Interlayer interaction of two-dimensional layered spin crossover complexes [FeIIH3L(Me)][FeIIL(Me)]X (X-=ClO4-, BF4-, PF6-, AsF6-, and SbF6-; H3L(Me)=tris[2-(((2-methylimidazol-4-yl)methylidene)amino)ethyl]amine)

A series of two-dimensional (2D) spin crossover complexes, [FeIIH3L(Me)][FeIIL(Me)]X (X-=ClO4-, BF4-, PF6-, AsF6-, SbF6-) 1-5, have been synthesized, where H3L(Me) denotes an hexadentate N6 tripodlike ligand containing three imidazole groups, tris[2-(((2-methylimidazol-4-yl)methylidene)amino)ethyl]amine. Compounds 1-5 exhibit a two-step (HS-[FeIIH3L(Me)](2+) + HS-[FeIIL(Me)]-) <--> (HS-[FeIIH3L(Me)](2+) + LS-[FeIIL(Me)]-) <--> (LS-[FeIIH3L(Me)](2+) + LS-[FeIIL(Me)]-) spin-transition. The crystal structure of [FeIIH3L(Me)][FeIIL(Me)]PF6 (3) was determined at 295, 200, and 100 K. The structure consists of homochiral extended 2D puckered sheets, in which the complementary [FeIIH3L(Me)](2+) and [FeIIL(Me)]- capped tripodlike components, linked together by imidazole-imidazolate hydrogen bonds, are alternately arrayed in an up-and-down mode. The Fe-N bond distances and angles revealed that the FeII sites of both constituting units are in the high-spin (HS) state at 295 K; at 200 K, the FeII sites of [FeIIH3L(Me)](2+) and [FeIIL(Me)]- are in the HS and low-spin (LS) states, respectively. The FeII sites of both constituting units are in the LS state at 100 K. The size of the counteranion affects significantly the intra- and interlayer interactions leading to modifications of the spin crossover behavior. The onset of the second spin-transition of the ClO4- (1) and BF4- (2) salts adjoins the first spin-transition, while a mixed (HS-[FeIIH3L(Me)](2+) + LS-[FeIIL(Me)]-) spin-state spans a temperature range as wide as 70 K for salts 3-5 with larger counteranions, PF6-, AsF6-, and SbF6-, respectively. Compounds 1 and 2 showed remarkable LIESST (light induced excited spin state trapping) and reverse-LIESST effects, whereas 3-5 showed no remarkable LIESST effect. The interlayer interaction due to the size of the counteranion is an important factor governing the spin crossover behavior and LIESST effect.     

A 2D layered spin crossover complex constructed by NH...Cl- hydrogen bonds: [FeIIH3LMe]Cl.I3 (H3LMe = tris[2-(((2-methylimidazoyl-4-yl)methylidene)amino)ethyl]amine

A 2D layered spin crossover complex, [FeIIH3L(Me)]Cl.I3, has been synthesized from the reaction of FeIIICl3, a tripod ligand (H3LMe = tris[2-(((2-methylimidazoyl-4-yl)methylidene)amino)ethyl]amine), and NaI in methanol. The compound showed an abrupt spin transition between the HS (S = 2) and LS (S = 0) states at T(1/2) = 110 K without hysteresis. The crystal structures of the HS and LS states were determined at 180 and 90 K. A 2D layered structure is composed of NH...Cl- hydrogen bonds between the Cl- ion and three neighboring imidazole groups of [FeIIH3LMe]2+. The green light irradiation at 5 K induced the LIESST effect, and the thermal relaxation process from the HS to LS state showed a sigmoid curve at T > 55 K.     

A new family of spin crossover complexes with a tripod ligand containing three imidazoles: synthesis, characterization, and magnetic properties of [FeIIH3LMe](NO3)2.1.5H2O, [FeIIILMe].3.5H2O, [FeIIH3LMe][FeIILMe]NO3, and [FeIIH3LMe][FeIIILMe](NO3)2 (H3LMe) = Tris[2-(((2-methylimidazol-4-yl)methylidene)amino)ethyl]amine)

