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1.
Ying Wang Dr. Tian‐Wei Wang Hong‐Ping Xiao Yi‐Zhi Li Dr. You Song Xiao‐Zeng You Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(31):7648-7655
By using cyclohexane‐1,2‐diamine (chxn), Ni(ClO4)2 ? 6H2O and Na3[Mo(CN)8] ? 4H2O, a 3D diamond‐like polymer {[NiII(chxn)2]2[MoIV(CN)8] ? 8H2O}n ( 1 ) was synthesised, whereas the reaction of chxn and Cu(ClO4)2 ? 6H2O with Na3[MV(CN)8] ? 4H2O (M=Mo, W) afforded two isomorphous graphite‐like complexes {[CuII(chxn)2]3[MoV(CN)8]2 ? 2H2O}n ( 2 ) and {[CuII(chxn)2]3[WV(CN)8]2 ? 2H2O}n ( 3 ). When the same synthetic procedure was employed, but replacing Na3[Mo(CN)8] ? 4H2O by (Bu3NH)3[Mo(CN)8] ? 4H2O (Bu3N=tributylamine), {[CuII(chxn)2MoIV(CN)8][CuII(chxn)2] ? 2H2O}n ( 4 ) was obtained. Single‐crystal X‐ray diffraction analyses showed that the framework of 4 is similar to 2 and 3 , except that a discrete [Cu(chxn)2]2+ moiety in 4 possesses large channels of parallel adjacent layers. The experimental results showed that in this system, the diamond‐ or graphite‐like framework was strongly influenced by the inducement of metal ions. The magnetic properties illustrate that the diamagnetic [MoIV(CN)8] bridges mediate very weak antiferromagnetic coupling between the NiII ions in 1 , but lead to the paramagnetic behaviour in 4 because [MoIV(CN)8] weakly coordinates to the CuII ions. The magnetic investigations of 2 and 3 indicate the presence of ferromagnetic coupling between the CuII and WV/MoV ions, and the more diffuse 5d orbitals lead to a stronger magnetic coupling interaction between the WV and CuII ions than between the MoV and CuII ions. 相似文献
2.
Liuqing He Wenbiao Zhang Qijie Mo Wenjie Huang Lichun Yang Qingsheng Gao 《Angewandte Chemie (International ed. in English)》2020,59(9):3544-3548
Heterostructured Mo2C‐MoOx on carbon cloth (Mo2C‐MoOx/CC), as a model of easily oxidized electrocatalysts under ambient conditions, is investigated to uncover surface reconfiguration during the hydrogen evolution reaction (HER). Raman spectroscopy combined with electrochemical tests demonstrates that the MoVI oxides on the surface are in situ reduced to MoIV, accomplishing promoted HER in acidic condition. As indicated by density functional theoretical calculations, the in situ reduced surface with terminal Mo=O moieties can effectively bring the negative ΔGH* on bare Mo2C close to a thermodynamic neutral value, addressing difficult H* desorption toward fast HER kinetics. The optimized Mo2C‐MoOx/CC only requires a low overpotential (η10) of 60 mV at ?10 mA cm?2 in 1.0 m HClO4, outperforming Mo2C/CC and most non‐precious electrocatalysts. In situ surface reconfiguration are shown on W2C‐WOx, highlighting the significance to boost various metal‐carbides and to identify active sites. 相似文献
3.
Pavel A. Zhizhko Florian Toth Christopher P. Gordon Ka Wing Chan Wei‐Chih Liao Victor Mougel Christophe Copret 《Helvetica chimica acta》2019,102(10)
5‐Coordinated methoxybenzylidene complexes M(=NAr)(=CH?C6H4?o‐OMe)(OtBuF3)2 (Ar=2,6‐iPr2C6H3; tBuF3=CMe2(CF3)) of Mo ( 1mMo ) and W ( 1mW ) were synthesized by cross‐metathesis from the corresponding neophylidene/neopentylidene precursors and o‐methoxystyrene. 1mMo and 1mW were grafted onto the surface of silica partially dehydroxylated at 700 °C to give well‐defined silica‐supported alkylidenes (≡SiO)M(=NAr)(=CH?C6H4?o‐OMe)(OtBuF3) (M=Mo ( 1Mo ), W ( 1W )). Supported methoxybenzylidene complexes were tested in metathesis of cis‐4‐nonene, 1‐nonene, and ethyl oleate, and compared to their molecular precursors and supported classical analogs (≡SiO)M(=NAr)(=CHCMe2R)(OtBuF3) (M=Mo, R=Ph ( 2Mo ), M=W, R=Me ( 2W )). Both grafted complexes 1Mo and 1W show significantly better performance as compared to their molecular precursors 1mMo and 1mW but are less efficient than the classical 4‐coordinated alkylidenes 2Mo and 2W . Noteworthy, both 1Mo and 1W can reach equilibrium conversion in metathesis of cis‐4‐nonene at catalyst loadings as low as 50 ppm. 相似文献
4.
