水体系中含卟啉基团的两亲高分子的自组装行为和性质的研究

在文中合成了两种不同的卟啉单体5-(4-acryloyloxyphenyl)-10,15,20-tris(4-carboxylphenyl)porphyrinate zinc(Ⅱ)(ZnAOTCPP)和5-(4-acrylo-yloxyphenyl)-10,15,20-tris(4-methoxycarboxylphenyl)porphyrinate zinc(Ⅱ)(ZnMeAOTCPP),它们分别与丙烯酰胺(Acrylamide,AM)聚合得到含有卟啉基团的两亲高分子.与对应的单体相比,含有三羧酸卟啉基团的高分子在水中形成了一个新的紫外吸收峰和一个新的荧光发射峰,而含有三羧酸甲酯卟啉基团的高分子除此之外在更长波的方向上还另外出现了一个新的紫外吸收峰和一个新的荧光发射峰.随着高分子水溶液浓度的提高,高分子中卟啉基团的光谱性质的变化趋势显示高分子在水中的自组装行为可以分为分子间缔合和分子内缔合的两种情况.此外,实验结果显示含有三羧酸甲酯卟啉基团的高分子相对于含有三羧酸卟啉基团的高分子更加有利于卟啉缔合物的形成.     

Pentanuclear and heptanuclear helicates by self-assembly of d10 metal ions and a rigid aromatic bis-bidentate chelator

The self-assembly of Zn(II) and Cd(II) ions with a bis-bidentate ligand 3,5-bis(benzimidazol-2-yl)pyrazole (H 3L) was studied by Electrospray ionization mass spectrometry, (1)H NMR measurements, and single-crystal X-ray diffraction analyses. Reaction of Zn(ClO 4) 2.6H 2O and Cd(ClO 4) 2.6H 2O with H 3L in DMF gave two pentanuclear complexes [(Zn 5(mu 3-O)(H 2L) 6)(ClO 4) 2.DMF.9.5H 2O ( 1) and [Cd 5(mu 3-O)(H 2L) 6](ClO 4)(OH).4.75DMF.0.25EtOH.10.5H 2O ( 2), in which the trigonal-bipyramidal core structures are bridged by mu 3-oxo and pyrazolate rings of the monodeprotonated H 2L. When Na 3PO 4.12H 2O was used in the reaction system of CdBr 2.4H 2O and H 3L, [Cd 5(mu 3-O)(H 2L) 6]Br 2.4.5DMF.6.5H 2O ( 3) and [Cd 7(mu 6-PO 4)(mu-Br) 3(H 2L) 6](HPO 4).DMF.10H 2O ( 4) were isolated. 3 displays the same core structure as that of 2, whereas 4 exhibits a turbinate, heptanuclear core which is bridged by a mu 6-PO 4, three mu-Br, and three pyrazolate rings. All of the pentanuclear and heptanuclear cores are surrounded by three pairs of bis-bidentate H 2L (-) ligands with offset pi-pi stacking, showing propeller-like molecular structures and triple-stand helicates. Electrospray ionization mass spectrometry studies and (1)H NMR measurements demonstrate that the pentanuclear complexes have different stability in the solution, depending on the metal ions and the counteranions. Furthermore, both 1 and 2 emit blue fluorescence with nanosecond luminescent lifetimes in DMF at room temperature.     

A mild and efficient method for the stereoselective formation of C-O bonds: palladium-catalyzed allylic etherification using zinc(II) alkoxides

[reaction: see text] A highly chemo- and stereoselective palladium-catalyzed allylic etherification reaction is described. The use of zinc(II) alkoxides proved effective in promoting the addition of the oxygen nucleophile derived from aliphatic alcohols to eta(3)-allylpalladium complexes. Using diethylzinc (0.5 equiv), 5 mol % of Pd(OAc)(2), and 7.5 mol % of 2-di(tert-butyl)phosphinobiphenyl in THF, the cross-coupling reaction between various aliphatic alcohols and allylic acetates proceeded at ambient temperature to furnish allylic ethers with high stereoselectivity.     

