卜啉与1,2-(1-吖啶-10’-基-2-氮-2-甲基-环丙-1,3-基)富勒烯非共价体的合成与表征

1,2-（1-Acridin-10＇-yl-2-aza-2-methylprop-1,3-ylene）fullerene was synthesized firstly and characterized by UV-Vis, ^1H NMR, ^13C NMR and electrospray ionization mass spectroscopy, which is capable of forming a stable complex with zinc tetraphenylporphyrin via the axial ligation. The steady state fluorescence studies show efficient quenching of the zinc tetraphenylporphyrin emission upon axial coordination of acridine attached to C60.     

Formation of heterocaryotic and homonuclear bridged–dimeric complexes on surface

The formation of coordinated dimeric complexes bridged by axial ligands on surface is observed with the help of a 1,3,5-tris(10-carboxydecyloxy)benzene(TCDB) template through scanning tunneling microscopy(STM). STM images of molecular adlayers of zinc tetraphenylporphyrin(Zn TPP), zinc phthalocyanine(Zn Pc), and their mixture are reported. Zn TPP and Zn Pc can spontaneously form highly an ordered structure with a 1:1 molar ratio, which is different from that of individual Zn Pc. The coordinated bimolecular complexes bridged with axial ligands, simply as Zn Pc–DPP–Zn TPP and Zn Pc–DPE–Zn Pc, are presented and the corresponding surface structures are compared. Zn Pc and Zn TPP can be connected by an axial ligand DPP and formed assembled structures out of surface. Two types of arrays with entirely new structure are obtained for the Zn Pc–DPE–Zn Pc complex. These bridged hybrid complexes provide an example of design of self-organized crystals on the basis of coordination through non-covalent interactions.     

Synthesis, spectroscopic and electrochemical property of an unsymmetrical porphyrin and its Zn compound

<正>In this article,a new 5-(p-maleicaminophenyl)-10,15,20-triphenylporphyrin(H_2P) and relative zinc compound(ZnP) were synthesized and characterized by means of elemental analyses,UV-vis,IR,MS and ~1H NMR spectroscopies.Furthermore,we have investigated the fluorescence spectroscopy of these compounds.The oxidation and reduction properties of the compounds were studied by the cyclic voltarnmetry,the oxidation-reduction potentials were obtained.     

Synthesis, Characterization and Weak Intramolecular Interactions of Porphyrins Bearing Nucleobases

5,10, 15-Triphenyl-20-{2- [α- (adenine-9 ) acetylamino]} phenyl porphyrin ( 1 ), 5,10, 15-triphenyl-20-{2-[α-(cytosine-1)acetylamino]} phenyl porphyrin (2), 5, 10, 15-triphenyl-20-{4-[α-(cytosine-1)ethoxy]} phenyl porphyrin (3) and their zinc complexes Zn-1, Zn-2 and Zn-3 have been prepared and characterized by ^1H NMR spectra, elemental analyses, electronic absorption spectra and mass spectra (FAB). Intramolecular π-π interactions and intramolecular metal-~ interaction for 1, 2, Zn-1,and Zn-2 have been investigated by several methods. ^1H NMR studies demonstrate that the porphyrin π-system in 1 and 2 is parallel to the adenine and the cytosine aromatic ring, respectively. The electronic absorption spectral properties of free porphyrin derivatives and their zinc complexes have been compared with those of H2TPP and ZnTPP. The results show that the UV-vis spectra of 1 and 2 are the same as that of H2TPP,whereas the spectra of their zinc complexes show 7 nm red shifts of the Soret bands compared to that of ZnTPP. The emission spectra of Zn-1 and Zn-2 are independent of excitation wavelength. From combination of the evidence of absorption and emission spectra it is suggested the existence of intramolecular metal-π interaction in Zn-1 and Zn-2. The results of conformational analysis agreed quite nicely with that of experiments, thus it was further to validate the experimental conclusions.     

The synthesis and spectroscopic investigation of vinylated meso-tetraphen ylporphyrin

A series of new vinylated 5,10,15,20-tetraphenylporphyrins have been synthesized and characterized by ~1H NMR,MS,UV-vis and fluorescence studies.Following selective excitation of the porphyfin compounds with UV light,the energy is transferred to the porphyrin core and reemitted as red light.In comparison to tetraphenylporphyrin (TPP),the luminescence properties are markedly improved.     

First synthesis of (±)-cedarmycin B

The synthesis of racemic cedarmycin B,an antibiotic from Streptomyces sp.TP-A0456 was achieved firstly fromγ- butyrolactone.The key step was a Barbier-type addition of 3-bromomethyl-5H-furan-2-one to formaldehyde mediated by zinc, which afforded the soleγ-addition product 4-hydroxymethyl-3-methylene-dihydrofuran-2-one.The final compound was confirmed by ~1H NMR,~(13)C NMR and HRMS.     