Qinyu Song Dr. Olaf Stefanczyk Guanping Li Dr. Kunal Kumar Kazuki Nakamura Dr. Koji Nakabayashi Prof. Shin-ichi Ohkoshi 《欧洲无机化学杂志》2023,26(30):e202300482
The spin-crossover (SCO) and charge-transfer (CT) phenomena, the switching processes between two distinguishable magnetic states, are promising for developing materials capable of sophisticated memory and sensing functionalities. The majority of SCO systems are based on iron(II) complexes. However, cobalt(II)-2,2′:6′,2′′-terpyridine (terpy) systems emerge as a promising alternative. In this work, new complex salts [CoII(terpy)2]2[MoIV(CN)8] ⋅ 15H2O, Co2Mo (H2O), and [CoII(terpy)2]3[WV(CN)8]2 ⋅ 12H2O, Co3W2 (H2O) were synthesized and physiochemically characterized. Structural studies for both compounds revealed [Co(terpy)2]2+ layers pillared by octacyanidometallate anions and completed with water molecules between them. Magnetic studies confirmed that the (de)solvated phases of both complexes exhibit partial SCO on the cobalt(II) centers: CoII−LS (SCo(II)-LS=1/2)↔CoII−HS (SCo(II)-HS=3/2). Moreover, handling dehydrated samples in a high-humidity environment leads to partial recovery of previous magnetic properties via humidity-induced SCO for Co2Mo : CoII−HS→CoII−LS, and the new phenomenon of isothermal humidity-activated charge-transfer-induced spin transition, which we define here as HACTIST, for Co3W2 : CoII−HS⋅⋅⋅WV (SCo(II)-HS=3/2 and SW(V)=1/2)→CoIII−LS⋅⋅⋅WIV (SW(IV)=0 and SCo(III)-LS=0). These comprehensive studies shed light on the water-solvation-dependent spin transitions in Co(II)-octacyanidometallate(IV/V) complexes. 相似文献
5.
《Polyhedron》2007,26(9-11):2054-2058
An intermediate in photoinduced magnetization process for the photomagnetic high-spin molecule [MoIV(CN)2(CN-CuL)6]8+ is studied with quantum chemistry calculations of the density functional theory and the ab initio multireference configuration interaction methods. It is found that the intramolecular electronic transfer from MoIV to CuII leads one trigonal-bipyamid coordinated CuII to be changed to the tetrahedral coordinated CuI with the light irradiation. The calculated magnetic properties show that the paramagnetic system [MoIV(CN)2(CN-CuIIL)6]8+ with six isolated spin 1/2 Cu ions is changed to ferromagnetic coupling high-spin system [MoV(CN)2(CN-CuIIL)5(CN-CuIL)]8+. These calculations will help to understand photoinduced magnetization phenomenon and provide a clue for the synthesization of new reversible photoinduced magnetic compounds. 相似文献
6.
Summary The kinetics of thermal reactions of photochemically generated aquaheptacyano MoIV and WIV complexes and their protonated and deprotonated forms have been studied spectrophotometrically in buffer solutions at pH 5.0–10.0, and ionic strength, 8×10–2 M at 25°C. A reaction scheme for the photochemical and thermal reactions of the MoIV and WIV octacyano complexes with ethylene diamine is proposed. Rate constants and quantum yields for these systems are maximal at pH 8.0. At pH>8.0, the reverse reaction, generating octacyano complexes from heptacyano species, is faster; at low pH the ligand is protonated and is less reactive. Quantum yields are higher for Mo than for W owing to the shorter life time of excited state species. This is because physical deactivation is expected to be more rapid in the heavier element due to enhanced spin-orbit coupling. Furthermore Mo-induced splitting is larger in [W(CN)8]4– as compared to [Mo(CN)8]4– which results in greater bond strength for tungsten. 相似文献
7.