Syntheses, structures, and photoluminescence properties of metal(II) halide complexes with pyridine-containing flexible tripodal ligands

Seven coordination compounds, [Zn(L3)Cl2] . MeOH . H2O (1), [Mn(L3)2Cl2] . 0.5EtOH . 0.5H2O (2), [Cu3(L2)2Cl6] . 2DMF (3), [Cu3(L2)2Br6] . 4MeOH (4), [Hg2(L4)Cl4] (5), [Hg2(L4)Br4] (6), and [Hg3(L4)2I6] . H2O (7), were synthesized by the reactions of ligands 1,3,5-tris(3-pyridylmethoxyl)benzene (L3), 1,3,5-tris(2-pyridylmethoxyl)benzene (L2), and 1,3,5-tris(4-pyridylmethoxyl)benzene (L4) with the corresponding metal halides. All the structures were established by single-crystal X-ray diffraction analysis. In complexes 1 and 2, L3 acts as a bidentate ligand using two of three pyridyl arms to link two metal atoms to result in two different 1D chain structures. In complexes 3 and 4, each L2 serves as tridentate ligand and connects three Cu(II) atoms to form a 2D network structure. Complexes 5 and 6 have the same framework structure, and L4 acts as a three-connecting ligand to connect Hg(II) atoms to generate a 3D 4-fold interpenetrated framework, while the structure of complex 7 is an infinite 1D chain. The results indicate that the flexible ligands can adopt different conformations and thus can form complexes with varied structures. In addition, the coordination geometry of the metal atom and the species of the halide were found to have great impact on the structure of the complexes. The photoluminescence properties of the complexes were investigated, and the Zn(II), Mn(II) and Hg(II) complexes showed blue emissions in solid state at room temperature.     

Metallacycles of iron, zinc, and cadmium assembled by polytopic bis(pyrazolyl)methane ligands and fluoride abstraction from BF4-

Reactions of the arene-linked bis(pyrazolyl)methane ligands m-bis[bis(1-pyrazolyl)methyl]benzene (m-[CH(pz)2]2C6H4, Lm) and 1,3,5-tris[bis(1-pyrazolyl)methyl]benzene (1,3,5-[CH(pz)2]3C6H3, L3) with BF4- salts of divalent iron, zinc, and cadmium result in fluoride abstraction from BF4- and formation of fluoride-bridged metallacyclic complexes. Treatment of Fe(BF4)2.6H2O and Zn(BF4)2.5H2O with Lm leads to the complexes [Fe2(mu-F)(mu-Lm)2](BF4)3 (1) and [Zn2(mu-F)(mu-Lm)2](BF4)3 (2), in which a single fluoride ligand and two Lm molecules bridge the two metal centers. The reaction of [Cd2(thf)5](BF4)4 with Lm results in the complex [Cd2(mu-F)2(mu-Lm)2](BF4)2 (3), which contains dimeric cations in which two fluoride and two Lm ligands bridge the cadmium centers. Equimolar amounts of the tritopic ligand L3 and Zn(BF4)2.5H2O react to give the related monofluoride-bridged complex [Zn2(mu-F)(mu-L3)2](BF4)3 (4), in which one bis(pyrazolyl)methane unit on each ligand remains unbound. NMR spectroscopic studies show that in acetonitrile the zinc metallacycles observed in the solid-state remain intact in solution.     

