Synthesis, Structure and Electrochemistry of Macrocyclic 1,1'-Bis(1,3-phenyleneoxyacetylpyrazoyl)ferrocene

1,1'-Diacetoacetylferrocene 1 reacted with phenylene-1,3-dioxyactyl hydrazine 2 in absolute ethanol to give the macrocyclic ferrocenyl dipyrazole compound in moderate yield. Determined by X-ray structure analysis, it crystallizes in monoclinic system, space group P21/c with a = 13.7509(4), b = 8.1277(2), c = 21.7472(6) , β = 103.1030(10)°, V = 2367.25(11) 3, Z = 4, Dc = 1.505 g/cm3, R = 0.0353 and wR = 0.0811. The electrochemical studies reveal that redox of Fe+/Fe in ferrocene is a reversible one-electron process.     

Synthesis and optical and electrochemical properties of glucose-cored ferrocenyl dendrimers

Triazole-based ferrocenyl glycoconjugates 1, 2, and 3 were synthesized by regiospecific copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) of azidoferrocenyl derivatives with glucose pentaacetylide. Higher generation ferrocenyl glycoconjugates form the stable ferrocenium cation and exhibit increased light harvesting property as revealed from cyclic voltammogram studies and ultraviolet–visible spectrum respectively due to the presence of more ferrocenyl and triazolyl units than the lower generation dendrimer.     

Synthesis,crystal structures and electrochemical properties of two new metal-centered ferrocene complexes

Two new metal-centered ferrocene complexes Ni(SCN)2(L)4 (1) and Cu(OAc)2(L)2 (2) (L = 1-[1-ferro- cenylmethyl]imidazole) have been synthesized and characterized by elemental analysis, single crystal X-ray diffraction analysis, spectroscopic and cyclic voltammetric measurements. The geometry of Ni(Ⅱ) in 1 is octahedral, with four ligands in the equatorial plan and two thiocyanate anions at the axial site, while that of Cu(Ⅱ) in 2 is a distorted octahedron formed by two chealted OAc- and two ligands. Single c...     

Isophorone‐based organometallic chromophores: Synthesis,characterization and investigation of electro‐optical properties

A series of hybrid donor–acceptor complexes with a ferrocene moiety and isophorone derivatives were synthesized. Data from ¹H NMR, ¹³C NMR, Fourier transform infrared, atomic absorption and mass spectroscopies and CHN analysis supported the predicted structure of the products. A comparative investigation was performed using UV–visible, cyclic voltammetry and fluorescence measurements. Density functional theory was used to optimize the chromophore structure and calculation of highest occupied and lowest unoccupied molecular orbital energy levels. The ferrocene/isophorone hybrids show useful properties for further development and studies as electro‐optic materials.     

Synthesis,characterization and electrochemical properties of amphiphilic axially-disubstituted silicon(IV) phthalocyanines

The new 2-[2-(6-tert-butyl-2H-1,3-benzoxazin-3(4H)-yl)ethoxy]ethanol 1 and 2-[2-(6-pentyl-2H-1,3-benzoxazin-3(4H)-yl)ethoxy]ethanol 2 have been synthesized. Axially disubstituted silicon phthalocyanines 3 and 4 have been synthesized by introducing 2-[2-(6-tert-butyl-2H-1,3-benzoxazin-3(4H)-yl)ethoxy]ethanol and 2-[2-(6-pentyl-2H-1,3-benzoxazin-3(4H)-yl)ethoxy]ethanol at the axial positions of silicon(IV) phthalocyanine, respectively. The electrochemical properties of silicon phthalocyanines 3 and 4 were also investigated by cyclic voltammetry (CV) and square wave voltammetry. Voltammetric studies show that while 3 showed two reversible reduction and one irreversible oxidation couples, 4 showed two quasi-reversible reduction and one irreversible oxidation couples.     

Synthesis, characterization and electrochemical properties of two new calix[4]arene derivatives bearing two ferrocene imine or ferrocene amine units at the upper rim