Ronny Neumann Prof. Daniella Goldfarb Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(33):10014-10020
An in‐depth spectroscopic EPR investigation of a key intermediate, formally notated as [PVIVVVMo10O40]6? and formed in known electron‐transfer and electron‐transfer/oxygen‐transfer reactions catalyzed by H5PV2Mo10O40, has been carried out. Pulsed EPR spectroscopy have been utilized: specifically, W‐band electron–electron double resonance (ELDOR)‐detected NMR and two‐dimensional (2D) hyperfine sub‐level correlation (HYSCORE) measurements, which resolved 95Mo and 17O hyperfine interactions, and electron–nuclear double resonance (ENDOR), which gave the weak 51V and 31P interactions. In this way, two paramagnetic species related to [PVIVVVMo10O40]6? were identified. The first species (30–35 %) has a vanadyl (VO2+)‐like EPR spectrum and is not situated within the polyoxometalate cluster. Here the VO2+ was suggested to be supported on the Keggin cluster and can be represented as an ion pair, [PVVMo10O39]8?[VIVO2+]. This species originates from the parent H5PV2Mo10O40 in which the vanadium atoms are nearest neighbors and it is suggested that this isomer is more likely to be reactive in electron‐transfer/oxygen‐transfer reaction oxidation reactions. In the second (70–65 %) species, the VIV remains embedded within the polyoxometalate framework and originates from reduction of distal H5PV2Mo10O40 isomers to yield an intact cluster, [PVIVVVMo10O40]6?. 相似文献
8.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(31):9219-9223
Ceric ammonium nitrate (CAN) or CeIV(NH4)2(NO3)6 is often used in artificial water oxidation and generally considered to be an outer‐sphere oxidant. Herein we report the spectroscopic and crystallographic characterization of [(N4Py)FeIII‐O‐CeIV(OH2)(NO3)4]+ ( 3 ), a complex obtained from the reaction of [(N4Py)FeII(NCMe)]2+ with 2 equiv CAN or [(N4Py)FeIV=O]2+ ( 2 ) with CeIII(NO3)3 in MeCN. Surprisingly, the formation of 3 is reversible, the position of the equilibrium being dependent on the MeCN/water ratio of the solvent. These results suggest that the FeIV and CeIV centers have comparable reduction potentials. Moreover, the equilibrium entails a change in iron spin state, from S =1 FeIV in 2 to S =5/2 in 3 , which is found to be facile despite the formal spin‐forbidden nature of this process. This observation suggests that FeIV=O complexes may avail of reaction pathways involving multiple spin states having little or no barrier. 相似文献
9.
Liuqing He Wenbiao Zhang Qijie Mo Wenjie Huang Prof. Dr. Lichun Yang Prof. Dr. Qingsheng Gao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(9):3572-3576
Heterostructured Mo2C-MoOx on carbon cloth (Mo2C-MoOx/CC), as a model of easily oxidized electrocatalysts under ambient conditions, is investigated to uncover surface reconfiguration during the hydrogen evolution reaction (HER). Raman spectroscopy combined with electrochemical tests demonstrates that the MoVI oxides on the surface are in situ reduced to MoIV, accomplishing promoted HER in acidic condition. As indicated by density functional theoretical calculations, the in situ reduced surface with terminal Mo=O moieties can effectively bring the negative ΔGH* on bare Mo2C close to a thermodynamic neutral value, addressing difficult H* desorption toward fast HER kinetics. The optimized Mo2C-MoOx/CC only requires a low overpotential (η10) of 60 mV at −10 mA cm−2 in 1.0 m HClO4, outperforming Mo2C/CC and most non-precious electrocatalysts. In situ surface reconfiguration are shown on W2C-WOx, highlighting the significance to boost various metal-carbides and to identify active sites. 相似文献
10.