A new family of spin crossover complexes, [Fe(II)H(3)L(Me)](NO(3))(2).1.5H(2)O (1), [Fe(III)L(Me)].3.5H(2)O (2), [Fe(II)H(3)L(Me)][Fe(II)L(Me)]NO(3) (3), and [Fe(II)H(3)L(Me)][Fe(III)L(Me)](NO(3))(2) (4), has been synthesized and characterized, where H(3)L(Me) denotes a hexadentate N(6) tripod ligand containing three imidazole groups, tris[2-(((2-methylimidazol-4-yl)methylidene)amino)ethyl]amine. It was found that the spin and oxidation states of the iron complexes with this tripod ligand are tuned by the degree of deprotonation of the imidazole groups and by the 2-methyl imidazole substituent. Magnetic susceptibility and M?ssbauer studies revealed that 1 is an HS-Fe(II) complex, 2 exhibits a spin equilibrium between HS and LS-Fe(III), 3 exhibits a two-step spin transition, where the component [Fe(II)L(Me)](-) with the deprotonated ligand participates in the spin transition process in the higher temperature range and the component [Fe(II)H(3)L(Me)](2+) with the neutral ligand participates in the spin transition process in the lower temperature range, and 4 exhibits spin transition of both the Fe(II) and Fe(III) sites. The crystal structure of 3 consists of homochiral extended 2D puckered sheets, in which the capped tripodlike components [Fe(II)H(3)L(Me)](2+) and [Fe(II)L(Me)](-) are alternately arrayed in an up-and-down mode and are linked by the imidazole-imidazolate hydrogen bonds. Furthermore, the adjacent 2D homochiral sheets are stacked in the crystal lattice yielding a conglomerate as confirmed by the enantiomeric circular dichorism spectra. Compounds 3 and 4 showed the LIESST (light induced excited spin state trapping) and reverse-LIESST effects upon irradiation with green and red light, respectively.     

Behaviour of [PdH(dppe)2]X (X=CF3SO3-, SbF6-, BF4-) as proton or hydride donor: relevance to catalysis

The synthesis, characterization and properties of [PdH(dppe)(2)](+)CF(3)SO(3) (-).0.125 THF (1; dppe=1,2-bis(diphenylphosphanyl)ethane) and its SbF(6) (-) (1') and BF(4) (-) (1") analogues, the missing members of the [MH(dppe)(2)](+)X(-) (M=Ni, Pd, Pt) family, are described. The Pd hydrides are not stable in solution and can react as proton or hydride donors with formation of dihydrogen, [Pd(dppe)(2)](2+) and [Pd(dppe)(2)]. Complexes 1-1" react with carbocations and carbanions by transferring a hydride and a proton, respectively. Such H(-) or H(+) transfer occurs also towards unsaturated compounds, for example, hydrogenation of a C=C double bond. Accordingly, 1 can hydrogenate methyl acrylate to methyl propionate. Complex 1" is an effective (hourly turnover frequency=16) and very selective (100 %) catalyst for the hydrogenation of cyclohexen-2-one to cyclohexanone with dihydrogen under mild conditions. Density functional calculations coupled with a dielectric continuum model were carried out to compute the energetics of the hydride/proton transfer reactions, which were used to rationalize some of the experimental findings. Theory provides strong support for the thermodynamic and kinetic viability of a tetracoordinate Pd complex as an intermediate in the reactions.     

New organic superconductors beta-(BDA-TTP)2X [BDA-TTP + 2,5-bis(1,3-dithian-2ylidene)-1,3,4,6-tetrathiapentalene; X(-) = SbF6(-), AsF6(-), and PF6(-)].

The synthesis, electrochemical properties, and molecular structure of a new pi-electron donor, 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP), is described. In contrast to the hitherto-known tetrachalcogenafulvalene pi-donors providing organic superconductors, this donor contains only the bis-fused 1,3-dithiole-2-ylidene unit as a pi-electron system, yet produces a series of ambient-pressure superconductors beta-(BDA-TTP)2X [X = SbF6 (magnetic T(c) = 6.9 K, resistive T(c) = 7.5 K), AsF6 (magnetic T(c) = 5.9 K, resistive T(c) = 5.8 K), and PF6 (magnetic T(c) = 5.9 K)], which are isostructural. The values of the intermolecular overlap integrals calculated on the donor layers of these superconductors suggest a two-dimensional (2D) electronic structure with loose donor packing. Tight-binding band calculations also indicate that these superconductors have the 2D band dispersion relations and closed Fermi surfaces.     