A novel calix[4]arene derivative with two ferrocenyl Schiff-base groups at the upper rim 3 has been synthesized from 5,17-diformyl-25,27-dipropoxy-26,28-dihydroxy calix[4]arene and 4-ferrocenylaniline via condensation reaction. Reduction of 3 with sodium borohydride led to calix[4]arene derivative 4 with two amino ferrocenyl groups at the upper rim. The ferrocenyl Schiff-base calix[4]arene and its corresponding reduced amine have been purified and characterized by elemental analysis,¹H NMR, FTIR, Mass and UV-vis spectral data. Electrochemical properties of compounds 3 and 4 have been investigated. Cyclic voltammograms of 3 and 4 show reversible redox couples of ferrocene/ferrocinium at E_1/2=0.401 V and 0.346 V, respectively. Electrochemical studies show these redox active compounds electrochemically recognize trivalent lanthanides La³⁺ and Ce³⁺ and divalent Pb²⁺ and Cu²⁺cations. With ferrocenyl Schiff-base calix[4]arene 3 an anodic shift as large as 130 mV is observed on addition of one equivalent of Ce³⁺ ion. Also extraction properties of compound 4 towards some metal cations have been described. It has been observed that compound 4 has a good selectivity for metal cations Fe³⁺, Cu²⁺, Pb²⁺ and Cd²⁺ against Ni²⁺ and Co²⁺.     

Novel nonperipheral octa-3-hydroxypropylthio substituted metallo-phthalocyanines: synthesis,characterization, and investigation of their electrochemical,photochemical and computational properties

The current study describes the synthesis, electrochemical, computational, and photochemical properties of octa (3-hydroxypropylthio) substituted cobalt (II) ( 4 ), copper (II) ( 5 ), nickel (II) ( 6 ) and zinc(II) ( 7 ) phthalocyanine derivatives. These novel compounds were characterized by elemental analysis,¹H,¹³C NMR, FT-IR, UV-Vis, and MS. The redox behaviors of these metallo-phthalocyanines were investigated by the cyclic voltammetric method. The optimized molecular structure and gauge-including atomic orbital (GIAO)¹H and¹³C NMR chemical shift values of these phthalocyanines in the ground state had been calculated by using B3LYP/6–31G(d,p) basis set. The outcomes of the optimized molecular structure were given and compared with the experimental NMR values. The photochemical properties including photodegradation and singlet oxygen generation of zinc(II) phthalocyanine were studied in DMSO solution for the determination of its photosensitizer behaviors.     

新型二茂铁三氮唑类Schiff碱的合成、晶体结构及其电化学性质

以乙酰二茂铁和氨基三氮唑为原料,合成了两种新型的二茂铁三氮唑Sch iff碱化合物,其结构通过IR,1H-NMR,元素分析和X-射线单晶衍射法确定。X射线单晶结构分析表明,固态时化合物1 a与一分子水通过分子间氢键形成-维无限链状结构,其晶体属单斜晶系,P21/n空间群,M r:312.16,a=11.679(2),b=9.862(2),c=12.717(3),β=108.60(3)0k,v=1388.3(5),Z=4,D c=1.493mg.m-3,μ=0.71073,F(000)=648,最终偏离因子R=0.0454,wR=0.0984。电化学分析表明1 a和1b的电化学性质相似,在电位0.4~1.1V范围内,都只有一对氧化-还原峰,对应于Fc/Fc 电对,且该过程是受扩散控制的可逆过程。     

Synthesis and characterization of functionalized ferrocenylsilanes bearing a bulky substituent

Several types of overcrowded ferrocenylsilanes, Tbt(Fc)SiX₂(Tbt=2, 4, 6-tris[bis(trimethylsilyl)methyl]phenyl, Fc=ferrocenyl, X = H, OH, and Br) were synthesized and characterized. In addition, DFT calculations for ferrocenylsilanediol systems indicated the existence of the intramolecular hydrogen bonding between the Fe atom and H–O moiety in Tbt(Fc)Si(OH)₂. Dedicated to Professor Mitsuo Kira on the occasion of his 2005 Wacker Awardy     

Synthesis,characterization and properties of novel polyamides containing ferrocene unit and flexible spacers

Synthesis and characterization of ferrocene‐containing main‐chain polyamides are reported in this article. A new, interesting type of organometallic monomer (FDADO) based on ferrocene was prepared by interfacial condensation of 1,1′‐dichlorocarbonyl ferrocene with 2 mol 1,8‐diamino‐3,6‐dioxaoctane (DADO). A series of ferrocene‐based polyamides was prepared via polycondensation of the ferrocenyl diamine (FDADO) with different diacid chlorides using two different methods. The monomer and polymers were characterized by elemental analysis, infrared and NMR spectroscopy. The thermal stability and behavior of the synthesized polymers were evaluated by thermal gravimetric analysis (TGA), dynamic mechanical thermal analysis (DMTA), and differential scanning calorimetry (DSC). The crystallinity of polymers was examined by X‐ray diffraction analysis. Inherent viscosity, solubility and flame‐retardancy of the polymers were also studied. The obtained polymers showed good heat‐resistance and flame‐retardancy, and improved solubility vs generally reported polyamides in some common organic solvents. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis of redox-active biscalix[4]quinones and their electrochemical properties

Biscalix[4]arenes, 7 and 8, have been synthesized by a one-pot coupling method and a stepwise approach, respectively. One-pot reaction in a pressurized vessel resulted in the symmetric biscalix[4]arene 7 in high yield. Oxidation of compounds 7 and 8 by Tl(CO₂CF₃)₃ in CF₃COOH yielded biscalix[4]quinones, 9 and 10, respectively. Preliminary electrochemical studies by cyclic voltammetry of 9 and 10 show significant changes of their voltammograms upon addition of Na⁺.     

