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1.
《Journal of Coordination Chemistry》2012,65(2):294-301
Two new binuclear copper(II) complexes containing four spin carriers with pyridyl-substituted nitroxide radicals have been synthesized and characterized structurally and magnetically. These complexes are formulated as [Cu2(oxap)(IM4py)2](ClO4)2 (1) and [Cu2(oxap)(NIT4py)2](ClO4)2 (2), respectively, in which oxap stands for N,N′-bis(2-aminopropyl). IM4py stands for 2-(4′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl and NIT4py for 2-(4′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide. The structures of the complexes consist of centro-symmetric trans oxamido-bridged copper(II) binuclear units and nitroxide radicals. In 1 and 2 the copper atoms are in a distorted square plane and radicals (IM4py and NIT4py) coordinate to copper via nitrogen atoms from pyridine rings. Magnetic analysis indicates that 1 and 2 exhibit strong metal-metal antiferromagnetic coupling through oxamido-bridged and antiferromagnetic exchange interactions between copper(II) ion and radicals, respectively. The magnetic behaviors are discussed with reference to their crystal structures. 相似文献
2.
A novel diamagnetic-metal Cd(Ⅱ) complex with four nitroxide radicals[Cd(IM4Py)4Cl2](IM4Py=2-(4'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl) was synthesized and characterized by elemental analyses,IR spectra,UV-Vis spectra and X-ray single crystal diffraction.The complex crystallized in triclinic space group P1 with a=0.93285(14) nm,b=1.16827(18) nm,c=1.3660(2) nm,α=112.759(2)°,β=104.524(2)°,γ=92.008(3)°,V= 1.3143(3) nm3,Z=1,Dc=1.335 g/cm3,the final R1=0.0423 and wR2=0.1009.In the title complex,each Cd(Ⅱ) ion adopting a distorted octahedral geometry is coordinated by two Cl-anions and four pyridyl-N atoms from four IM4Py ligands.The magnetic measurements show the weak antiferromagnetic interactions between the nitroxide radicals. 相似文献
3.
《Journal of Coordination Chemistry》2012,65(9):929-936
A new binuclear copper(II) complex [Cu2(oxpn)(IM2py)2](ClO4)2, containing four spin carriers with pyridyl-substituted nitroxide radicals has been synthesized and characterized structurally and magnetically (oxpn?=?N,N′-bis(3-aminopropyl)oxamido, IM2py?=?2-(2′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl). The structure of the complex consists of centrosymmetric trans oxamido-bridged copper(II) binuclear units and nitroxide radicals. The coordination geometry around each copper atom is distorted square pyramidal and the apical position is occupied by a nitrogen atom of the imidazoline ring of a radical ligand. Magnetic analysis indicates that the complex exhibits strong antiferromagnetic coupling between copper(II) ions through the oxamido bridge and a ferromagnetic interaction between copper(II) ions and radical ligands. The magnetic behaviour is discussed with reference to the crystal structure. 相似文献
4.
5.
1-Ferrocenyl- and 1,9-diferrocenyl-thianthrenes have been synthesized by using palladium-catalyzed cross-coupling reactions of 1-bromo- and 1,9-dibromo-thianthrenes with ferrocenylzinc chloride. The structure of 1-ferrocenylthianthrene was determined by X-ray crystallographic analysis. 1-Ferrocenyl- and 1,9-diferrocenyl-thianthrenes show well-defined separated two-steps two-electrons and three-steps three-electrons reversible redox waves derived from the ferrocenium cation and the thianthrene radical cation, respectively, by the cyclic voltammetry in dichloromethane containing the supporting electrolyte anion of [B(C6F5)4]−. 相似文献
6.
