Synthesis and characterization of meso-ferrocenylethynyl 5,15-diphenylporphyrins

A series of four meso-ferrocenylethynyl (5,15-diphenylporphyrinato)nickel(II) derivatives have been synthesized by Sonogashira coupling reactions. Three of these compounds contain the electron-withdrawing groups including -CHO, -CHC(CN)₂, and -CCC₆H₄NO₂ at the remaining meso position, with a view to preparing push-pull chromophores, in which ferrocene serves as the electron donor. All the new compounds have been characterized spectroscopically and the molecular structure of one of these porphyrins (compound 11) has also been determined. The studies show that although the ferrocenylethynyl group can extend the π system of the central porphyrin core, the cyclopentadienyl rings of ferrocene are almost orthogonal to the porphyrin ring. This hinders ferrocene serving as a good electron donor in these systems.     

C-甲基取代的1-二茂铁酰氧基杂氮硅三环化合物的合成、表征及FcCOOSi(OCHCH3CH2)(OCH2CH2)2N的晶体结构

报道11个新的C-甲基取代的1-二茂铁酰氧基杂氮硅三环化合物.     

Radial tetra(ferrocenyl)- and tetra(cymantrenyl)cyclobutadienecobalt complexes: Synthesis and structures

Novel radial tetra(ferrocenyl)- and tetra(cymantrenyl)cyclobutadienecobalt complexes were prepared by metal carbonyls free protocol of [2 + 2] cycloaddition reaction of 1,2-diferrocenyl- or 1,2-dicymantrenylethynes with chlorotris(triphenylphospine)cobalt(I) and carboethoxycyclopentadienide sodium with good yields. The molecular structure of these products was confirmed with X-ray analysis, and their electrochemical behavior was studied.     

两种含偶氮苯共轭桥新型生色团分子的合成及性能

通过重氮化偶合反应和羟醛缩合反应合成了以偶氮苯为共轭桥、以2,2,3-三甲基-4-氰基-5-二氰基亚甲基-2,5-二氢呋喃为电子受体, 而给体分别为二甲氨基和二乙氨基的两种有机非线性光学生色团分子MFNC和EFNC. 利用IR、1H NMR和元素分析对分子的结构进行了表征. TGA和DSC测试发现, MFNC的热稳定性略好于EFNC, 其热分解温度最高达266 ℃. 通过测定两种材料在氯仿、丙酮和DMSO中的紫外-可见光谱, 用溶致变色法计算得到两种材料在激光波长为1064 nm处的二阶非线性品质系数μgβ, 对比发现EFNC的μgβ值高于MFNC, 其值达59706×10-48 esu(1 esu=3.34×10-10C).     

Synthesis of a 2-benzocymantrenylpyridine and further mechanistic insights

The synthesis of a new benzocymantrene derivative containing an appended pyridyl moiety was attempted by reacting a lithioindenylpyridine with (CO)₅MnBr. The reaction led to the formation of small amounts of the targeted benzocymantrene, which was subsequently characterized by structural X-ray diffraction analysis. Alternative treatment of the same ligand with (η¹-benzyl)pentacarbonylmanganese led to the formation of a five-membered manganacycle resulting from the C-H bond activation at the five-membered ring of the indenyl group. To rationalize the origin of the poor yield in the benzocymantrene derivative a complete study of the reaction profile was carried out by means of a state-of-the-art DFT-D2 method. The theory indicated that the main difficulty in producing the targeted benzocymantrene stems from the relatively high activation energy barrier necessary to convert a (η¹-indenyl)Mn(CO)₅ intermediate into a (η³-indenyl)Mn(CO)₄ transient species.     

Push-pull structures with a pyrazine core and hexatriene chain: synthesis and light-emitting properties

In this paper, we describe the synthesis of various push-pull molecules with a central pyrazine unit connected to a hexatriene chain terminated by various p-substituted phenyl groups. The key steps involve metallation and subsequent transmetallation of 2-chloro and 2,6-dichloropyrazine followed by a Negishi cross-coupling reaction of the intermediate organozinc derivative with (2E,4E)-5-bromopentadienal. The aldehydes are then submitted to a Wittig reaction with the appropriate phosphonium salts readily obtained from various substituted benzyl alcohols. The light-emitting properties of the so obtained molecules are then investigated in terms of absorption and emission spectra and non-linear optics experiments have been carried out in two cases.     

Introduction of a planar chirality onto steroid substrates: synthesis of (S) and (R)-2′-formylcymantrenyl-17α-ethynylestradiols using (S) and (R)-1-formyl-2-iodo-cymantrenes

We report the synthesis and characterisation of (S) and (R)-2′-formylcymantrenyl-17α-ethynylestradiol synthesized using the Sonogashira cross-coupling reaction between optically pure (S) and (R) 1-formyl-2-iodo cymantrenes and ethynylestradiol. (S) and (R) 1-formyl-2-iodo cymantrenes were obtained from the same precursor: (2R,4R)-4-(methoxymethyl)-2-cymantrenyl-1,3-dioxane.     

