Different delocalized ranges in mixed valence cyanido-metal-bridged Fe-Ru-Fe complexes controlled by terminal ligand substitution modification.

In order to investigate the properties of metal to metal charge transfer (MMCT) influenced by the relative energy level between the bridging unit and the terminal unit, two groups of heterotrimetallic cyanido-metal-bridged complexes, trans-[Cp(dppe)Fe-CN-Ru(MeOpy)4-NC-Fe(dppe)Cp][X]n (1[X]n; n = 2, 3, or 4; X = PF6 or BF4) (Cp = cyclopentadiene, dppe = 1,2-bis(diphenylphosphino)ethane, MeOpy = 4-methoxypyridine) and [Cp*(dppe)Fe-CN-Ru(MeOpy)4-NC-Fe(dppe)Cp*] [X]n (2[X]n; Cp* = 1,2,3,4,5-pentamethylcyclopentadiene; n = 2, 3, or 4; X = PF6 or BF4) were synthesized and fully characterized. The crystallography data suggest different oxidation sites in the ground state for one-electron oxidation products 13+ and 23+, and the electrochemical and Mössbauer spectra suggest that in the one-electron oxidation compounds 13+, the charge is delocalized all along the trimetal backbone Fe-Ru-Fe, while in 23+, the charge is rather delocalized between the two metal parts Fe-Ru. Further oxidation of N3+ gives N4+ (N = 1 or 2), during which a spin transfer towards the terminal units is observed in both series.

Metal-Metal Charge Transfer Properties of a Series of Trinuclear Fe2 Ru and Corresponding Pentanuclear Fe2 Ru2 Ag Cyanido-Bridged Complexes.

A series of trimetallic cyanidometal-bridged compounds [Men Cp(dppe)FeII -(µ-NC)-RuII (MeOpy)4 -(µ-CN)-FeII (dppe)CpMen ] - [PF6 ]2 (N[PF6 ]2 , n=0, N =1; n=1, N=2; n=3, N=3; Cp=cyclopentadiene, dppe=1,2-bis(diphenylphosphino)ethane, MeOpy=4-methoxypyridine) and their one- and two-electron oxidized compounds N3+ and N4+ were synthesized and characterized. Meanwhile, a series of corresponding linear cyanido-bridged pentanuclear compounds [Men Cp(dppe)FeIII -(µ-NC)-RuII (MeOpy)4 -(µ-NC)-AgI -(µ-CN)-RuII (MeOpy)4 -(µ-CN)-FeIII (dppe)CpMen ][BF4 ]5 (M[BF4 ]5 , n=0, M=4; n=1, M=5; n=3, M=6) were also obtained and well characterized. The investigations suggest that in the trinuclear system there exists remote interaction between the two Fe centers, but no significant interactions exist across the central silver unit between the metals on the two sides of the silver center in the pentanuclear system. In both the trinuclear N4+ and the pentanuclear M5+ complexes, there exists the neighboring RuII →FeIII MM'CT transitions, and the MM'CT energy in the corresponding trinuclear system is higher than those in the pentanuclear system in which no remote metal-metal interaction occurs. Meanwhile, as the substituted methyl groups on the cyclopentadiene increases, the redox potential of the ruthenium in the trinuclear N4+ series increases, but that in the pentanuclear M5+ complexes decreases.

Electronic Transition and Magnetic Coupling Regulation in Trimetallic Complexes Featuring a New Bridging Ligand Obtained by Oxidative Addition.