ZHANG Zhongqiang DI Di ZHAI Jingshuo WU Lili ZHU Qinlei XU Yanqing HUANG Rudan 《高等学校化学研究》2014,(2):185-189
Two complexes,Co(Hbim)2(NCS)2(Hbim=benzimidazole)(1) and [Cu(Hbzt)SCN]n(Hbzt=benzothiazole) (2) were synthesized by the same synthesis method and characterized by elemental analysis,infrared spectroscopy(IR),thermogravimetric analysis(TGA),X-ray powder diffraction(XRPD) and single-crystal X-ray diffraction.The results from the single-crystal X-ray diffraction indicate that complex 1 is zero-dimensional(0D) framework and complex 2 is 2-dimensional(2D) framework.In complex 2,the 3-dimensional(3D) supermolecular architecture was built up by means of π-π stacking interaction,and two helical chains existed in its structure.The luminescence properties and the magnetic properties of the two complexes were investigated. 相似文献
7.
Masaru Sato Yuta Miyagawa Shizuka Okada Noboru Saito 《Journal of organometallic chemistry》2007,692(14):3089-3093
Mono- and di-t-butyl substituted 2,2′-bis(1,3-dithia[3]ferrocenophane-2-ylidene) derivatives were prepared. These derivatives showed the E1/2(1) in lower potential region than that of differrocenyl-ethene and -ethyne. Also, the ΔE1/2 value declined according to the increase of a t-butyl group. 相似文献
8.
Jose Ramon Garabatos Perera Holger Butenschön 《Journal of organometallic chemistry》2004,689(22):3541-3549
Some triferrocenylmethane derivatives were prepared by reaction of triferrocenylmethanol (5) with triphenylcarbenium tetrafluoroborate followed by a nucleophile. Crystal structure analyses of triferrocenylmethane (7) and of 1,1,1-triferrocenyl-2,2-dimethylpropane (11) show that the conformation adopted by the triferrocenylmethyl group differs significantly with the steric bulk of the substituent at the central carbon atom. Treatment of 1,1′-bis(tributylstannyl)ferrocene (13) with 1 equiv. of butyllithium followed by chloroethylformiate affords complexes with one (14), two (15) or three ferrocenyl units (16) depending on the amount of chloroethylformiate used. Compound 16 is the first triferrocenylmethane derivative with substituents at the opposite cyclopentadienyl ring. Threefold lithiation of this compound is shown to work using butyllithium followed by dimethylformamide. 相似文献
9.
Tomoyuki Mochida Hirotaka Shimizu Takahiro Akasaka 《Journal of organometallic chemistry》2006,691(23):4882-4889
4-Ferrocenyltriazole, 4-(4-ferrocenylphenyl)triazole, 4-ferrocenyltetrazole, and 4-(4-ferrocenylphenyl)tetrazole have been prepared. Redox potentials and decomposition temperatures were evaluated and all the compounds were crystallographically characterized; in most cases, weak intermolecular CH?N hydrogen bonds (H?N dist. = 2.3-2.5 Å) were formed between the azole moieties. Two polymorphs were found for 4-ferrocenyltetrazole, formed with either CH?N or π-π interactions. 相似文献
10.
V. Sai Sudhir 《Tetrahedron》2010,66(6):1327-2694
This work reports the synthesis of a wide range of ferrocenyl-amino acids and other derivatives in excellent yield. Diverse amino acid containing azides were synthesized and ligated to ferrocene employing click reaction to access ferrocenyl amino acids. Chiral alcohols, esters, diols, amines containing azido group were tagged to ferrocene via click reaction to generate ferrocene derived chiral derivatives. A novel strategy for direct incorporation of ferrocene into a peptide and a new route to 1, 1′disubstituted ferrocene amino acid derivative are reported. 相似文献
11.