Electronic properties of polyoxometalate derivatives [(C2B9H11) M'M5O18]n‐ (M' = TiIV,MoVI, WVI; M = MoVI,WVI): Protonation,Electronic Spectra,and Redox Properties
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Nana Ma Shujun Li Likai Yan Wenyong Wang Yongqing Qiu Guisheng Zhang 《International journal of quantum chemistry》2016,116(5):396-404
Density functional theory is used to study the electronic structures and properties of Lindqvist‐type polyoxometalates‐supported organometallic compounds [LM'M5O18]n– (L = [C2B9H11]2– (Cb), [C5H5]– (Cp); M' = TiIV, MoVI, WVI; M = MoVI, WVI). [(Cb)M'M5O18]n– are a series of novel compounds designed in this work, based on related experiment. The calculated results reveal that the Cb ligand is able to form a σ, 2π triple bond with M', which is similar to the bond character in [(Cp)M'M5O18]n–. However, comparing with the protonation, electronic spectra and redox properties of [(Cp)M'M5O18]n– and [M'M5O19]n–, [(Cb)M'M5O18]n– species show the advantageous electronic properties owning to the superior electron donating ability of the Cb ligand. © 2015 Wiley Periodicals, Inc. 相似文献
11.
Mayilmurugan R Harum BN Volpe M Sax AF Palaniandavar M Mösch-Zanetti NC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(2):704-713
The asymmetric molybdenum(VI) dioxo complexes of the bis(phenolate) ligands 1,4‐bis(2‐hydroxybenzyl)‐1,4‐diazepane, 1,4‐bis(2‐hydroxy‐4‐methylbenzyl)‐1,4‐diazepane, 1,4‐bis(2‐hydroxy‐3,5‐dimethylbenzyl)‐1,4‐diazepane, 1,4‐bis(2‐hydroxy‐3,5‐di‐tert‐butylbenzyl)‐1,4‐diazepane, 1,4‐bis(2‐hydroxy‐4‐flurobenzyl)‐1,4‐diazepane, and 1,4‐bis(2‐hydroxy‐4‐chlorobenzyl)‐1,4‐diazepane (H2(L1)–H2(L6), respectively) have been isolated and studied as functional models for molybdenum oxotransferase enzymes. These complexes have been characterized as asymmetric complexes of type [MoO2(L)] 1–6 by using NMR spectroscopy, mass spectrometry, elemental analysis, and electrochemical methods. The molecular structures of [MoO2(L)] 1–4 have been successfully determined by single‐crystal X‐ray diffraction analyses, which show them to exhibit a distorted octahedral coordination geometry around molybdenum(VI) in an asymmetrical cis‐β configuration. The Mo? Ooxo bond lengths differ only by ≈0.01 Å. Complexes 1 , 2 , 5 , and 6 exhibit two successive MoVI/MoV (E1/2, ?1.141 to ?1.848 V) and MoV/MoIV (E1/2, ?1.531 to ?2.114 V) redox processes. However, only the MoVI/MoV redox couple was observed for 3 and 4 , suggesting that the subsequent reduction of the molybdenum(V) species is difficult. Complexes 1 , 2 , 5 , and 6 elicit efficient catalytic oxygen‐atom transfer (OAT) from dimethylsulfoxide (DMSO) to PMe3 at 65 °C at a significantly faster rate than the symmetric molybdenum(VI) complexes of the analogous linear bis(phenolate) ligands known so far to exhibit OAT reactions at a higher temperature (130 °C). However, complexes 3 and 4 fail to perform the OAT reaction from DMSO to PMe3 at 65 °C. DFT/B3LYP calculations on the OAT mechanism reveal a strong trans effect. 相似文献
12.
Ning Li Jiang Liu Jing‐Jing Liu Long‐Zhang Dong Shun‐Li Li Bao‐Xia Dong Yu‐He Kan Ya‐Qian Lan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(48):17420-17424
Over the past 200 years, the most famous and important heteroatom Keggin architecture in polyoxometalates has only been synthesized with Mo, W, V, or Nb. Now, the self‐assembly of two phosphate (PO43?)‐centered polyoxo‐titanium clusters (PTCs) is presented, PTi16 and PTi12, which display classic heteroatom Keggin and its trivacant structures, respectively. Because TiIV has lower oxidate state and larger ionic radius than MoVI, WVI, VV, and NbV, additional TiIV centres in these PTCs are used to stabilize the resultant heteroatom Keggin structures, as demonstrated by the cooresponding theoretical calculation results. These photoactive PTCs can be utilized as efficient photocatalysts for highly selective CO2‐to‐HCOOH conversion. This new discovery indicates that the classic heteroatom Keggin family can be assembled with Ti, thus opening a research avenue for the development of PTC chemistry. 相似文献
13.