A series of trimetallic complexes [FeIII(µ-L)(py)]2MII(py)n (n = 2, MII = MnII, 1; FeII, 2; CoII, 3; ZnII, 4; n = 3, MII = CdII, 5) with a new bridging ligand L4- (deprotonated 1,2-N1,N2-bis(2-mercaptoanil) oxalimidic acid) were synthesized and fully characterized by elemental analysis, single-crystal X-ray crystallography, IR, and Mössbauer spectra. Interestingly, the bridging ligand was obtained by oxidative addition of the (gma•)3- ligand from the mononuclear precursor Fe(gma)py (gma = glyoxal-bis(2-mercaptoanil)). In the obtained complexes, the bridging ligand L4- coordinates to the terminal FeIII ions (intermediate-spin with SFe = 3/2) by the N, S atoms, and coordinate to the central metal MII ion by the four O atoms. The resonance structure of the bridging ligand can be described as the two 4π-electron delocalized systems connected by one single-bond (C1-C2), which is different from the electronic structure of the precursor Fe(gma)py. Remarkably, the magnetic coupling interaction can be regulated through the central metal. The ferromagnetic coupling constant J gradually decreases as MII changes from FeII to CoII and MnII, while the paramagnetic behaviors are presented when MII = ZnII and CdII, confirmed by the magnetic susceptibility measurements and further supported by using the PHI program. Furthermore, the bridging ligand to the terminal FeIII charge transfer (LMCT) transitions emerged in all complexes but the central FeII to terminal FeIII charge transfer (MMCT) only presented in complex 2, strongly supported by the UV/vis-NIR electronic spectra and TDDFT calculations.

Influence of the CN Orientation on the Degree of Electron Delocalization of Ru-Ru-Ru Mixed-Valent Complexes.

Investigations on mixed-valent complexes in the Class II/Class III frontier have been a particularly interesting issue due to their special electron delocalization. In this work, a pair of cyanidometal-/isocyanidometal-bridged Ru-Ru-Ru compounds, cis-[Cp(dppe)Ru-B-Ru(dppe)Cp]2+ (B = NCRu(bpy)2CN, 12+; B = CNRu(bpy)2NC, 22+; Cp = 1,3-cyclopentadienyl, dppe = 1,2-bis(diphenlyphosphine)ethane, bpy = 2,2'-bipyridine), and one-electron oxidized 13+ and 23+ were synthesized and well characterized. For the two-electron oxidized 14+ and 24+, their Fourier transform infrared (FTIR) and UV-vis-NIR spectra were investigated by employing spectroelectrochemical methods. The time-dependent density-functional theory (TDDFT) calculations and the experimental results indicate that the one-/two-electron oxidized mixed-valent compounds belong to Class II-III systems.

Investigation of the electron transfer properties between metal centers in binuclear and trinuclear cyanido-bridged mixed valence complexes with cis/trans-configuration.

To investigate the electron transfer properties between metal centers and their influencing factors in binuclear and trinuclear cyanido-bridged mixed valence complexes with cis/trans-configuration, binuclear cis-[Cp(dppe)Fe(µ-NC)Ru(5,5'-dmbpy)2(µ-CN)][PF6]n (cis-1[PF6]n, n = 1, 2) and trinuclear cis/trans-[Cp(dppe)Fe(µ-NC)Ru(5,5'-dmbpy)2(µ-CN)Fe(dppe)Cp][PF6]n (cis/trans-2[PF6]n, n = 2, 3, 4) (Cp = 1,3-cyclopentadiene, dppe = 1,2-bis(diphenylphosphino)ethane, 5,5'-dmbpy = 5,5'-dimethyl-2,2'-bipyridyl) cyanido-bridged complexes were synthesized and well characterized. The experimental results indicate that the presence of the other terminal fragment Cp(dppe)FeIII in cis-2[PF6]4 results in higher MMCT energy than that of cis-1[PF6]2. In addition, the trans-configuration is more conducive to electron transfer between metal centers than the cis-configuration in trinuclear cyanido-bridged mixed valence complexes. Moreover, these mixed valence complexes cis-1[PF6]2 and cis/trans-2[PF6]n (n = 3, 4) could be assigned to Class II systems according to Robin and Day.

Effects of cis/trans-Configuration and Ligand Substitution of the Cyanidometal Bridge on Metal to Metal Charge Transfer Properties in Mixed Valence Complexes.