Photochemical hydrogen production with molecular devices comprising a zinc porphyrin and a cobaloxime catalyst

Two new noble-metal-free molecular devices,[{Co(dmgH) 2 Cl}{Zn(PyTPP)}](1,dmgH = dimethyloxime,PyTPP = 5-(4pyridyl)-10,15,20-triphenylporphyrin) and [{Co(dmgH) 2 Cl}{Zn(apPyTPP)}](2,apPyTPP = 5-[4-(isonicotinamidyl)phenyl]10,15,20-triphenylporphyrin),for light-driven hydrogen generation were prepared and spectroscopically characterized.The zinc porphyrin photosensitizer and the Co III-based catalyst unit are linked by axial coordination of a pyridyl group in the periphery of zinc-porphyrin to the cobalt centre of catalyst with different lengths of bridges.The apparent fluorescence quenching and lifetime decays of 1 and 2 were observed in comparison with their reference chromophores,Zn(PyTPP)(3) and Zn(apPyTPP)(4),suggesting a possibility for an intramolecular electron transfer from the singlet excited state of zinc porphyrin unit to the cobalt centre in the molecular devices.Photochemical H2-evolving studies show that complexes 1 and 2 are efficient molecular photocatalysts for visible light-driven H2 generation from water with triethylamine as a sacrificial electron donor in THF/H2 O,with turnover numbers up to 46 and 35 for 1 and 2,respectively.In contrast to these molecular devices,the multicomponent catalyst of zinc porphyrin and [Co(dmgH) 2 PyCl] did not show any fluorescence quenching and as a consequence,no H2 gas was detected by GC analysis in the presence of triethylamine with irradiation of visible light.The plausible mechanism for the photochemical H2 generation with these molecular devices is discussed.     

Synthesis and Spectroscopic Characterizations of an Insulinomimetic Peroxovanadate Complex in Aqueous Solution

The reaction system of diperoxooxalatovanadate {K_3 [VO (O_2)_2-(C_2O_4)]·H_2O, bpV(Oxa)} and imidazole was studied in anaqueous solution by 1D multinuclear (~1H, ~(13)C and ~(51)V) NMR,2D NMR diffusion ordered spectroscopy (DOSY), and variabletemperature NMR techniques. It was shown that DOSY was auseful tool for the study of a mixture. All of the ~1H and ~(13)CNMR signals of the peroxovanadate (V) complexes were as-     

FREE RADICAL RING OPENING POLYMERIZATION OF CYCLIC ACRYLATES

Cyclic acrylates, 2,2- dimethyl-5-methylene-1 , 3-dioxolan-4 -one and 2- phenyl-5-methylene-1,3-dioxolan-4-one, were synthesized successfully. The monomers were characterized by ~1H NMR, ~(13)C NMR, IR and elemental analysis or HRMS. Polymerization of the monomers were carried out at 120℃with di-t-butylperoxide as initiator. The polymers were studied by ~1H NMR, ~(13)C NMR, UV and hydrolysis. The molecular weights of the resulting polymers were estimated by viscosity measurement and the extent of ring opening was estimated also by ~1H NMR and hydrolysis of the polymers and further confirmed by UV spectra.     

Cobalt porphyrin immobilized on the TiO_2 nanotube electrode for CO_2 electroreduction in aqueous solution

Herein we report CO₂ electrochemical reduction reaction(CO₂ ERR)on the cobalt tetraphenylporphyrin(Co TPP)modified TiO₂ nanotube(TNT)electrode.It was found the axial coordination of drop-casting solvent to Co TPP and the porphyrin structure are the major factors that have significant effects on the catalytic performance of the electrode.As confirmed by spectrophotometric titration,pyridine has a stronger coordination bond to Co TPP than DMF and THF thus leading to the highest efficiency among the dropcasting solvents tested in the study.Based on the spectrophotometric analysis,possible coordination mechanism between drop-casting solvents and Co TPP is put forward.On the other hand,introduction of-COOMe substituents in phenyl rings of Co TPP weakens the coordination bond between pyridine and Co TPP as clearly evidenced by deuterium NMR spectra,resulting in a detrimental effect on CO₂ ERR.Therefore,the manipulation of the coordination environment around the metal center of immobilized catalyst is crucial in designing an efficient electrocatalytic system.     

