me-NP]Al(CH(2)SiMe(3))(2). The aluminum complexes were all characterized by (1)H, (13)C, (31)P, and (27)Al NMR spectroscopy. The solid-state structures of monomeric, four-coordinate [Me-NP]AlEt(2) and [iPr-NP]AlMe(2) and five-coordinate [Me-NP]AlCl(2)(THF) were determined by X-ray crystallography. The (1)H NMR studies of [Me-NP]AlEt(2), [Me-NP]Al(CH(2)SiMe(3))(2), and [iPr-NP]AlEt(2) indicate diastereotopic alpha-hydrogen atoms in these molecules. Heteronuclear COSY and NOE experiments suggest that the phosphorus donor in [Me-NP]Al(CH(2)SiMe(3))(2) and [iPr-NP]AlEt(2) is coupled to only one of the diastereotopic alpha-hydrogen atoms that is virtually antiperiplanar with respect to the phosphorus atom.     

X-ray crystallographic and Mössbauer spectroscopic applications in dependence of partial quadrupole splitting, [R], on the C-Sn-C angle in seven-coordinated diorganotin(IV) complexes

The synthesis and the IR, NMR (1H, 13C, and 119Sn), and M?ssbauer spectroscopies and single-crystal X-ray diffraction studies of seven-coordinated diorganotin(IV) complexes, namely, [Ph2Sn(Hdapsc)]Cl.H2O.DMF [7; H(2)dapsc = 2,6-diacetylpyridine bis(semicarbazone)], [Me(2)Sn(H2,6Achexim)]Br.H2O [8; H(2)2,6Achexim = 2,6-diacetylpyridine bis(3-hexamethyleneiminylthiosemicarbazone)], [Me(2)Sn(dapmts)] [9; H(2)dapmts = 2,6-diacetylpyridine bis(4-methythiosemicarbazone)], and [nBu2Sn(dapmdtc)] [10; H(2)dapmdtc = 2,6-diacetylpyridine bis(S-methydithiocarbazate)], were done. The determination of the structures of [Ph(2)Sn(Hdapsc)]+, [Me2Sn(H2,6Achexim)]+ and [Me2Sn(dapmts)], [nBu2Sn(dapmdtc)] revealed the presence of monocationic and neutral complexes, respectively. The structures consist of monomeric units in which the Sn(IV) ions exhibit distorted pentagonal-bipyramidal geometries, with the X,N,N,N,X-donor (X = O, S) systems of the ligands lying in the equatorial plane and the organic groups in the apical positions. The C-Sn-C angle in the seven-coordinated diorganotin(IV) complexes was estimated using a correlation between M?ssbauer and X-ray data based on the point-charge model and using new values obtained in this work for [alkyl] = -1.00 mm s(-1) and [aryl] = -0.80 mm s(-1) for complexes containing O,N,N,N,O-pentadentate ligands and new values for [alkyl] = -0.87 mm s(-1) and [aryl] = -0.75 mm s(-1) for complexes containing S,N,N,N,S-pentadentate ligands.     

Syntheses and solid-state and solution structures of [Ba[(C5Me5)2Ti2F7]2(hmpa)] and [Ba8Ti6F30I2(C5Me5)6(hmpa)6][I3]2

The complexes [Ba[(C5Me5)2Ti2F7]2(hmpa)].(THF), 1.hmpa.(THF), and [Ba8Ti6F30I2(C5Me5)6(hmpa)6][I3]2.10(THF), 2[I3]2.10(THF), were prepared from [Hdmpy](+)[(C5Me5)2Ti2F7]- (dmpy = 2,6-dimethylpyridine), BaI2, and hmpa (hmpa = hexamethylphosphoramide). They were characterized by 1H and 19F NMR and IR spectroscopy and examined by single-crystal X-ray crystallography. The complexation equilibrium of the barium ion in 1 with hmpa and the dynamics of the barium ion moving on the fluorine surfaces of [(C5Me5)2Ti2F7]- in 1.hmpa have been studied by variable-temperature 19F NMR spectroscopy. The core of the complex 2[I3]2.10(THF) resembles the basic structural unit of the cubic perovskite.