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1.
InIII-Phthalocyanines: Synthesis, Properties, and Crystal Structure of Tetra(n-butyl)ammonium-cis-di(nitrito-O,O')phthalocyaninato(2–)indate(III) [In(Cl)Pc2?] reacts with (nBu4N)NO2 in acetone yielding green-blue (nBu4N)cis[In(NO2)2Pc2?], which crystallizes in the monoclinic space group P21/n (No. 14). Both nitrite anions are coordinated as chelating nitrito-O,O'(NO2) ligands to InIII in cis-geometry. Consequently InIII is octa-coordinated within a distorted “quadratic” antiprism and directed towards the Pc2?-ligand. One of the NO2 ligands has equivalent N? O bonds similar to free nitrite, while the other has asymmetric N? O bonds. Both (In,O,N,O) rings are approximately planar with a dihedral angle of 80°. The Pc2? ligand is distorted in an asymmetrically convex manner. Partially overlapping pairs of Pc2? ligands related by an inversion center form double layers, which are separated by layers containing the (nBu4N)+ cations. The cyclic voltammogram shows three electrode processes, which are assigned to the redox pairs: Pc3?/Pc2? (?0.94 V) < InI/InIII (-0.78 V) < Pc2?/Pc? (0.64 V). The UV-VIS-NIR spectra and vibrational spectra are discussed.  相似文献   

2.
In this study, the titanyl and vanadyl phthalocyanine (Pc) salts (Bu4N+)2[MIVO(Pc4?)]2? (M=Ti, V) and (Bu3MeP+)2[MIVO(Pc4?)]2? (M=Ti, V) with [MIVO(Pc4?)]2? dianions were synthesized and characterized. Reduction of MIVO(Pc2?) carried out with an excess of sodium fluorenone ketyl in the presence of Bu4N+ or Bu3MeP+ is exclusive to the phthalocyanine centers, forming Pc4? species. During reduction, the metal +4 charge did not change, implying that Pc is an non‐innocent ligand. The Pc negative charge increase caused the C?N(pyr) bonds to elongate and the C?N(imine) bonds to alternate, thus increasing the distortion of Pc. Jahn–Teller effects are significant in the [eg(π*)]2 dianion ground state and can additionally distort the Pc macrocycles. Blueshifts of the Soret and Q‐bands were observed in the UV/Vis/NIR when MIVO(Pc2?) was reduced to [MIVO(Pc . 3?)] . ? and [MIVO(Pc4?)]2?. From magnetic measurements, [TiIVO(Pc4?)]2? was found to be diamagnetic and (Bu4N+)2[VIVO(Pc4?)]2? and (Bu3MeP+)2[VIVO(Pc4?)]2? were found to have magnetic moments of 1.72–1.78 μB corresponding to an S=1/2 spin state owing to VIV electron spin. As a result, two latter salts show EPR signals with VIV hyperfine coupling.  相似文献   

3.
《Chemical physics letters》1987,137(2):107-112
Near infrared absorption spectra (700–1800 nm) of various lanthanide bis-phthalocyanines (Pc2Lu, Pc2Yb, Pc2Tm, Pc2Dy) show two relatively intense bands (ϵmax≈104 M−1 cm−1). The higher energy band is assigned to the 1eg→alu transition of the radical macrocycle (Pc) while the lower energy one may be related to an intramolecular charge transfer from one macrocyclic ligand (Pc2−) to the other (Pc). The corresponding spectra for the reduced and oxidized species (Pc2Ln, Pc2Ln+) are in agreement with these assignments.  相似文献   

4.
Summary. The molecular precursors Nb(OiPr)2[OSi(OtBu)3]3 and {Nb(OiPr)4[O2P(OtBu)2]}2 have been prepared. The first compound undergoes facile thermal conversion to high surface area, acidic niobia silica, whereas the second one thermally decomposes to a low surface area niobium phosphate.  相似文献   

5.
The molecular precursors Nb(OiPr)2[OSi(OtBu)3]3 and {Nb(OiPr)4[O2P(OtBu)2]}2 have been prepared. The first compound undergoes facile thermal conversion to high surface area, acidic niobia silica, whereas the second one thermally decomposes to a low surface area niobium phosphate.  相似文献   