Synthesis and electrochemical studies of ferrocene-dithiafulvalenes (Fc-DTF) and 1,1′-bis(dithiafulvalenyl)ferrocene (DTF-Fc-DTF). An approach towards new conducting organic materials

Novel π-conjugated donor compounds based on the strong electron-donating ferrocene moiety and dithiafulvalene donors exhibited increased electron donor ability. The ferrocenylketones 4a,b, 5, 8 and 9 were synthesized via described methods, and allowed to react with 2-dimethoxyphosphinyl-1,3-benzodithiole (13) in the presence of n-BuLi at −78°C in dry THF to afford the corresponding ferrocene-dithiafulvalenes 14a,b, 18, 19 and 1,1′-bis(benzo-1,3-dithiol-2-ylidene)ethyl]ferrocene (15). Electrochemical properties of these new donor compounds were studied using cyclic voltammetry (CV) and UV-Vis spectra. CV and absorption spectra of the new compounds were studied in comparison with ferrocene (6) and dibenzo-tetrathiafulvalene DB-TTF 3. Two-electron and three-electron redox behaviors were observed as two waves. The absorption spectra showed a red-shift with a slight increase in the absorption intensities.     

二茂铁及其衍生物的电化学特性与结构理论研究

研究了二茂铁及其衍生物(甲酰二茂铁,乙酰二茂铁,甲醇二茂铁和乙酸二茂铁)的电化学行为,运用结构理论给出了二茂铁D5点群群轨道能级图与二茂铁衍生物的前线轨道能级图,得出在二茂铁分子结构中1e2(dx2-y2,dxy)与3a1(dz2,4s)分别属于分子前线轨道中的HOMO和LUMO。同时用密度泛函理论(DFT)在LANL2DZ基组水平上对其结构进行了全优化,得到了二茂铁及其衍生物前线最高被占轨道(HOMO)能量值,Fe原子净电荷,对其电化学行为与前线轨道能级相对大小进行了验证。     

2-[(4-Aminobutyl)ferrocenylmethylidene]-5,6-dimethoxy-1-indanone derivatives: Synthesis,characterization, and investigation of electro-optical properties

A ferrocenyl-based, chromophore-containing 1-indanone derivative was synthesized through crotonic condensation between 4-chlorobutylferrocenecarboxaldehyde and 5,6-dimethoxy-1-indanone followed by the nucleophilic substitution of chlorine atom of the obtained dyad with different aromatic and aliphatic amines. The electrochemical and optical properties of the synthesized compounds were investigated to explore the relationship between their structures and optical and electrochemical properties. The bandgaps determined from optical absorption spectra ranged from 2.05 to 2.15 eV. The important electrochemical parameters, including the peak potential separation, peak current ratios, and the dependence of peak currents on the scan rate, were studied. Results showed an electrochemically reversible redox system with diffusion-controlled redox process for the synthesized compounds. The study of quantum chemistry was performed on the synthesized compounds using the density functional theory approach. The B3LYP method and 6-311 G(d) basis set were used for optimizing the structures in the gas phase. The theoretical and experimental results show that these compounds can be considered as candidates to be used in optical applications.     

Synthesis of polyamines with pendant cyanoimidazole units and their electrochemical properties

The 2-(1-methyl-4,5-dicyanoimidazolyl) group was attached to poly(diallylamine) and polyethylenimine, affording polymers containing an electron-withdrawing pendant group. The key to their preparation is high reactivity of 1-methyl-2-fluoro-4,5-dicyanoimidazole (1) toward nucleophilic aromatic substitution (NAS) reactions with aliphatic amines. Cyclic voltammograms of these polymers show reduction waves at −2.6 to −2.7 V vs. Ag/Ag⁺ but no reoxidation waves, unlike those of monomeric and oligomeric model compounds, which are quasi-reversible. The cyclic voltammetry studies of oligomeric model compounds with different alkyl spacers show that the degree of quasi-reversibility decreases as dicyanoimidazoles are crowded together in a molecule, suggesting that a certain degree of chemical reaction occurs between reduced dicyanoimidazole groups. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2619–2629, 1998     