Syntheses, structures, and second-harmonic generating properties in new quaternary tellurites: A2TeW3O12 (A=K, Rb, or Cs)

The syntheses, structures, and characterization of a new family of quaternary alkali tungsten tellurites, A₂TeW₃O₁₂ (A=K, Rb, or Cs), are reported. Crystals of the materials were synthesized by supercritical hydrothermal methods using 1 M AOH (A=K, Rb, or Cs), TeO₂, and WO₃ as reagents. Bulk, polycrystalline phases were synthesized by standard solid-state methods combining stoichiometric amounts of A₂CO₃, TeO₂, and WO₃. Although the three materials are not iso-structural, each exhibits a hexagonal tungsten oxide layer comprised of corner-sharing W⁶⁺O₆ octahedra. Te⁴⁺O₃ groups connect the WO₆ layers in K₂TeW₃O₁₂, whereas the same groups cap the WO₆ layers in Rb₂TeW₃O₁₂ and Cs₂TeW₃O₁₂. This capping results in non-centrosymmetric structures for Rb₂TeW₃O₁₂ and Cs₂TeW₃O₁₂. Powder second-harmonic generation measurements on Rb₂TeW₃O₁₂ and Cs₂TeW₃O₁₂ revealed strong SHG efficiencies of 200 and 400×SiO₂, respectively. These values indicate an average non-linear optical susceptibility, 〈d_eff〉_exp of 16 and 23 pm/V for Rb₂TeW₃O₁₂ and Cs₂TeW₃O₁₂, respectively. Crystallographic information: K₂TeW₃O₁₂, monoclinic, space group P2₁/n (No. 14), a=7.3224(13) Å, b=11.669(2) Å, c=12.708(2) Å, β=90.421(3)°, Z=4; Rb₂TeW₃O₁₂, trigonal, space group P31c (No. 159), a=b=7.2980(2) Å, c=12.0640(2) Å, Z=2.     

Cymantrene-derived monodentate phosphites: New ligands for Rh-catalyzed enantioselective hydrogenation

Novel chiral monodentate phosphite ligands bearing cymantrene fragment have been prepared. Phosphite 4 with PPh₃, instead of CO-ligand, in cymantrene moiety provided higher enantioselectivity than its unsubstituted analogue 3 in hydrogenation of (Z)-methyl-2-acetamido-3-phenylacrylate.     

Photochromic bipyridyl metal complexes: Photoregulation of the nonlinear optical and/or luminescent properties

The combination of transition metals and ligands featuring photochromic units is receiving much attention and opens up new perspectives for the design of metal-based photoswitchable molecules. This account summarizes some of our recent works made in the area of photochromic organometallic and coordination compounds, which have been used for the photomodulation of the quadratic non-linear optical (NLO) properties, as well as of the photoregulation of the emission properties of the resulting systems. For this purpose, we have designed new chromophores combining dithienylethene (DTE)-based bipyridine ligands with different metallic fragments (Re^I, Fe^II, Ru^II, Ir^III, Cu^I, Zn^II), giving rise to multi-photochromic metal complexes containing from two to six DTE units, and studied the photocontrol of both NLO and luminescence properties.     

Synthesis and electrochemical studies of organometallic cobalt(III) complexes with substituted benzonitrile chromophores: NMR spectroscopic data as a probe on the second-order non-linear optical properties

The family of organometallic Co(III) benzonitrile derivatives of general formula [CoCp(dppe)(p-NCR)][PF₆]₂ (R = C₆H₄NMe₂, C₆H₄NH₂, C₆H₄OMe, C₆H₄C₆H₅, C₆H₅, C₆H₄C₆H₄NO₂, and C₆H₄NO₂) have been synthesized. Spectroscopic and electrochemical data were analyzed in order to evaluate the extent of electronic coupling between the organometallic fragment and the nitrile ligands. An attempt of correlation between NMR spectroscopic data and the second-order non-linear optical properties is presented, based on this work and available published data for related η⁵-monocyclopentadienyliron, ruthenium and nickel complexes.     

Synthesis of 4,5-diarylquinazolines: a system with cofacial aromatic rings. Diazines. Part 39

Using metallation reactions and Pd-catalyzed coupling, we report here two synthetic routes leading to eight new 4,5-di(hetero)arylquinazolines. Non-linear activity has been highlighted for some of these compounds with stacked aromatic rings.     