6.
AlIII Phthalocyanines: Synthesis, Properties, and Crystal Structure of Tetra(n-butyl)-ammonium-trans-di(nitrito(O))phthalocyaninato(2?)aluminate(III) [Al(Cl)Pc2?] reacts with excess (nBu4N)NO2 in dimethylformamide yielding less soluble blue tetra(n-butyl)ammonium-trans-di(nitrito(O))phthalocyaninato(2?)aluminate(III), (nBu4N)trans[Al(ONO)2Pc2?], which crystallizes in the monoclinic space group C2/c (No. 15) with Z = 4. The Al atom is in the special position 4 d in the center of the Pc2? ligand and the two nitrit ions are monodentate O-coordinated in a mutually trans arrangement to the Al atom. The Al? O and average Al? Niso bond distances are 1.927(2) and 1.956 Å, respectively. The geometric data of the coordinated nitrite ion are: d(N? O) = 1.277(4) Å; d(N? O) = 1.221(4) Å; ?(O? N? O) = 114.3(3)°; ?(Al? O? N) = 121.3(2)°. The non-bonded O atoms are trans to the Al atom. The Pc2? ligand is slightly ruffled. The UV-VIS-NIR spectra and the vibrational spectra are discussed.  相似文献   

7.
OsII Phthalocyaninates(2?): Synthesis and Properties of (Halo)(carbonyl)phthalocyaninato-(2?)osmate(II) Soluble, blue tetra(n-butyl)ammonium (halo)(carbonyl)phthalocyaninato(2?)osmate(II), (nBu4N)[Os(X)(CO)Pc2?] (X = Cl, Br, I) is obtained by the reaction of [Os(THF)(CO)Pc2?] (THF: tetrahydrofurane) with (nBu4N)X in THF. In the cyclovoltammograms there are three reversible electrode processes at ?1.21 ± 0.01, 0.18 ± 0.04 and 0.65 ± 0.01 V assigned to the three redox pairs Pc2?/Pc3?, OsII/OsIII and Pc2?/Pc3?. In the electronic absorption spectra only the intense B and Q regions are observed at ~ 15800 resp. 27500, 33000 cm?1. The infrared and resonance Raman spectra closely resemble those of other phthalocyaninates(2?) of low valent osmium. In the infrared spectrum v(C? O) is detected at 1896 ± 4 cm?1 and v(Os? X) at 260 (X = Cl), 175 (X = Br) or 143 cm?1 (X = I).  相似文献   

8.
《化学:亚洲杂志》2017,12(8):910-919
Reduction of aluminum(III), gallium(III), and indium(III) phthalocyanine chlorides by sodium fluorenone ketyl in the presence of tetrabutylammonium cations yielded crystalline salts of the type (Bu4N+)2[MIII(HFl−O)(Pc.3−)].−(Br) ⋅ 1.5 C6H4Cl2 [M=Al ( 1 ), Ga ( 2 ); HFl−O=fluoren‐9‐olato anion; Pc=phthalocyanine] and (Bu4N+) [InIIIBr(Pc.3−)].− ⋅ 0.875 C6H4Cl2 ⋅ 0.125 C6H14 ( 3 ). The salts were found to contain Pc.3− radical anions with negatively charged phthalocyanine macrocycles, as evidenced by the presence of intense bands of Pc.3− in the near‐IR region and a noticeable blueshift in both the Q and Soret bands of phthalocyanine. The metal(III) atoms coordinate HFl−O anions in 1 and 2 with short Al−O and Ga−O bond lengths of 1.749(2) and 1.836(6) Å, respectively. The C−O bonds [1.402(3) and 1.391(11) Å in 1 and 2 , respectively] in the HFl−O anions are longer than the same bond in the fluorenone ketyl (1.27–1.31 Å). Salts 1 – 3 show effective magnetic moments of 1.72, 1.66, and 1.79 μB at 300 K, respectively, owing to the presence of unpaired S= 1/2 spins on Pc.3−. These spins are coupled antiferromagnetically with Weiss temperatures of −22, −14, and −30 K for 1 – 3 , respectively. Coupling can occur in the corrugated two‐dimensional phthalocyanine layers of 1 and 2 with an exchange interaction of J /k B=−0.9 and −1.1 K, respectively, and in the π‐stacking {[InIIIBr(Pc.3−)].−}2 dimers of 3 with an exchange interaction of J /k B=−10.8 K. The salts show intense electron paramagnetic resonance (EPR) signals attributed to Pc.3−. It was found that increasing the size of the central metal atom strongly broadened these EPR signals.  相似文献   