Self-assembly of coordination polymers from AgX (X = SbF(6)(-), PF(6)(-), and CF(3)SO(3)(-)) and oxadiazole-containing ligands

The coordination chemistry of the oxadiazole-containing rigid bidentate ligands 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (L1), 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (L2), and 2,5-bis(3-aminophenyl)-1,3,4-oxadiazole (L3) with inorganic Ag(I) salts has been investigated. Four new coordination polymers (1, 2, 3, and 5) and one new bimetallic macrocyclic supramolecular complex (4) were synthesized from solution reactions of L1-L3 with inorganic Ag(I) salts, respectively. Compounds [[Ag(L1)]SbF(6)](n) (1) (1, monoclinic, P2(1)/c, a = 6.6846(4) A, b = 27.1113(15) A, c = 8.6802(5) A, beta = 94.1080(10) degrees, Z = 4) and [[Ag(L1)]PF(6)](n) (2) (2, monoclinic, P2(1)/c, a = 6.6753(3) A, b = 27.2824(14) A, c = 8.2932(4) A, beta = 94.6030(10) degrees, Z = 4) were obtained from the reactions of L1 with AgSbF(6) and AgPF(6) in a CH(2)Cl(2)/CH(3)OH mixed solvent system, respectively. Compounds 1 and 2 are isostructural and feature a novel two-dimensional zeolite-like net with two different individual rings. [[Ag(L2)]SbF(6)](n) (3) (3, monoclinic, P2(1)/c, a = 5.5677(3) A, b = 17.3378(9) A, c = 15.6640(8) A, beta = 94.4100(10) degrees, Z = 2) and [Ag(2)(L2)(2)](SbF(6))(2) (4) (4, triclinic, P1, a = 8.7221(5) A, b = 9.2008(6) A, c = 10.7686(7) A, alpha = 70.6270(10) degrees, beta = 75.7670(10) degrees, gamma = 73.7560(10) degrees, Z = 1) were obtained from one-pot reaction of L2 with AgSbF(6) in a CH(2)Cl(2)/CH(3)OH mixed solvent system. Compound 3 features a one-dimensional chain pattern, while compound 4 adopts a novel bimetallic macrocyclic structural motif which consists of Ag(2)(L2)(2) ringlike units (crystallographic dimensions, 8.06 x 7.42 A(2)). [[Ag(L3)]SO(3)CF(3)](n) (5) is generated from L3 and AgSO(3)CF(3) in a CH(2)Cl(2)/CH(3)OH mixed solvent system and crystallizes in the unusual space group Pbcn, with a = 9.8861(5) A, b = 20.2580(10) A, c = 17.5517(8) A, Z = 8. It adopts novel two-dimensional sheets that are cross-linked to each other by strong interlayer N-H...O hydrogen bonding interactions into a novel H-bonded three-dimensional network.     

Rates of electronic excitation hopping in anisotropic ionic crystals of [Ru(2,2'-bipyridine)3]X2 (X = ClO4-, PF6-, SbF6-); Monte Carlo simulation of single- and multi-exponential emission decays

Emission decays of triplet metal-to-ligand charge transfer states in anisotropic crystals of [Ru(1 - x)Os(x)(bpy)(3)]X(2) (bpy = 2,2'-bipyridine, X = PF(6)-, ClO(4)-, SbF(6)-, and 0.115 > x > 0.001) at approximately 300 K were measured by means of time-correlated single-photon counting. Rates of excitation hopping calculated on the basis of an interaction between transition dipoles of a donor cation and an acceptor cation are insufficient to simulate the single-exponential decays (x = 0.0099) and the multiexponential decays (x = 0.060 and 0.115) of the PF(6)- salt crystals. A limiting rate of excitation hopping to an imaginary cation at the van der Waals distance via a super-exchange interaction between d orbitals through the bpy ligands was determined to be 0.83 x 10(10) s(-1) on average by means of a step-by-step Monte Carlo simulation, assuming an distance-attenuation factor, beta, of the exchange interaction of 10 nm-1. The total rate of excitation hopping via both a dipole-dipole mechanism and a super-exchange mechanism to the neighboring sites of the cation was calculated to be 5.4 x 10(9) s(-1) for the PF(6)- crystal. Anisotropic diffusion constants estimated from the hopping rates and lengths in the PF(6)- crystal are 9.3 x 10(-6), 9.1 x 10(-6), and 1.4 x 10(-6) cm(2)s(-1) along the a axis, the b axis, and the c axis, respectively, which are compared with an isotropic diffusion constant, 1.3 x 10(-6) cm(2) s(-1), estimated from the pseudo-bimolecular rate constant of excitation transfer to [Os(bpy)(3)](2+), using an isotropic Smoluchowski equation. A multiexponential emission decay of [Ru(0.885)Os(0.115)(bpy)(3)](PF(6))(2) was also simulated to determined the limiting rate of excitation transfer to [Os(bpy)(3)](2+) at the van der Waals distance (2.6 x 10(11) s(-1)). The magnitude of beta determined is 6.5 and 11.5 nm(-1) for the ClO(4)- and the SbF(6)- salt crystals, respectively, on reference to that of beta (10 nm(-1)) for the PF(6)- salt crystal.     