Cyanide-bridged iron(II,III) cube with multistepped redox behavior

A building unit of Prussian blue was isolated as a cyanide-bridged iron cube of [Fe(II)4Fe(III)4(CN)12(tp)8] x 12 DMF x 2 Et2O x 4 H2O [tp(-) = hydrotris(pyrazolyl)borate]. A cyclic voltammogram showed quasi-reversible four-stepped redox waves, which correspond to [Fe(III)4Fe(II)4]/[Fe(III)5Fe(II)3](+), [Fe(III)5Fe(II)3](+)/[Fe(III)6Fe(II)2](2+), [Fe(III)6Fe(II)2](2+)/[Fe(III)7Fe(II)1](3+), and [Fe(III)7Fe(II)1](3+)/[Fe(III)8](4+) processes. Controlled potential absorption spectral measurements revealed two intervalence charge-transfer bands at 816 and 1000 nm, which were assigned to charge transfers from Fe(II) ions to adjacent and remote Fe(III) ions, respectively, in the cube.     

Coordination complexes exhibiting anion...pi interactions: synthesis, structure, and theoretical studies

The polydentate ligand 2,4,6-tris(dipyridin-2-ylamino)-1,3,5-triazine (dpyatriz) in combination with the Cu(ClO 4) 2/CuX 2 salt mixtures (X (-) = Cl (-), Br (-), or N 3 (-)) leads to the formation of molecular coordination aggregates with formulas [Cu 3Cl 3(dpyatriz) 2](ClO 4) 3 ( 2), [Cu 3Br 3(dpyatriz) 2](ClO 4) 3 ( 3), and [Cu 4(N 3) 4(dpyatriz) 2(DMF) 4(ClO 4) 2](ClO 4) 2 ( 4). These complexes consist of two dpyatriz ligands bridged via coordination to Cu (II) and disposed either face-to-face in an eclipsed manner ( 2 and 3) or parallel and mutually shifted in one direction. The copper ions complete their coordination positions with Cl (-) ( 2), Br (-) ( 3), or N 3 (-), ClO 4 (-), and N, N-dimethylformamide (DMF) ( 4) ligands. All complexes crystallize together with noncoordinate ClO 4 (-) groups that display anion...pi interactions with the triazine rings. These interactions have been studied by means of high level ab initio calculations and the MIPp partition scheme. These calculations have proven the ClO 4 (-)...[C 3N 3] interactions to be favorable and have revealed a synergistic effect from the combined occurrence of pi-pi stacking of triazine rings and the interaction of these moieties with perchlorate ions, as observed in the experimental systems.     

Diruthenium complexes [((acac)2RuIII)2(mu-OC2H5)2], [((acac)(2RuIII)2(mu-L)](ClO4)2, and [((bpy)(2RuII)2(mu-L)](ClO4)4 [L = (NC5H4)2-N-C6H4-N-(NC5H4)2, acac = acetylacetonate, and bpy = 2,2'-bipyridine]. synthesis, structure, magnetic, spectral, and photophysical aspects