9.
New niobium imido complexes (RN)Nb(NEt2)3 (R = Prn, Pri and But), potential precursors to grow niobium containing thin films by chemical vapor deposition (CVD), were prepared by reacting the corresponding (RN)NbCl3py2 complexes (R = Prn, Pri and But; py = pyridine) with LiNEt2 in hydrocarbon solvents. The structures of (RN)NbCl3py2 (R = Pri and But), determined by X-ray crystallography, are mononuclear with distorted octahedral geometries, For each complex, three chloride ligands are cis to the imido ligand and occupy meridional positions. One of two py ligands is cis to and the other is trans to the imido ligand. For (PriN)NbCl3py2, the Nb=NPri bond distance (Å) is 1.733(3) and the ∠Nb=N-Pri angle (°) is 178.0(3). Crystal data: monoclinic, space group P21/n, a = 8.805(2), b = 14.930(4), c = 13, 407(3) Å, β = 93.37(2)°, V = 1759.5(7) Å3, Z = 4, Dc = 1.565 g cm3. For (ButN)NbCl3py2, the Nb=NBut bond distance (Å) is 1.734(4) and the ∠Nb=N-Bul angle (°) is 174.8(4). Crystal data: monoclinic, space group P21/c, a = 9.609(1), b = 13.591(6), c = 14.615(2) Å, β = 90.05(1)°, V = 1908.5(9) Å3, Z = 4, Dc = 1.492 g cm?3.  相似文献   

10.
Praseodymium(III) complexes with tetra-15-crown-5-phthalocyanine—the neutral radical [(R4Pc)Pr3+(R4Pc2?)]0 and one-electron reduced [(R4Pc2?)Pr3+(R4Pc2?)]? forms of the sandwich double-decker complex and the triple-decker complex Pr2(R4Pc)3 (R4Pc2? is [4,5,4′,5′,4″,5t",4″′,5″′-tetrakis(1,4,7,10,13-pentaoxatridecamethylene)phthalocyaninate ion])—have been synthesized and spectrally characterized. These compounds have been obtained by direct interaction of tetra-15-crown-5-phthalocyanine with praseodymium(III) acetate or acetylacetonate. The salt anion has an effect on the yield and structure of the reaction products. The complexes have been obtained in high yields, isolated, and characterized by different physicochemical methods: UV and visible electronic absorption spectroscopy, 1H NMR, and MALDI-TOF mass spectrometry. The double-decker complex is stable in the solid state and in solutions. The triple-decker complex is stable only in the solid state. In a chloroform-methanol (10 vol %) solution, it slowly decomposes.  相似文献   

11.
The specific features of electric conductivity and photoconductivity in films of composites based on poly(vinyl alcohol) doped with the complex [Fe(bipy)3][Zn(NCS)4] (where bipy is 2,2′-bipyridyl) and the effect of magnetic field on these properties were studied. It was found that photocurrent decreases with an increase in the magnetic field strength up to 5.5 kOe. It was assumed that the photoconductivity of these composites and its dependence on magnetic field are affected by paramagnetic iron(III) complex particles produced as a result of internal photoelectric effect. The effect of magnetic field on the photoconductivity is associated with the spin-dependent recombination of photogenerated charge pairs.  相似文献   

12.
Phthalocyanine compounds of novel type based on a bridged bis‐ligand, denoted “intracavity” complexes, have been prepared. Complexation of clamshell ligand 1,1′‐[benzene‐1,2‐diylbis(methanediyloxy)]bis[9(10),16(17),23(24)‐tri‐tert‐butylphthalocyanine] (clam,tBuPc2H4, 1 ) with lanthanide(III) salts [Ln(acac)3] ? n H2O (Ln=Eu, Dy, Lu; acetylacetonate) led to formation of double‐deckers clam,tBuPc2Ln ( 2 a – c ). Formation of high molecular weight oligophthalocyanine complexes was demonstrated as well. The presence of an intramolecular covalent bridge affecting the relative arrangement of macrocycles was shown to result in specific physicochemical properties. A combination of UV/Vis/NIR and NMR spectroscopy, MALDI‐TOF mass‐spectrometry, cyclic voltammetry, and spectroelectrochemistry provided unambiguous characterization of the freshly prepared bis‐phthalocyanines, and also revealed intrinsic peculiarities in the structure–property relationship, which were supported by theoretical calculations. Unexpected NMR activity of the paramagnetic dysprosium complex 2 b in the neutral π‐radical form was observed and examined as well.  相似文献   