Die Dihydrate [Me6X]X · 2H2O mit Me = Mo,W; X = Cl,Br, J

The dihydrates mentioned in the title are particularly suitable for the characterisation of the [Me₆X] complex groups. Reported are the preparation of known and unknown compounds of this type. Lattice constants are given. The compounds are isotypic with the known structure of [Mo₆Br₈]Br₄ · 2 H₂O. Moreover, infrared data and the thermal decomposition of the compounds are reported.     

Zum Reaktionsverhalten der Tris(dialkylthiophosphinyl)phosphane – Die Kristallstruktur von [Ag{O[P(S)Me2]2}2] [AsF6]

Reactivity of Tris(dialkylthiophosphinyl)phosphines – Crystal Structure of [Ag{O[P(S)Me₂]₂}₂][AsF₆] In contrast to tris(dialkylphosphoryl)phosphines the reaction of tris(dimethylthiophosphinyl)phosphine with transition metal hexafluoroarsenates of the type [M(SO₂)_m [AsF₆]_n (M = Ag, m = 0, n = 1; M = Fe, Cd, m = n = 2) forms no molecular 2 : 1-complexes but polymeric products. The silver polymer is transformed into [Ag{O[P(S)Me₂]₂}₂][AsF₆], which is also formed by the reaction of Ag[AsF₆] with O[P(S)Me₂]₂. It crystallizes in the space group P1 with a = 862.5(2), b = 1 241.4(2), c = 1 254.0(3)pm, α = 80.34(1), β = 101.99(6), γ= 73.75(1)° (at 20°C) and Z = 2. The central silver atom is surrounded by four sulphur atoms in a slighly distorted tetrahedron. The average (Ag? S) and (P? S) bond lengthes are 259.4(2) pm and 194.9(2)pm, respectively.     

Mesomorphism of ionic allylpalladium(II) complexes containing pz(R2)py as ligands and [BF4]-, [PF6]- or [CF3SO3]- as counteranions

The synthesis and thermal behaviour is reported of some ionic liquid-crystalline complexes formed when a mesogenic, two-chained, pyrazolylpyridine ligand is bound to a eta3-allylpalladium(II) fragment. The phase behaviour of the complexes is dominated by the formation of the SmA phase and, while the stability of the crystal phase appears to be controlled by intermolecular solid-state interactions, the stability of the liquid crystal phases is controlled by the length of the ligand alkoxy chains. Some of the complexes also show a complex polymorphism leading to the observation of double-melting behaviour.     

Darstellung der Iminiumsalze CF3?NXCF2+MF6− (X = CH3, F und M = As,Sb) und CF3?NCl = CF2+ AsF6−

Preparation of the Iminium Salts CF₃? NX?CF₂⁺MF₆^? (X = CH₃, F and M = As, Sb) and CF₃? NCl?CF₂⁺ AsF₆^? The preparation of the iminiumsalts CF₃? NX?CF₂⁺ MF₆^? (X = CH₃, F and M = As, Sb) and CF₃? NCl?CF₂⁺ AsF₆^? is reported. The salts were characterized by NMR and infrared spectroscopy. CF₃? NCH₃?CF₂⁺MF₆^? decompose into MF₅ and (CF₃)₂NCH₃.     