SYNTHESIS, SPECTRA AND ELECTROCHEMICAL PROPERTIES OF OXYGEN ADDUCTS OF TETRAKIS(2-ANILINOPYRIDINATO) DIRHODIUM COMPLEXES

Two oxygen adducts of different geometric isomers of the tetrakis(μ-2-anilinopyridinato) dirhodium unit, Rh_2(ap)_4~+, have been synthesized and characterized. Rh_2(ap)_4O_2(4,0) is the oxygen adduct 1 of 4, 0 isomer; and Rh_2(ap)_4O_2(2, 2) is the oxygen adduct 2 of 2, 2 isomer. The ESR spectra of both oxygen adducts show that there is a characteristic signal of a superoxide ion, g=2.03. The 4, 0 isomer with different axial ligands gives the order of A_Ⅱ values; O_2~-≈ClO_4~-相似文献   

THE SYNTHESIS AND STRUCTURE OF 4,5-DIOXO-2-THIO-1,3,2,4-DIAZADIPHOSPHOLANES

A new type of diphosphorus heterocycles, 4,5- dioxo- 2- thio- 1,3, 2,4- diazadiphospholanes,has been synthesized by the condensation of carbamyl phosphoryl amidate and 4- substitutedphenyl phosphine dichloride, and then sulfurization. The cis- and trans-isomers of the com-pounds were separated by HPLC, and their structures were studied with ~1H NMR and ~(31)PNMR. It has been found that the cis- and trans-isomers have different chemical shifts (δ) anddifferent coupling constants. The preliminary bioassay shows that some of them possessstrong herbicidal activity.     

Synthesis and photoactivity of pH-responsive amphiphilic block polymer photosensitizer bonded zinc phthalocyanine

A zinc tetraaminophthalocyanine derivative, zinc tetra(methacryloyl moiety)aminophthalocyanine (MeZnAPc) (with a double bond) was synthesized by the reaction between zinc tetraaminophthalocyanine (ZnTAPc) and methacryloyl chloride. Atom transfer radical polymerization (ATRP) was employed as the polymerization technique to obtain a novel pH-responsive polymeric photosensitizer (PEG110-b-P(DPAn-co-MeZnAPcm)) by copolymerizing of methoxypolyethylene glycols (MPEG) (as reducing agent), 2-(isopropylamino)ethyl methacrylate (DPA) and MeZnAPc. This photosensitizer was characterized by UV-vis spectroscopy, FTIR, H NMR, etc. The results indicated that the photosensitizer presented the well pH-responsive be 1 havior around the pH range 6.0-6.5 and the high photoactivity to 1,3-diphenylisobenzofuran (DPBF). The result of photocatalysis oxidation of L-tryptophan (L-Try) suggested that zinc phthalocyanine could present high photoactivity due to its dispersivity at pH 5.5 without formation of micelles, and its photoactivity decreased dramatically at pH 7.4 due to wrapping ZnTAPc into the micelles. Therefore, the novel pH-responsive polymeric photosensitizer has better application prospects in the field of photodynamic therapy.     

Synthesis,structural characterization and solubility of 2-(1-substituted-1,11-undecylidene)-5-arylimino-△~3 -1,3,4-thiadiazolines

A series of novel 2-(1-substituted-1,11-undecylidene)-5-arylimino-△~3-1,3,4-thiadiazolines(4) were synthesized and their structure was characterized by ~1H NMR,~(13)C NMR and elemental analysis.Their solubility in both polar and non-polar solvents is significantly improved owing to the introduction of ethyl or methylthio group at cyclododecyl ring as compared with parent compounds[1,2-(1,11-undecylidene)-5-arylimino-△~3-1,3,4-miadiazolines].However,their fungicidal activity against Rhizoctonia solani is ...     

Synthesis,Characterization and Molecular Structure of a Diiron Complex(μ-SCH_2CH_2CH_2S-μ)Fe_2(CO)_5(Ph_2PCH_3)

The title complex,(μ-pdt)Fe_2(CO)_5(Ph_2PCH_3)(pdt = SCH_2CH_2CH_2S),was obtained by the reaction of the parent complex(μ-pdt)Fe_2(CO)_6 with Ph_2PCH_3 and Me_3NO·2H_2O in good yield(90%). The title complex was characterized by IR,~1H NMR,~(31)P{~1H} NMR and ~(13)C{~1H} NMR spectroscopy as well as by single-crystal X-ray diffraction analysis. The molecular structure shows that the title complex contains a butterfly diiron propanedithiolate cluster with five terminal carbonyls and a monophosphine ligand Ph_2PCH_3. The crystal packing diagram reveals that intermolecular C H···O hydrogen bonds between CH_2 and carbonyls,π-π stacking interactions and van der Waals' interactions stabilize the solid state to form a three-dimensional network.     