13.
Synthesis and Spectroscopical Characterization of Di(halo)phthalocyaninato(1–)rhodium(III), [RhX2Pc1?] (X = Cl, Br, I) Bronze-coloured di(halo)phthalocyaninato(1–)-rhodium(III), [RhX2Pc1?] (X = Cl, Br) and [RhI2Pc1?] · I2 is prepared by oxidation of (nBu4N)[RhX2Pc2?] with the corresponding halogene. Irrespective of the halo ligands, two irreversible electrode reactions due to the first ringreduction (ER = ?0,90 V) and ringoxidation (EO = 0,82 V) are present in the cyclovoltammogram of (nBu4N)[RhX2Pc2?]. The optical spectra show typical absorptions of the Pc1?-ligand at 14.0 kK and 19.1 kK. Characteristic vibrational bands are at 1 366/1 449 cm?1 (i. r.) and 569/1 132/1 180/1 600 cm?1 (resonance Raman (r. r.)). The antisym. (Rh? X)-stretching vibration is observed at 294 cm?1 (X = Cl), 240 cm?4 (Br) and 200 cm?1 (I). Only the sym. (Rh? I)-stretching vibration at 133 cm?1 is r. r. enhanced together with a strong line at 170 cm?1, which is assigned to the (I? I)-stretching vibration of the incorporated iodine molecule. Both modes show overtones and combinationbands.  相似文献   

14.
The electrochemical potentials of seven redox transitions for green forms and eight redox transitions for blue forms of neutral octa-tert-butylsubstituted diphthalocyanine cornplexes of lanthanides Pct 2Ln (Ln=Pr, Sm, Dy, and Lu) in solutions were measured by cyclic voltammetry and rotating disc electrode techniques. The spectroelectrochemical investigation of the products of two-electron oxidation and reduction of the green form of Pct 2Lu was performed. The frontier molecular orbitals, total charge densities, total spin densities, electrostatic potentials, and heats of ion formation for (Pc2Y) m+,n− (m=0, 1, 2 and 3;n=1, 2, 3 and 4), which can model the products of the redox transitions of the diphthalocyanines under study, were calculated using the semiempirical ZINDO/1 method. The calculations for (Pc2Y) m+,n− and absorption spectra show that the electron changes in all redox transitions of the green forms of Pct 2Ln are mainly localized on the ligands. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya No. 12, pp. 2149–2156, December, 1997.  相似文献   

15.
Compounds of general formula Au{SSi(OR)3}(PPh3), R = Pri ( 1 ), Bus ( 2 ) or But ( 3 ), have been obtained by reaction of AuCl(PPh3) with triethylammonium salts of respective silanethiols, (RO)3SiSH. Molecular and crystal structures of 1 , 2 , and 3 have been determined by the single crystal X‐ray structural analysis. Compounds 1 and 2 are the first structurally characterized metal derivatives of hydrolytically unstable trialkoxysilanethiols (PriO)3SiSH and (BusO)3SiSH.  相似文献   

16.
New Phosphido-bridged Multinuclear Complexes of Ag and Zn. The Crystal Structures of [Ag3(PPh2)3(PnBu2tBu)3], [Ag4(PPh2)4(PR3)4] (PR3 = PMenPr2, PnPr3), [Ag4(PPh2)4(PEt3)4]n, [Zn4(PPh2)4Cl4(PRR′2)2] (PRR′2 = PMenPr2, PnBu3, PEt2Ph), [Zn4(PhPSiMe3)4Cl4(C4H8O)2] and [Zn4(PtBu2)4Cl4] AgCl reacts with Ph2PSiMe3 in the presence of tertiary Phosphines (PnBu2tBu, PMenPr2, PnPr3 and PEt3) to form the multinuclear complexes [Ag3(PPh2)3(PnBu2tBu)3] 1 , [Ag4(PPh2)4(PR3)4] (PR3 = PMenPr2 2 , PnPr3 3 ) and [Ag4(PPh2)4(PEt3)4]n 4 . In analogy to that ZnCl2 reacts with Ph2PSiMe3 and PRR′2 to form the multinuclear complexes [Zn4(PPh2)4Cl4(PRR′2)2] (PRR′2 = PMenPr2 5 , PnBu3 6 , PEt2Ph 7 ). Further it was possible to obtain the compounds [Zn4(PhPSiMe3)4Cl4(C4H8O)2] 8 and [Zn4(PtBu2)4Cl4] 9 by reaction of ZnCl2 with PhP(SiMe3)2 and tBu2PSiMe3, respectively. The structures were characterized by X-ray single crystal structure analysis. Crystallographic data see “Inhaltsübersicht”.  相似文献   