Synthesis,characterization, and electrochemical studies of Co(II,III) dithiocarbamate complexes

Cobalt(II) complexes of N-methyl phenyl, 1-phenylpiperazyl, and morpholinyl dithiocarbamates have been synthesized and characterized by UV–Visible, FTIR, ¹H-, ¹³C-NMR, and mass spectrometry. The spectroscopic data indicated that two ligands coordinated in bidentate chelating to the metal ion to form four-coordinate cobalt(II) complexes (1–3), which was confirmed by mass analysis (TOF MS ES⁺) of the complexes with m/z [M]⁺ = 450.98, 382.94, and 382.94 for 1, 2, and 3, respectively. Single crystal analysis of 2A and 3A show centrosymmetric mononuclear cobalt(III) bonded to three dithiocarbamate ligands forming a distorted octahedral geometry, indicating the cobalt(II) undergoes aerial oxidation to cobalt(III) during recrystallization. In addition, 2A crystallized with one solvated molecule of toluene. The redox behaviors of the complexes were studied by cyclic and square wave voltammetry in dichloromethane; the result revealed a metal centered redox process consisting of a one-electron quasi-reversible process assigned to Co(III)/Co(IV) oxidation and a corresponding Co(IV)/Co(III) reduction. Randles–Sevcik plots (anodic peak current versus the square root of the scan rate (I_p,a versus ν^1/2)) for the redox couples revealed diffusion-controlled behavior.     

Synthesis of thiophene-substituted aza-BODIPYs and their optical and electrochemical properties

A series of novel thiophene-substituted aza-BODIPY dyes were synthesized by means of a standard procedure and complemented by a Stille-coupling of a brominated species with 2-tributylstannylthiophene. The optical as well as the electrochemical properties of the compounds were investigated and compared to result of density functional theory (DFT) calculations. The influence of the thiophene substituents is discussed in dependence of the position at the aza-BODIPY core regarding the HOMO and LUMO frontier orbitals. The different distributions of the HOMO and LUMO coefficients over the BODIPY core lead to a variable influence of the thiophene substituents on the HOMO and LUMO energies, being the origin of the tunable optical and electrochemical properties.     

The electrochemistry of some ferrocene derivatives: redox potential and substituent effects

Fifteen ferrocene derivatives I–IX (four of which have been prepared for the first time: II, IIIf, V and VIII) have been prepared by Friedel–Crafts acetylation, Claisen condensation, Michael reaction, and ring closure by hydrazine hydrate. The anodic behaviour of these compounds has been studied by cyclic voltammetry at a platinum electrode in an aprotic solvent. All these substituted ferrocenes exhibit a reversible one‐electron oxidation reduction centred at each iron centre, and the effect of substituents on the half‐wave oxidation potential is discussed in terms of their electronic properties. Linear correlations have been observed between these potentials and the Hammett σ_x constant for the substituents. Cyclic voltammetry has been carried out for ferrocene derivatives IIIa, V and IX. Copyright © 2003 John Wiley & Sons, Ltd.     

含吡唑配体的VIB金属羰基配合物的合成与电化学性质研究

研究了吡唑类配体与M(CO)6(M=Cr,W)的光化学反应,合成了一系列的含吡唑配体的五羰基铬钨配合物。研究了该类化合物的电化学性质。结果表明：铬系列化合物存在一对准可逆的氧化还原峰,而钨系列化合物只存在一个不可逆的氧化峰,用X射线单晶衍射测定了化合物3,4,5－三甲基吡唑五羰基铬的晶体结构。该晶体为单斜晶系,空间群为P2(1)/m,晶胞参数为a=0.9106(3)nm,b=07627(2)nm,c=0.9637(3)nm,β＝91.855(5)°,V=0.6689(3)nm^3,Z=2,R=0.042,Cr为六配位的变形八面体构型。     

Synthesis of liquid crystal ferrocene derivatives and their complexes with Cu2+

A series of liquid crystal ferrocene-containing Schiff bases of general formula C₅H₅FeC₅H₄-C₆H₄-N=CN-(X)C₆H₃-O(O)-C₆H₄-OC_nH_2n+1 (X=H, OH, n=3–12) was obtained, together with several analogs, 1,1-bis-substituted at the ferrocene fragment, having a thermotropic nematic mesophases. Derivatives with X=OH were used to obtain Cu²⁺ chelate complexes, of which the compounds with n=10 and n=12 displayed nematic liquid crystalline properties.Physicotechnical Institute, Kazan Scientific Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 402–407, February, 1992.