Phase separation in liquid crystalline mesophases of [Co(H2O)6]X2:P65 Systems (X = NO3-, Cl-, or ClO4-)

Transition-metal aqua complex salts [M(H2O)6]X2 (where M is Mn(II), Co(II), Ni(II), Zn(II), or Cd(II) and X is NO3-, Cl-, or ClO4-) can be dissolved in triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) copolymers (Pluronics, such as P65) to form homogeneous liquid crystalline (LC) mesophases. However, the [Co(H2O)6]X2:P65 LC mesophases slowly undergo phase separation into a disordered ion-free phase and an ordered ion-rich LC mesophase. The phase separation also takes place in the two-salt systems [Co(H2O)6](NO3):[Co(H2O)6](ClO4)2:P65 in which the ion-free disordered domains separate out from the initially ordered homogeneous mesophase. The phase separation results in a physical mixture of a hexagonal nitrate-rich and cubic perchlorate-rich LC and disordered ion-free domains in the mixed salt systems. The driving force in the phase separation in the [Co(H2O)6]X2:P65 system is Co(II)-catalyzed aerobic oxidation of P65 into ester and/or other oxidation products. The separation of ions in the [Co(H2O)6](NO3)2:[Co(H2O)6](ClO4)2:P65 system is related to the mesostructures of the two-salt systems that are different, hexagonal in the [Co(H2O)6](NO3)2:P65 system and cubic in the [Co(H2O)6](ClO4)2:P65 system. There is no visible phase separation in the other transition-metal salt:P65 systems. The phase separation in the [Co(H2O)6]X2:P65 systems can also be eliminated by keeping the mesophase under a N2 atmosphere.     

Highly luminescent complexes [Mo6X8(n-C3F7COO)6]2- (X=Br, I)

New complexes (Bu(4)N)(2)[Mo(6)X(8)(n-C(3)F(7)COO)(6)] (X = Br, I) display extraordinarily bright long-lived red phosphorescence both in solution and solid phases, with the highest emission quantum yields and the longest emission lifetimes among hexanuclear metal cluster complexes of Mo, W and Re, hitherto reported.     

N,N-coordinated pi radical anions of S-methyl-1-phenyl-isothiosemicarbazide in two five-coordinate ferric complexes [Fe III(L Me*)(2)X] (X = CH3S-, Cl-)

The reaction between [Fe(III)(dmf)(6)](ClO(4))(3) and the ligand S-methyl-1-phenyl-isothiosemicarbazide, H(2)[L(Me)], and triethylamine (1:3:6) in methanol under an argon blanketing atmosphere at elevated temperatures (reflux) yields a purple solution from which upon cooling to 20 degrees C dark green crystals of [Fe(III)(L(Me)(*))(2)(SCH(3))] (1) were obtained in 15% yield. From a similar reaction mixture using FeCl(3) as starting material in the solvent acetone under anaerobic conditions at -80 degrees C, dark green crystals of [Fe(III)(L(Me)(*))(2)Cl] (2) were obtained in 21% yield. The structures of complexes 1 and 2 have been determined by single-crystal X-ray crystallography at 100 K. Both complexes are five-coordinate square base pyramidal ferric species containing two N,N-coordinated, monoanionic pi radicals, (L(Me)(*))(1)(-), of the parent S-methyl-1-phenyl-isothiosemicarbazide(2-) dianion in the basal positions whereas the axial position is occupied by methylthiolate in 1 and chloride in 2, respectively. The electronic structure of both species has been elucidated by their electronic spectra, magnetic properties, and X-band EPR and M?ssbauer spectra. Both possess an S(t) = (1)/(2) ground state which is attained via an antiferromagnetic coupling between the spins of an intermediate spin ferric ion (S(Fe) = (3)/(2)) and two ligand pi radical anions (S(rad) = (1)/(2)).     

Temperature dependent emission of hexarhenium(III) clusters [Re6(mu3-S)8X6]4- (X = Cl-, Br-, and I-): analysis by four excited triplet-state sublevels

Temperature (T) dependences of the emission spectra and lifetimes of hexarhenium(III) clusters, [Re6(mu3-S)8X6]4- (X = Cl-, Br-, and I-), in the crystalline phase were studied in detail. An increase in T from 30 to 70 K resulted in a red-shift of the emission spectrum of the cluster, while an increase in T above 70 K gave rise to a gradual blue-shift of the spectrum. On the other hand, the emission lifetime of the cluster decreased sharply from 30-40 to 13-20 micros on going from 30 to 60 K, while that decreased gradually above 60 K: 5-6 micros at 290 K. Such emission behaviors of [Re6(mu3-S)8X6]4- were observed irrespective of X. The results were then analyzed by assuming the contributions of the emissions from the lowest-energy excited triplet-state sublevels. The present study demonstrated that the characteristic T dependent emission spectra and lifetimes of [Re6(mu3-S)8X6]4- were explained reasonably by a single context of the contributions of the emissions from four excited triplet-state sublevels.     