To investigate the effects of cis/trans-configuration of the cyanidometal bridge and the electron donating ability of the auxiliary ligand on the cyanidometal bridge on metal to metal charge transfer (MMCT) in cyanidometal-bridged mixed valence compounds, two groups of trinuclear cyanidometal-bridged compounds cis/trans-[Cp(dppe)Fe(µ-NC)Ru(4,4'-dmbpy)2 (µ-CN)Fe(dppe)Cp][PF6 ]n (n=2 (cis/trans-1[PF6 ]2 ), 3 (cis/trans-1[PF6 ]3 ), 4 (cis/trans-1[PF6 ]4 )) and cis/trans-[Cp(dppe)Fe(µ-NC)Ru(bpy)2 (µ-CN)Fe(dppe)Cp][PF6 ]3 (cis/trans-2[PF6 ]3 ) were synthesized and fully characterized. The experimental results indicate that for these one- and two-electron oxidation mixed valence compounds, the trans-configuration compounds are more beneficial for MMCT than the cis-configuration compounds, and increasing the electron donating ability of the auxiliary ligand on the cyanidometal bridge is also conductive to MMCT. Moreover, compounds cis/trans-1[PF6 ]n (n=3, 4) and cis/trans-2[PF6 ]3 belong to localized compounds by analyzing the experimental characterization results, supported by the TDDFT calculations.

Influence of Fine Ligand Substitution Modification of the Isocyanidometal Bridge on Metal-to-Metal Charge Transfer Properties in Class II-III Mixed Valence Complexes.

The synthesis and characterization of Class II-III mixed valence complexes have been an interesting topic due to their special intermediate behaviour between localized and delocalized mixed valence complexes. To investigate the influence of the isocyanidometal bridge on metal-to-metal charge transfer (MMCT) properties, a family of new isocyanidometal-bridged complexes and their one-electron oxidation products cis-[Cp(dppe)Fe-CN-Ru(L)2 -NC-Fe(dppe)Cp][PF6 ]n (n=2, 3) (Cp=1,3-cyclopentadiene, dppe=1,2-bis(diphenylphosphino)ethane, L=2,2'-bipyridine (bpy, 1[PF6 ]n ), 5,5'-dimethyl-2,2'-bipyridyl (5,5'-dmbpy, 2[PF6 ]n ) and 4,4'-dimethyl-2,2'-bipyridyl (4,4'-dmbpy, 3[PF6 ]n )) have been synthesized and fully characterized. The experimental results suggest that all the one-electron oxidation products may belong to Class II-III mixed valence complexes, supported by TDDFT calculations. With the change of the substituents of the bipyridyl ligand on the Ru centre from H, 5,5'-dimethyl to 4,4'-dimethyl, the energy of MMCT for the one-electron oxidation complexes changes in the order: 13+ <23+ <33+ , and that for the two-electron oxidation complexes decreases in the order 14+ >34+ >24+ . The potential splitting (ΔE1/2 (2)) between the two terminal Fe centres for N[PF6 ]2 are the largest potential splitting for the cyanido-bridged complexes reported so far. This work shows that the smaller potential difference between the bridging and the terminal metal centres would result in the more delocalized mixed valence complex.

Tuning metal to metal charge transfer properties in cyanidometal-bridged complexes by changing the auxiliary ligand on the bridge.

In order to investigate the influence of the auxiliary ligand of the cyanidometal bridge on metal to metal charge transfer (MMCT) in cyanidometal-bridged complexes, two groups of heterotrimetallic cyanidometal-bridged complexes, trans-[Cp*(dppe)Fe-NC-Ru(L)2-CN-Fe(dppe)Cp*][PF6]n (L = bpy, 1(PF6)n; L = 4,4'-dmbpy, 2(PF6)n; n = 2, 3, 4) (Cp* = 1,2,3,4,5-pentamethylcyclopentadiene, dppe = 1,2-bis(diphenylphosphino)ethane, bpy = 2,2'-bipyridine, 4,4'-dmbpy = 4,4'-dimethyl-2,2'-bipyridyl) were synthesized and fully characterized. The MMCT of the one-electron oxidation mixed valence complexes is mainly attributed to RuII and FeII → FeIII MMCT transitions, and the MMCT of the two-electron oxidation complexes is mainly attributed to RuII → FeIII MMCT transitions. The energy of the MMCT of the four complexes decreases with the increase of the electron donating ability of the auxiliary ligand of the cyanidometal bridge. The IR, EPR, and Mössbauer spectra, and the solvent independence of MMCT characterizations indicate that the one-electron oxidation mixed valence complexes may belong to Class II-III systems, and the two-electron oxidation complexes may be localized at low temperature but delocalized at room temperature on the EPR timescale.