Two coordination polymers {[Co3L3(Me2NH)2]·(Me2NH)}n(1) and [CuL(bpy)]n(2)(L=2,2'-biphenyl dicarboxylate ion, bpy=4,4'-bipyridine) were obtained and characterized. Compound 1 was synthesised via solvothermal method, with the L ligands adopting syn-syn-μ2-η1:η1- and μ2-η2-coordination modes and Co(II) centers being linked to form a 1D coordination chain with trinuclear Co3 cluster as sub-units. Compound 2 was synthesized at room temperature, with the L ligand chelating the Cu(II) centers to form a 1D chain, which was further linked by the auxiliary 4,4'-bpy ligand to form a 3D coordination network. The results of variable temperature susceptibility studies reveal that there were ferromagnetic and antiferromagnetic interactions between the paramagnetic metal centers in compounds 1 and 2, respectively. 相似文献
12.
Scott L. Ingham Muhammad S. Khan Jack Lewis Nicholas J. Long Paul R. Raithby 《Journal of organometallic chemistry》1994,470(1-2):153-159
The reactions of alkynyltrimethylstannanes with 1,1′-dilithioferrocene have given several ferrocenylacetylides, namely 1-pheny]-ethynyl-1′-iodo-ferrocene (1), 1,1′-bis(phenylethynyl)ferrocene (2), 1,4-di(1′-iodoferrocenylethynyl)benzene (3) and poly[1,4-(1′-ferrocenylethynyl)ethynylbenzene] (4). The versatility of this reaction for the formation of ferrocenylacetylides is demonstrated. The crystal structure of 2 has been determined, and shown to involve a linear array of the groups with a cis arrangement of the phenylethynyl ligands. 相似文献
13.
The photostability of nine ferrocene derivatives of varying functionality was investigated using cyclic voltammetry. Derivatives with carbonyl groups (aldehyde or ketone) directly attached to the cyclopentadiene ring system were found to decompose in aqueous (pH 7.4) solution over a period of 10 min when exposed to light. The kinetics of the photodecomposition process were investigated and the relative values of the rate constants for the photodecomposition tabulated. The implications for biosensor applications are assessed. 相似文献
14.
Organometallic charge-transfer salts composed of decamethyl-, octamethyl-, and dimethylferrocene with N,N′-dicyano-1,4-benzoquinonediimine (DCNQI) derivatives were prepared. [Fe(C5Me5)2][(MeO)2DCNQI] (1) and [Fe(C5Me4H)2][Me2DCNQI] (2) were 1:1 DA salts with mixed-stack structures, whereas [Fe(C5Me4H)2][(MeO)2DCNQI]2 (3) and [Fe(C5MeH4)2][DCNQI]2 (4) were 1:2 DA salts. 3 exhibited a segregated-stack structure, in which charge separation was observed in the acceptor column. 1 became a metamagnet below TN = 5.0 K, whereas the other salts were paramagnets. Valence states and charge-transfer (CT) transitions in these complexes are discussed based on the neutral-ionic (NI) phase diagram. 相似文献
15.
2,3-Diferrocenylbenzo[b]thiophene and 1,3-diferrocenylbenzo[c]thiophene have been systematically and selectively synthesized from benzo[b]thiophene and phthaloyl dichloride, respectively. Characterization of the molecules was performed by physical and spectroscopic means and X-ray crystallographic analyses. The cyclic voltammograms of the novel thiophene derivatives containing ferrocene fragments showed a well-defined reversible cathodic step derived from the unusually stable thiophene radical anions and two distinct reversible anodic steps derived from ferrocenium cations separated from each other by a thiophene heterocycle. 1,3-Diferrocenylbenzo[c]selenophene was also synthesized in a similar manner for formation of 1,3-diferrocenylbenzo[c]thiophene by the use of bis(dimethylaluminum) selenide as a selenating reagent. 相似文献
16.
N.N. Meleshonkova 《Journal of organometallic chemistry》2007,692(24):5339-5344
Novel Schiff bases of ferrocenecarboxaldehyde bearing 2,6-di-tert-butyphenol fragments N-(3,5-di-tert-butyl-4-hydroxyphenyl)iminomethylferrocene (1) and N-(3,5-di-tert-butyl-4-hydroxybenzyl)iminomethylferrocene (2) have been synthesized and characterized. The oxidation of the compounds 1 and 2 by PbO2 in solution leads to the formation of stable phenoxyl radicals 1′ and 2′ studied by EPR spectroscopy. The redox properties of ferrocenes 1 and 2 were studied using cyclic voltammetry. 相似文献
17.