SYNTHESIS AND POLYMERIZATION OF 2-OXO-3-METHYLENE-1,4-DIOXANES

A new kind of monomers was successfully synthesized by the reaction between 2-chloro methyl cycloketal and trimethylsilyl cyanide, followed by ring closure and dehaiogenation. Polymerizations of the monomers were carried out in benzene solution at 80℃with benzoyl peroxide as initiator. Both the structures of monomers and polymers were characterized by IR, ~1H NMR, ~(13)C NMR and elemental analysis.     

SYNTHESIS AND POLYMERIZATION OF 2-OXO-3-METHYLENE-5, 6-DIPHENYL-1,4-DIOXAN

A new cyclic monomer, 2-oxo-3-methylene-5, 6-diphenyl-1, 4-dioxan, was synthesized. Thestructure of the intermediates and the monomer were determined by IR,~1H NMR,~(13)C NMR andelemental analysis. This new monomer is different from other cyclic monomers in this series,it isa solid (mp 108--109℃)and not very reactive, but still can undergo free radical ring-openingpolymerization. The free radical polymerization was carried out at 130℃. The structure of theresulting polymer was discussed and charaterized by IR, ~1H NMR, ~(13)C NMR and elementalanalysis. The molecular weight of the polymer was estimated by viscosity determination.     

SYNTHESIS AND FREE RADICAL RING-OPENING POLYMERIZATION OF 2-METHYL-AND 2-METHYL-9-n-BUTYL-(-7-METHYLENE-1,4,6-TRIOXA-SPIRO (4, 4)NONANE)

This paper describes the synthesis and free radical ring-opening polymerization of 2-methyl-and 2-methyl-9-n-butyl (-7-methylene-1, 4, 6-trioxaspiro (4, 4) nonane). The structures of the two polymers were verified by IR, 'H and ~(13)C NMR spectra. The substituent on 9-position of 7-methylene-trioxaspiro (4, 4) nonane affects the structure of polymer and polymerization activity. The polymerization mechanism is discussed.     

Synthesis of dimethyl 3-perfluoroalkyl-4-(3-oxo-2-triphenyl-phosphoranylidenbutanylidene)-pent-2-enedioate and its cyclization

The title compounds 5a-5c were prepared via the reaction of methyl 2-perfluoroal-kynoates (4) with methyl 5-oxo-4-(triphenylphosphoranylidene)hex-2-enoate (3), which was obtained from the reaction of methyl propynate (2) with acetylmethylenetriphenylphosphorane (1) at -5-0℃. Intramolecular elimination of Ph3PO took place when compound 5 was heated in aqueous methanol at 115-120℃ in sealed tube, yielding dimethyl 2-trifluoromethyl-4-methylisophthalate (6a) from 5a and methyl 5-acetyl-4-hydroxy-2-heptafluoropropanylbenzoate (6b) from 5b, respectively. The structures of compounds 5, 6a and 6b were confirmed by IR, MS, 1H NMR, 19F NMR and 13C NMR spectroscopy and elemental analyses. Rection mechanisms for the formation of compounds 5, 6a and 6b were proposed.     

Synthesis, Crystal Structure and Properties of Complex VO（C10H9NO3） （C13H10NO2）

Complex VO(C10H9NO3)(C13H10NO2)(C10H9NO2-3=N-salicylidene-L-alaninate, C13H10NO-2=N-phenylbenzohydroxamate) was synthesized and characterized by means of elemental analysis, IR, UV, 1H NMR spectroscopies, cyclic voltammetry and single crystal X-ray diffraction. The complex crystallized in a monoclinic system with space group P21 and crystal cell parameters a=0.9720(1) nm, b=1.8274(2) nm, c=1.2542(1) nm, β=104.868(9)°, V=2.1532(4) nm3, Mr=470.34, Z=2. The two oxygen atoms and the one nitrogen atom of the tridentate Schiff base ligand and the one oxime oxygen atom of the hydroxamate ligand coordinate to the vanadium atom, forming an equatorial plane, the two axial positions are respectively occupied by the oxygen atom of the oxovanadium and the carbonyl oxygen atom of the hydroxamate and the vanadium atom exhibits a distorted octahedral VO(ONO)(OO) coordination sphere. The 1H NMR spectrum suggests that the two isomers, endo and exo in a molar ratio of 1/1.7, coexist in the solution of the title complex in CDCl3. There exists a quasi-reversible one-electron redox reaction corresponding to VⅤ/VⅥ couple in the three non-aqueous solvents, and the redox potential E1/2 of the title complex substantially shifts in the direction of the positive voltage increase in the order: CH2Cl2＜CH3CN＜DMF.