Paramagnetic diruthenium(III) complexes (acac)(2)Ru(III)(mu-OC(2)H(5))(2)Ru(III)(acac)(2) (6) and [(acac)(2)Ru(III)(mu-L)Ru(III)(acac)(2)](ClO(4))(2), [7](ClO(4))(2), were obtained via the reaction of binucleating bridging ligand, N,N,N',N'-tetra(2-pyridyl)-1,4-phenylenediamine [(NC(5)H(4))(2)-N-C(6)H(4)-N-(NC(5)H(4))(2), L] with the monomeric metal precursor unit (acac)(2)Ru(II)(CH(3)CN)(2) in ethanol under aerobic conditions. However, the reaction of L with the metal fragment Ru(II)(bpy)(2)(EtOH)(2)(2+) resulted in the corresponding [(bpy)(2)Ru(II) (mu-L) Ru(II)(bpy)(2)](ClO(4))(4), [8](ClO(4))(4). Crystal structures of L and 6 show that, in each case, the asymmetric unit consists of two independent half-molecules. The Ru-Ru distances in the two crystallographically independent molecules (F and G) of 6 are found to be 2.6448(8) and 2.6515(8) A, respectively. Variable-temperature magnetic studies suggest that the ruthenium(III) centers in 6 and [7](ClO(4))(2) are very weakly antiferromagnetically coupled, having J = -0.45 and -0.63 cm(-)(1), respectively. The g value calculated for 6 by using the van Vleck equation turned out to be only 1.11, whereas for [7](ClO(4))(2), the g value is 2.4, as expected for paramagnetic Ru(III) complexes. The paramagnetic complexes 6 and [7](2+) exhibit rhombic EPR spectra at 77 K in CHCl(3) (g(1) = 2.420, g(2) = 2.192, g(3) = 1.710 for 6 and g(1) = 2.385, g(2) = 2.177, g(3) = 1.753 for [7](2+)). This indicates that 6 must have an intermolecular magnetic interaction, in fact, an antiferromagnetic interaction, along at least one of the crystal axes. This conclusion was supported by ZINDO/1-level calculations. The complexes 6, [7](2+), and [8](4+) display closely spaced Ru(III)/Ru(II) couples with 70, 110, and 80 mV separations in potentials between the successive couples, respectively, implying weak intermetallic electrochemical coupling in their mixed-valent states. The electrochemical stability of the Ru(II) state follows the order: [7](2+) < 6 < [8](4+). The bipyridine derivative [8](4+) exhibits a strong luminescence [quantum yield (phi) = 0.18] at 600 nm in EtOH/MeOH (4:1) glass (at 77 K), with an estimated excited-state lifetime of approximately 10 micros.     

以杯芳烃为基体的仿细胞色素P-450单加氧酶模型的合成

用对叔丁基杯[4]芳烃与卟啉羧酸的酰氯化物反应,并引入金属,合成了杯芳烃-金属卟啉仿细胞色素P-450单加氧酶模型A,A及前体化合物6的结构经IR,^1H NMR,MS和元素分析确定,并确证A中杯环呈"锥体"构象     

Synthesis and characterization of manganese(II) and iron(III) d5 tripodal imidazole complexes. Effect of oxidation state, protonation state and ligand conformation on coordination number and spin state

The 1 : 3 Schiff base condensates of tris(2-aminoethyl)amine (tren) or tris(3-aminopropyl)amine (trpn) with 4-methyl-5-imidazolecarboxaldehyde, H3L1 and H3L2, respectively, were generated in situ and used to prepare complexes with manganese(II) and iron(III). The resultant complexes, [MnH3L1](ClO4)2, [MnH3L1](ClO4)2.EtOH.H2O, [MnH3L2](ClO4)2, [FeH3L1](ClO4)3.1.5(EtOH) and [FeHL1](I3) (0.525)(I)(0.475).2.625H2O, have been characterized by EA, IR, ES MS, variable temperature magnetic susceptibility, X-ray crystallography, and M?ssbauer spectroscopy for the iron complexes. The three manganese(II) complexes are high spin with [MnH3L2](ClO4)2 exhibiting coordination number seven while the others are six coordinate. [FeH3L1](ClO4)3.1.5(EtOH) has two iron sites, a seven coordinate and a pseudo seven coordinate site. The complex is high spin at room temperature but exhibits a magnetic moment that decreases with temperature corresponding to conversion of one of the sites to low spin. [FeHL1](I3) (0.525)(I)(0.475).2.625H2O is low spin even at room temperature. In the present complexes the apical nitrogen atom, N(ap), of the tripodal ligand is pyramidal and directed toward the metal atom. The data show that the M-N(ap) distance decreases as the oxidation state of the metal increases, as the number of bound imidazole protons on the ligand increases, and as the number of carbon atoms in the backbone of the ligand (tren vs. trpn) increases. In a limiting sense, short M-N(ap) distances result in high spin seven coordinate mono capped octahedral complexes and long M-N(ap) distances result in low spin six coordinate octahedral complexes.     