17.
《Tetrahedron letters》1986,27(42):5143-5146
Reaction of the cyclopropenes (3, R1 = Me, R2 = Me), (3, R1 = H, R2 = Pri) and (3, R1 = H, R2 = But) and with one equivalent of m-chloroperbenzoic acid leads to the enones (4) and (7, R = Pri and But respectively, in the last two cases accompanied by about 15% of the regioisomer (8, R = Pri or But. In the case of (3, R1 = Me, R2 = H) oxidation with excess reagent led to the formate (9, R = SiMe3) and two intermediates (11) and (10, R = SiMe3) could be identified.  相似文献   

18.
Studying the reaction of PcSiX2 (X = Cl, OH) with KOH in DMSO we first discovered red D-A complexes [(Pc2−)·PcSiX2] and [(Pc2−)·O2] in which silicon phthalocyanine dianion Pc2− is a donor, and the parent phthalocyanine silicon or oxygen are acceptors of electron density. The complexes were characterized by electron absorption, NMR, and ESR spectra. In the reactions with Me3SiCl, H2O, or CH3COOH the complexes regenerate phthalocyanine and O2. In O2 atmosphere the [(Pc2−)·O2] complex gradually degrades affording a product of unknown nature.  相似文献   

19.
Preparation and Properties of Tetragonal α-Di(phthalocyaninato(1?))praseodymium(III)-polyhalides; Crystal Structure of α-[Pr(Pc?)2]Br1.5 Brown red di(phthalocyaninato(1?))-praseodym(III)-polyhalides [Pr(Pc?)2]Xy (X = Br, I) of variable composition (1 ≤ y ≤ 2.5) are formed by (electro)chemical oxidation of [Pr(Pc2?)2]?. The thermical decomposition of these polyhalides at 250°C yields partially oxidized, green α-[PrPc?Pc2?]. Due to strong spin–spin coupling of the phthalocyanin-π-radicals only PrIII contributes to the magnetic moment of ca. 3.0 B.M. for all complexes. Green metallic prisms of [Pr(Pc?)2]Br1.5 crystallize in the tetragonal α-modification: space group P4/nnc with a = 19.634(5) Å, c = 6.485(2) Å; Z = 2. In the sandwich complex PrIII is eightfold coordinated by the isoindoline N-atoms of the two staggered (41°), nearly planar Pc?- ligands. The quasi-onedimensional character of the structure along [001] is due to the infinite columns of Pc? ligands. The superperiod along [001] is a consequence of the distribution of the Pr atoms onto two incompletely filled crystallographic positions at a distance of c/2 and the disordered chains of the bromine atoms extending in the same direction. Powder diffractograms of Pr(Pc )2Br2, [Pr(Pc?)2]I2 und [PrPc Pc2?] confirm the tetragonal α-modification of these complexes, too. The content of tribromide correlates with the population of the Pr(2)-site. In the UV-VIS-NTR absorption spectrum of a thin film of Pr(Pc )2Br, the intense bands at 13.9 and 19.5 kK are assigned to the B and Q transition, respectively. The D band at 9. kK is characteristic for isolated dimeric Pc?-π-radicals. Due to increasing electron delocalisation as a result of the growing columns the D band is shifted to lower energy appearing successively at 6.05 and 3.3 kK. The mir and resonance Raman (RR) spectra of α-[Pr(Pr?)2]Xy, (X = Br, I) show the well known diagnostic bands for Pc?-π-radicals. Thc RR spectrum of the polyiodide is dominated by the overtone progression of the totally symmetric (I-I) stretching vibration of the triiodide at 108cm?1. The FT-Raman spectra are also marked by the totally symmetric stretching vibration of the polyhalides (Br3 : 145cm 1; 13?:105cm?1; I5? 151 cm?1).  相似文献   

20.
The electric conductivity and photoconductivity of films based on polyvinylbutyral and containing Fe2O3 and CdS nanoparticles and an organic compound with intramolecular charge transfer as photoconductivity sensitizer in the visible and near infrared regions were investigated. In the absorption region of the sensitizer the activation energy of the photocurrent is somewhat greater than 0.1 eV and is close to the activation energy of the electric conductivity current.  相似文献   

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