Xinghui Qi Sbastien Pillet Coen de Graaf Micha Magott El‐Eulmi Bendeif Philippe Guionneau Mathieu Rouzires Valrie Marvaud Olaf Stefaczyk Dawid Pinkowicz Corine Mathonire 《Angewandte Chemie (International ed. in English)》2020,59(8):3117-3121
The photoinduced properties of the octacoordinated complex K4MoIV(CN)8?2 H2O were studied by theoretical calculations, crystallography, and optical and magnetic measurements. The crystal structure recorded at 10 K after blue light irradiation reveals an heptacoordinated Mo(CN)7 species originating from the light‐induced cleavage of one Mo?CN bond, concomitant with the photoinduced formation of a paramagnetic signal. When this complex is heated to 70 K, it returns to its original diamagnetic ground state, demonstrating full reversibility. The photomagnetic properties show a partial conversion into a triplet state possessing significant magnetic anisotropy, which is in agreement with theoretical studies. Inspired by these results, we isolated the new compound [K(crypt‐222)]3[MoIV(CN)7]?3 CH3CN using a photochemical pathway, confirming that photodissociation leads to a stable heptacyanomolybdate(IV) species in solution. 相似文献
14.
M. Nieves Corella‐Ochoa Dr. Haralampos N. Miras Dr. De‐Liang Long Prof. Leroy Cronin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(43):13743-13754
Five mixed‐metal mixed‐valence Mo/V polyoxoanions, templated by the pyramidal SeO32? heteroanion have been isolated: K10[MoVI12VV10O58(SeO3)8]?18 H2O ( 1 ), K7[MoVI11VV5VIV2O52(SeO3)]?31 H2O ( 2 ), (NH4)7K3[MoVI11VV5VIV2O52(SeO3)(MoV6VV‐ O22)]?40 H2O ( 3 ), (NH4)19K3[MoVI20VV12VIV4O99(SeO3)10]?36 H2O ( 4 ) and [Na3(H2O)5{Mo18?xVxO52(SeO3)} {Mo9?yVyO24(SeO3)4}] ( 5 ). All five compounds were characterised by single‐crystal X‐ray structure analysis, TGA, UV/Vis and FT‐IR spectroscopy, redox titrations, and elemental and flame atomic absorption spectroscopy (FAAS) analysis. X‐ray studies revealed two novel coordination modes for the selenite anion in compounds 1 and 4 showing η,μ and μ,μ coordination motifs. Compounds 1 and 2 were characterised in solution by using high‐resolution ESI‐MS. The ESI‐MS spectra of these compounds revealed characteristic patterns showing distribution envelopes corresponding to 2? and 3? anionic charge states. Also, the isolation of these compounds shows that it may be possible to direct the self‐assembly process of the mixed‐metal systems by controlling the interplay between the cation “shrink‐wrapping” effect, the non‐conventional geometry of the selenite anion and fine adjustment of the experimental variables. Also a detailed IR spectroscopic analysis unveiled a simple way to identify the type of coordination mode of the selenite anions present in POM‐based architectures. 相似文献
15.
Dr. Maria F. Espada Soukaina Bennaamane Dr. Qian Liao Dr. Nathalie Saffon‐Merceron Dr. Stéphane Massou Dr. Eric Clot Dr. Noel Nebra Dr. Marie Fustier‐Boutignon Dr. Nicolas Mézailles 《Angewandte Chemie (International ed. in English)》2018,57(39):12865-12868
Intermolecular, stepwise functionalization by BH bonds of a (triphosphine)MoIV–nitrido complex generated by N2 splitting is reported. The imido–hydride and di‐hydride–amido MoIV complexes have been isolated and characterized. Addition of PinBH to the [Mo(H)2(N(BPin)2)]+ complex at room temperature results in the liberation of borylamines from the metal center. 相似文献
16.
The photolysis of MoCl4(MeCN)2 in MeCN in the presence of small amounts of H2O proceeds according to the equation MoIVCl4·H2OMoVIOCl4 + H2. It is suggested that a ligand field excited state of MoCl4(H2O)
n
, which is initially populated by light absorption, is deactivated to a reactive metal-to-ligand (MoIVH2O) charge transfer state. 相似文献
17.