Two two-dimensional coordination complexes, {[Cu4(BTM)6(OPA)4] · 4DMF · 3H2O}
n
(1) and {[Cu(BDTM)(OH)](ClO4) · 2H2O}
n
(2) (BTM = bis(1,2,4-triazol-1-yl)methane, BDTM = bis(3,5-dimethyl-1,2,4-triazol-1-yl)methane, OPA2− = ortho-phthalic dianion, DMF = N,N-dimethylformamide), were synthesized and structurally characterized. Each Cu(II) ion locates in a distorted square pyramidal
geometry in 1, in which OPA2− ligands bridge Cu2+ ions along a axis to form a magnetic transmission chain and BTM ligands act as flexible spacers to construct the two-dimensional layer
structure. In 2, each Cu2+ ion adopts tetra-coordination geometry to two hydroxyl groups and two triazolyl nitrogen atoms from two different BDTM ligands.
Two hydroxyl groups bridge two Cu2+ ions to form a rhombic diamond, and four BDTM ligands connect four diamonds to form a 36-membered macrocyclic structure with
large channels along a axis. Magnetic properties revealed that both OPA2− and OH− mediate anti-ferromagnetic interactions between Cu2+ ions with J = − 0.06(3) and −301.9(2) cm−1 for 1 and 2, respectively.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
18.
Robert F. Kirchner Gilda H. Loew Ulrich T. Mueller-Westerhoff 《Theoretical chemistry accounts》1976,41(1):1-6
An iterative extended Hückel molecular orbital calculation was used to obtain wave functions for the ground state of ferrocene and several low lying states of the ferrocenium ion. Photoemission spectra in terms of relative ionization potentials and the electric field gradient at the iron nucleus were calculated for ferrocene andg values and the electric field gradient were calculated for the ferrocenium ion. These values are in good agreement with experiment. The nature of the molecular orbitals was compared with results of previous semi-empirical andab initio calculations. 相似文献
19.
Yaqiu Sun Guangming Yang Daizheng Liao Zonghui Jiang Shiping Yan Peng Cheng 《Structural chemistry》2007,18(5):599-603
The novel oxamidato-bridged dinuclear [(CuL)VO(H2O)(C2O4)] complex incorporating a macrocyclic oxamide has been synthesized, spectroscopically, structurally, and magnetically characterized,
where (CuL = [5,6: 14,15-dibenzo-1,4,8,12- tetraazacyclopentadeca-7,13-diene-2,3-dione(2-)]copper(II)). Magnetic measurements
indicate ferromagnetic interaction between Cu(II) and VO(IV) ions within the complex. 相似文献
20.
《Journal of Coordination Chemistry》2012,65(17):1573-1579
A series of new complexes of multi-sulfur 1,2-dithiolene ligands, [Ru(bipy)3][Ni(L)2]2 (bipy?=?2,2′-bipyridine; L?=?pddt (6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate), dddt (5,6-dihydro-1,4-dithiin-2,3-dithiolate)), have been synthesized and characterized. One typical complex, [Ru(bipy)3][Ni(pddt)2]2·2H2O (1), crystallized in an acentric space group of P212121, with the cell dimensions of a?=?8.634(1), b?=?14.560(1), c?=?49.889(5)?Å, α?=?β?=?γ?=?90°, and Z?=?4. It consists of alternating columns of cations and anions along the a direction. The structure was refined by full matrix least squares methods to R 1?=?0.0340, wR 2?=?0.0670. Magnetic studies on [Ph2Cr][Ni(dddt)2] are also reported. 相似文献