Six new metal-organic frameworks based on polycarboxylate acids and V-shaped imidazole-based synthon: syntheses, crystal structures, and properties

Solvothermal reactions of 4,4'-bis(imidazol-1-yl)diphenyl ether (BIDPE) with deprotonated 5-hydroxy-isophthalic acid (5-OH-H(2)bdc), and benzene-1,3,5-tricarboxylic acid (H(3)btc) in the presence of cadmium(II), zinc(II), cobalt(II), nickel(II), and manganese(II) salts in H(2)O or H(2)O/DMF produced six new complexes, namely, [Cd(BIDPE)(5-OH-bdc)·H(2)O](n) (1), [Co(BIDPE)(5-OH-bdc)·H(2)O](n) (2), [Zn(3)(BIDPE)(3)(5-OH-bdc)(3)·4H(2)O](n) (3), [Ni(BIDPE)(2)(5-OH-bdc)(H(2)O)·3H(2)O](n) (4), {[Mn(2)(BIDPE)(2)(5-OH-bdc)(2)](n) (5), and [Ni(BIDPE)(2)(Hbtc)(H(2)O)](n) (6). These complexes were characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Compounds 1 and 2 reveal the same two-dimensional (2D) sheets with a 32-membered [(Cd/Co)(2)(BIDPE)(2)] metallocyclic ring constructed from BIDPE and 5-OH-H(2)bdc with Cd or Co salts. For compound 3, six identical 2D sheets are polycatenated in parallel to form a rare 2D → 2D framework; it displays ferroelectric behavior with a remnant electric polarization (P(r)) of 0.033 μC/cm(2) and an electric coercive field (E(c)) of 11.15 kV/cm. In compounds 4 and 6, only one carboxyl group coordinated to the Ni atom from 5-OH-H(2)bdc or H(3)btc. Compound 5 exists as binuclear Mn clusters, which are linked by BIDPE and 5-OH-H(2)bdc to generate a 2D sheet and displays weak antiferromagnetic character. In addition, the thermal stabilities and photochemical properties of these new complexes have been studied.     

Time-dependent density functional molecular orbital and excited state calculations on bis(porphyrinyl)butadiynes in the monocationic, neutral, monoanionic, and dianionic oxidation states

We report a theoretical study of the multiple oxidation states (1+, 0, 1-, and 2-) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis[10,15,20-tris[3',5'-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl]butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the "fully delocalized" or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.     

Self-assembly of homochiral porous solids based on 1D cadmium(II) coordination polymers

A family of homochiral 1D cadmium(II) coordination polymers based on the (S)-2,2'-dimethoxy-1,1'-binaphthyl-3,3'-bis(4-vinylpyridine) (L) bridging ligand were synthesized from the same building blocks under slightly different conditions, and characterized by single-crystal X-ray crystallography. While [CdL(DMF)4](ClO4)2 x EtOH x 0.5H2O (1) adopts a 1D zigzag chain structure, [CdL2(ClO4)2] x 3EtOH x H2O (2) and [CdL2(ClO4)(H2O)] (ClO4) x 1.5(o-C6H4Cl2) x 3EtOH x 6H2O (3) both exhibit 1D polymeric structures that are built from 38-membered macrocycles. These 1D coordination polymers further pack into chiral porous frameworks via pi...pi interactions with a large percentage of void spaces that are occupied by solvent molecules and counterions.     

Photodynamic studies and photoinactivation of Escherichia coli using meso-substituted cationic porphyrin derivatives with asymmetric charge distribution