Structural dependence of non-linear optical properties of 4-Dimethylamino-3-cyanobiphenyl

 4-Dimethylamino-3-cyanobiphenyl (4-DMA-3-CB) was characterized with respect to linear and nonlinear optical properties in a crystal as well as in solution. The crystal structure was studied dependent on the crystallization conditions. It is shown that the crystal structure exhibiting NLO-activity can completely be solved by a combination of electron diffraction and computer modeling. There are four molecules per unit cell in the space group Pna2₁ with dimensions a=10.28 Å, b=22.64 Å, c=5.27 Å. From this model structure the values and orientation of the dipole μ and static second order polarizability β can be calculated. Their relevance to the values obtained by a combination of polarization dependent measurements of Electric Field Induced Second Harmonic Generation (EFISH) and Hyper-Rayleigh-Scattering (HRS) in solution are discussed. The molecular second order polarizability tensor was found to be dominated by one single component. The orientations of the dipole and the vectorial parts of the second order polarizability delivered by the semiempirical calculations are in good agreement with the results of the EFISH and HRS-measurements and allow a deeper insight into the nonlinear optical properties of the crystal. Received: 15 April 1996 Accepted: 21 June 1996     

3,5—（二硝基苯甲酸）与（二乙醇胺）加合物的合成和晶体结构

合成了具有非线性光学特性的标题加合物.以降温法培养出24 mm×15 mm×38 mm大尺寸单晶,该单晶在1064 nm的Nd3+:YAG激光束照射下,产生绿色的532 nm倍频光.以X射线衍射法测定了此1:1加合物的晶体结构,晶体属P1空间群,a=0.4609(2)nm,b=0.7405(5)nm,c=1.0684(6)nm,a=95.50(5)°,β=98.72(3)°,γ=104.33(5)°,Z=1;R=0.076.3,5-二硝基苯甲酸与二乙醇胺之间,以氢键相联,构成平行于001晶面的二维网络.     

具有生物活性的有机硅化合物的研究（ⅩⅢ）──1－（O，O－二烷基－二硫代磷酸酯）亚甲基－2，8，9－三氧杂－5－氮－1－硅杂三环［3，3，3，0~（1，5）］十一烷的合成

合成了９种１－（Ｏ，Ｏ－二烷基－二硫代磷酸酯）亚甲基－２，８，９－三氧杂－５－氮杂－１－硅杂三环［３，３，３，０~（１，５）］十一烷。合成方法简便，易于后处理，经元素分析、ＩＲ、１ＨＮＭＲ、ＭＳ确定了新化合物的结构，并对其进行了生物活性的研究。     

具有生物活性的有机硅化合物的研究(Ⅷ)——1-烷酰氧基杂氮硅三环的合成及抗癌活性的研究

报道了用1-溴代Silatrane合成1-烷酰氧基-2,8,9-三氧-5-氮-1-硅杂三环[3,3,3,0~(1.5]十一碳烷的新方法。讨论了反应条件对该类化合物合成的影响,用各种方法确证了产物的结构,对某些化合物进行了抗癌活性实验。     

Photoinduced processes of newly synthesized bisferrocene- and bisfullerene-substituted tetrads with a triphenylamine central block

Photoinduced electron transfer processes of two newly synthesized tetrads with a triphenylamine (TPA) as central building block, to which bisfullerenes (C₆₀) and bisferrocenes (Fc) are covalently connected, have been studied. One of them has a TPA linked with one C₆₀ moiety and two ferrocene moieties C₆₀-TPA-(Fc)₂ and another tetrad has a TPA linked with two C₆₀ moieties and one ferrocene unit (C₆₀)₂-TPA-Fc. The photophysical properties of (C₆₀)_m-TPA-(Fc)_n have been investigated by applying the picosecond time-resolved fluorescence and nanosecond transient absorption techniques in both polar and nonpolar solvents. The charge separation process via the excited singlet state of the C₆₀ moiety of the C₆₀-TPA-(Fc)₂ is more efficient than that of the (C₆₀)₂-TPA-Fc. It is found that the ratio of Fc-donor to C₆₀-acceptor affects charge separation efficiency via the excited singlet state of the C₆₀ moiety.     

Site-selective and covalent labelling of the cysteine-containing peptide glutathione with a ferrocenyl group

Site-specific labelling of the cysteine-containing peptide glutathione with a ferrocene group was achieved by reaction with ferrocenylmethanol in aqueous acidic medium. The resulting peptide was shown to be a potent competitive inhibitor of the biologically important enzyme glutathione-(S)-transferase. This approach may prove general for the labelling of proteins with ferrocene.     

二茂铁及其衍生物作为电化学传感器的研究进展

本文对近二十年来国内外对二茂铁及其衍生物作为电化学传感器的研究进展做了较全面的综述。主要讨论了二茂铁及其衍生物修饰电极的制备、表征,介绍了二茂铁及其衍生物作为电化学传感器的应用情况,并探讨了今后的研究方向。