A photochemical method for the preparation of K6[Mo6[Mo2IVMoIV(CN)8O6]2H2O is discussed. The synthesis of this complex was achieved by photolysing aqueous solutions of K4Mo(CN)8 in contact with atmospheric oxygen. 相似文献
18.
The binaphthyl macrocyclic ligand, N,N′-diethyl-[3,3′-(2,2′-dihydroxy-1,1′-binaphthyl)carboxamide]-2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylic acid (DDCDB),
has been synthesized and investigated. The ligand (DDCDB) and its metal complexes involving CuII, ZnII, UO
2
II
, ThIV, CeIII, MoVI and WVI ions have been prepared and characterized by spectral (i.r., u.v.–vis.), elemental analyses, magnetic moments and thermal
analyses measurements. DDCDB behaves as a tridentate ligand towards CuII, ZnII and UO
2
II
ions coordinating via CO, NH and the deprotonated naphthyl OH groups in a ratio of 2:1 (M:L). On the other hand, DDCDB behaves in a bidentate manner
coordinatingvia the NH and the deprotonated naphthyl OH groups only in case of the ThIV, CeIII, MoVI, and WIV ions and in ratio 1:1 (M:L). Results of thermal measurements confirm the existence of solvent molecules inside and outside
the coordination sphere. ThVI complex has been applied for the hydrolysis of phosphodiester and the results show a significant rate enhancement of ~5.8 million
fold with respect to the auto-hydrolysis of bis-(p-nitrophenyl) phosphate (BNPP) under the same conditions Also, CuII complex accelerates the photodegradation of the hazardous pollutant (acid green dye) in the presence of hydrogen peroxide
by degrading 90% of the dye within 23 min. 相似文献
19.
The crystal structure of La5Mo6O21 (pentalanthanum hexamolybdenum henicosaoxide) is made up of Mo3O13 units containing triangular {MoIV}3 clusters, three distorted MoVO6 octahedral units and six interstitial LaIII atoms. The Mo3O13 unit consists of three edge‐sharing MoIVO6 units involving Mo—Mo bonding. The three MoVO6 octahedra share their corners or edges with each other and with the Mo3O13 units. 相似文献
20.
Oxophthalocyaninato(2–)molybdenum(IV), activated by bromine oxidation prior to use, reacts with fused triphenylphosphine in the presence of bis(triphenylphosphine)iminium bromide to yield linear-bis(triphenylphosphine)iminium trans-dibromophthalocyaninato(2–)molybdate(III), l(PNP)trans[Mo(Br)2pc2?]. It crystallizes triclinic with crystal data: a = 10.506(1) Å, b = 12.436(2) Å, c = 12.918(2) Å, α = 76.186(1)°, β = 67.890(1)°, γ = 68.689(1)°; space group P1 (No. 2); Z = 1. MoIII is in a pseudo-octahedral coordination geometry with the bromo ligands in trans-arrangement. The Mo? Np and Mo? Br distance is 2.043(10) and 2.588(1) Å, respectively. The PNP cation adopts a linear conformation. In the IR spectrum vas(Mo? Br) is observed at 218 cm?1 and vas(P? N) of the linear (P? N? P) core at 1406 cm?1. Cyclic and differential-pulse voltammetry show two quasi-reversible cathodic processes at ?1.15 and ?0.53 V vs. Ag/AgCl. The first is assigned to a phthalocyaninate directed reduction (pc2?/pc3?), while the latter arises from a Mo directed reduction (MoIII/MoII). Spectral monitoring confirms the reversible MoIII/MoII reduction. Two quasi-reversible anodic processes at 0.60 and 1.27 V are assigned to the successive Mo directed oxidation with redox couples MoIII/MoIV and MoIV/MoV. For the first time, three very intense spin-allowed trip-quartet transitions are observed in the electronic absorption spectra at 7140 (TQI), 16890 (TQ2) and 18700 cm?1 (TQ3) together with a sing-quartet transition at 15850 cm?1 and characteristic ?Q”? region with maximum at 28500 cm?1 and ?N”? region at 37400 cm?1. All electronic excitations are of comparable intensity. A prominent low temperature emission at 6690 cm?1 is assigned to a spin-forbidden trip-sextet. 相似文献