The photodynamic activities of novel asymmetrically meso-substituted cationic porphyrins, 5,10-di(4-methylphenyl)-15,20-di(4-trimethylammoniumphenyl)porphyrin iodide 1 and 5-(4-trifluorophenyl)-10,15,20-tris(4-trimethylammoniumphenyl)porphyrin iodide 2 and its metal complex with Pd(II) 3, have been investigated in both homogeneous medium bearing photooxidizable substrates and in vitro on a typical gram-negative bacterium Escherichia coli. The amphiphilic character of porphyrin 2 was increased by the presence of a high-lipophilic trifluoromethyl group and its photophysical properties changed by forming a complex with Pd(II). Absorption and fluorescence spectroscopic studies were compared in different media. Fluorescence quantum yields (phi(F)) of 0.16 for 1 in tetrahydrofuran and 0.08 for 2 in N, N-dimethylformamide (DMF) were calculated, whereas no significant emission was detected for Pd(II) porphyrin 3. The singlet molecular oxygen, O(2)((1)Delta(g)), production was evaluated using 9,10-dimethylanthracene in DMF yielding relative values of 1, 0.55 and 0.47 for porphyrins 3, 2 and 1, respectively. A faster decomposition of l-tryptophan was obtained using Pd(II) porphyrin 3 as sensitizer with respect to the free-base porphyrins 1 and 2. In biological medium, the behavior of cationic porphyrins 1-3 were compared with that of 5-(4-carboxyphenyl)-10,15,20-tris(4-methylphenyl)porphyrin 4, which was used as a noncationic sensitizer. These porphyrins are rapidly bound to E. coli cells in 5 min and the amount of cell-bound sensitizer is not appreciably changed incubating the cultures for longer times. The recovered porphyrin 2 after one washing step reaches a value of approximately 2.9 nmol/10(6) cells and this amount remains high even after three washes, indicating that this sensitizer is tightly bound to cells. Photosensitized inactivation of E. coli was analyzed using cells without and with one washing step. In both cases, a higher photoinactivation of cells was found for tricationic porphyrin 2 and 3, causing a approximately 5.5 log (99.999%) decrease of cell survival, when treated with 10 microM of sensitizer. Under these conditions, a lower effect was found for porphyrin 1 (approximately 4 log) whereas sensitizer 4 did not produce appreciable photodamage. The results were also confirmed by growth delay experiments. These studies show that the amphiphilic tricationic porphyrin 2 and 3 bearing a trifluoromethyl group can be a promising model for phototherapeutic agents with potential applications in inactivation of bacteria by photodynamic therapy.     

二氟二碘甲烷与乙烯基乙醚的反应及其产物的化学转化

二氟二碘甲烷(CF2I2,1)与乙烯基乙醚和Na2S2O4在DMSO和乙醇的混合溶剂中反应得3,3-二氟-3-碘丙醛的乙缩醛[ICF2CH2CH(OEt)2](3).3在锌粉的作用下发生偶联反应生成二缩醛[(EtO)2CHCH2CF2CF2CH2CH(OEt)2](5)。缩醛3或5与烯醇硅醚在SnCl4作用下发生交叉偶联反应。3在锌粉或保险粉的引下与烯醇硅醚发生加成反应。3和5分别转化成硫缩醛ICF2CH2CH(SR)2(13),(RS)2CHCH2CF2CF2CH2CH(SR)2(14)或O,S-缩醛。13消HI得1,1-二氟乙烯衍生物。     

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.     

新型卟啉衍生物的合成、结构表征和电化学性质的研究

以合成的[5-(4-溴苯基)-10,15,20-三苯基卟啉]锌为底物,通Stille偶联的方法合成5-(4’-氨基-4-联苯基)-10,15,20-三苯基卟啉,[5-(4’-氨基-4-联苯基)-10,15,20-三苯基卟啉]锌配合物以及[5- (4’-甲硫基-4-联苯基)-10,15,20-三苯基卟啉]锌配合物。并用Uv,‘H NMR, IR, Ms, Fs等表征确证了该系列配合物的结构,并用循环伏安法对以上部分产物进行了电化学性质的研究.     