Preparation and Structural Characterization of [CpRu(1,10-phenanthroline)(CH3CN)][X] and Precursor Complexes (X=PF6, BArF,TRISPHAT-N)

Cationic [Ru(η⁵-C₅H₅)(CH₃CN)₃]⁺ complex, tris(acetonitrile)(cyclopentadienyl)ruthenium(II), gives rise to a very rich organometallic chemistry. Combined with diimine ligands, and 1,10-phenanthroline in particular, this system efficiently catalyzes diazo decomposition processes to generate metal-carbenes which undergo a series of original transformations in the presence of Lewis basic substrates. Herein, syntheses and characterizations of [CpRu(Phen)(L)] complexes with (large) lipophilic non-coordinating (PF₆⁻ and BAr_F⁻) and coordinating TRISPHAT-N⁻ anions are reported. Complex [CpRu(η⁶-naphthalene)][BAr_F] ( [1][BAr_F] ) is readily accessible, in high yield, by direct counterion exchange between [1][PF₆] and sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBAr_F) salts. Ligand exchange of [1][BAr_F] in acetonitrile generated stable [Ru(η⁵-C₅H₅)(CH₃CN)₃][BAr_F] ( [2][BAr_F] ) complex in high yield. Then, the desired [CpRu(Phen)(CH₃CN)] ( [3] ) complexes were obtained from either the [1] or [2] complex in the presence of the 1,10-phenanthroline as ligand. For characterization and comparison purposes, the anionic hemilabile ligand TRISPHAT−N (TTN) was introduced on the ruthenium center, from the complex [3][PF₆] , to quantitatively generate the desired complex [CpRu(Phen)(TTN)] ( [4] ) by displacement of the remaining acetonitrile ligand and of the PF₆⁻ anion. Solid state structures of complexes [1][BAr_F] , [2][BAr_F] , [3][BAr_F] , [3][PF₆] and [4] were determined by X-ray diffraction studies and are discussed herein.     

Theoretical studies on blue versus red shifts in diglyme-M+-X- (M=Li, Na, and K and X=CF3SO3, PF6, and (CF3SO2)2N))

Ab initio Hartree-Fock calculations have been used to obtain the electronic structure and the frequencies of normal vibrations in the 1:1:1 solid polymer electrolytes CH3(OCH2CH2)2OCH3-M+-X- (M=Li, Na, and K and X=CF3SO3, PF6, (CF3SO2)2N). These calculations predict stronger binding for the lithium ion toward the ether oxygens of diglyme in these electrolytes. Consequences of diglyme-MX interactions to the infrared spectra have been presented. Natural bond analysis and the electron density topography have been used to explain the direction of the frequency shifts of the normal vibrations of the anions in these electrolytes.     

联吡啶钌配合物[Ru(Htcterpy)X3]3-[X=NCS,CN,Cl]的电子结构和光谱性质的理论研究

利用DFT中的B3LYP方法优化了3个联吡啶钌配合物[Ru(Htcterpy)X3]3-[tcterpy=4,4',4"-tricarboxy-2,2'∶6',2"-terpyridine, X=NCS(1), CN(2), Cl(3)]的基态几何结构, 得到的几何参数与实验结果吻合得很好. 采用TD-DFT方法, 得到了配合物1~3在气态和溶液(乙醇溶液和水溶液)中的激发态电子结构和电子吸收光谱. 利用SCRF方法中的CPCM模型来模拟溶剂化效应. 研究结果表明, 配合物1~3在气态和溶液中的吸收跃迁性质相似, 低能吸收均被指认为MLCT和LLCT的混合跃迁, 高能吸收均被指认为三联吡啶配体内的π→π*跃迁. 溶剂化效应使配合物1~3在溶液中的吸收光谱蓝移.