Hierarchically ordered homochiral metal-organic frameworks built from exceptionally large rectangles and squares

Hierarchically ordered homochiral metal-organic frameworks were built from the Cu(II) connecting point and the new (R)-6,6'-dichloro-2,2'-diethoxy-1,1'-binaphthyl-4,4'-bis(p-ethynylpyridine) bridging ligand (L). [Cu(3)L(4)(DMF)(6)(H(2)O)(3)(ClO(4))][ClO(4)](5).10DMF.10EtOH.7H(2)O (1) adopts a unique three-dimensional framework structure via simultaneous interlocking and interpenetration of one-dimensional ladders formed by linking rectangles of 24.8 x 48.6 A(2) in dimensions, whereas [Cu(3)L(5)(DMF)(8)][ClO(4)](6).6DMF.8EtOH.Et(2)O.6H(2)O (2) exhibits an interesting network topology by threading two-dimensional coordination square grids with one-dimensional coordination polymers.     

Synthesis of 5-(4-hydroxyphenyl)-10,15,20-tris[3,5-di(<Emphasis Type="Italic">tert-</Emphasis>butyl)-4-hydroxyphenyl]porphine and 5-(4-palmitoyloxyphenyl)-10,15,20-tris[3,5-di(<Emphasis Type="Italic">tert-</Emphasis>butyl)-4-hydroxyphenyl]porphine and generation of phenoxyl radicals from them

A porphyrin with a lipophilic hydrocarbon substituent, 5-(4-palmitoyloxyphenyl)-10,15,20-tris[3,5-di(tert-butyl)-4-hydroxyphenyl]porphine, was synthesized for the first time by acylation of 5-(4-hydroxyphenyl)-10,15,20-tris[3,5-di(tert-butyl)-4-hydroxyphenyl]porphine. Oxidation of these compounds with PbO₂ in toluene leads to the corresponding phenoxyl radicals. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 800–803, April, 2007.     

A family of 13 tetranuclear zinc(II)-lanthanide(III) complexes of a [3+3] Schiff-base macrocycle derived from 1,4-diformyl-2,3-dihydroxybenzene

A family of thirteen tetranuclear heterometallic zinc(II)-lanthanide(III) complexes of the hexa-imine macrocycle (L(Pr))(6-), with general formula Zn(II)(3)Ln(III)(L(Pr))(NO(3))(3)·xsolvents (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or Yb), were prepared in a one-pot synthesis using a 3:1:3:3 reaction of zinc(II) acetate, the appropriate lanthanide(III) nitrate, the dialdehyde 1,4-diformyl-2,3-dihydroxybenzene (H(2)L(1)) and 1,3-diaminopropane. A hexanuclear homometallic zinc(II) macrocyclic complex [Zn(6)(L(Pr))(OAc)(5)(OH)(H(2)O)]·3H(2)O was obtained using a 2:0:1:1 ratio of the same reagents. A control experiment using a 1:0:1:1 ratio failed to generate the lanthanide-free [Zn(3)(L(Pr))] macrocyclic complex. The reaction of H(2)L(1) and zinc(II) acetate in a 1:1 ratio yielded the pentanuclear homometallic complex of the dialdehyde H(2)L(1), [Zn(5)(L(1))(5)(H(2)O)(6)]·3H(2)O. An X-ray crystal structure determination revealed [Zn(3)(II)Pr(III)(L(Pr))(NO(3))(2)(DMF)(3)](NO(3))·0.9DMF has the large ten-coordinate lanthanide(III) ion bound in the central O(6) site with two bidentate nitrate anions completing the O(10) coordination sphere. The three square pyramidal zinc(II) ions are in the outer N(2)O(2) sites with a fifth donor from DMF. Measurement of the magnetic properties of [Zn(II)(3)Dy(III)(L(Pr))(NO(3))(3)(MeOH)(3)]·4H(2)O with a weak external dc field showed that it has a frequency-dependent out-of-phase component of ac susceptibility, indicative of slow relaxation of the magnetization (SMM behaviour). Likewise, the Er and Yb analogues are field-induced SMMs; the latter is only the second example of a Yb-based SMM. The neodymium, ytterbium and erbium complexes are luminescent in the solid phase, but only the ytterbium and neodymium complexes show strong lanthanide-centred luminescence in DMF solution.