Novel fused D-A dyad and A-D-A triad incorporating tetrathiafulvalene and p-benzoquinone

Novel fused donor-acceptor dyad (TTF-Q or D-A) and acceptor-donor-acceptor triad (Q-TTF-Q or A-D-A) incorporating the donor tetrathiafulvalene (TTF) and the acceptor p-benzoquinone (Q) have been synthesized. The solution UV-vis spectra of these molecules display a low-energy absorption band that is attributed to an intramolecular charge transfer between both antagonistic units. The presence of reversible oxidation and reduction waves for the donor and acceptor moieties was shown by cyclic voltammetry, in agreement with the ratio TTF/quinone(s) units. The successive generation from these compounds of the cation radical and anion radical obtained upon (electro)chemical oxidation and reduction, respectively, was monitored by optical and ESR spectroscopies. The anion radical Q-TTF-Q(-.) triad was demonstrated to be a class II mixed-valence system with the existence of a temperature-dependent intramolecular electron transfer. The crystallographic tendency of these fused systems to overlap in mixed stacks of alternating A-D-A units is also discussed.     

Concerning the electronic coupling of MoMo quadruple bonds linked by 4,4'-azodibenzoate and comparison with t2g 6-Ru(II) centers by 4,4'-azodiphenylcyanamido ligands

From the reactions between Mo2(O2CtBu)4 and each of terephthalic acid and 4,4'-azodibenzoic acid, the compounds [Mo2(O2CtBu)3]2(mu-O2CC6H4CO2) (1) and [Mo2(O2CtBu)3]2(mu-O2CC6H4N2C6H4CO2) (2) have been made and characterized by spectroscopic and electrochemical methods. Their electronic structures have been examined by computations employing density functional theory on model compounds where HCO2 substitutes for tBuCO2. On the basis of these studies, the two Mo2 units are shown to be only weakly coupled and the mixed-valence ions 1+ and 2+ to be valence-trapped and Class II and I, respectively, on the Robin-Day classification scheme for mixed-valence compounds. These results are compared to t2g6-Ru centers linked by 1,4-dicyanamidobenzene and azo-4,4'-diphenylcyanamido bridges for which the mixed-valence ions [Ru-bridge-Ru]5+ have been previously classified as fully delocalized, Class III [Crutchley et al. Inorg. Chem. 2001, 40, 1189; Inorg. Chem. 2004, 43, 1770], and on the basis of results described herein, it is proposed that the latter complex ion is more likely a mixed-valence organic radical where the bridge is oxidized and not the Ru(2+) centers.     

Optical transitions of symmetrical mixed-valence systems in the Class II-III transition regime

In the Robin and Day classification, mixed-valence systems are characterized as Class I, II or III depending on the strength of the electronic interaction between the oxidized and reduced sites, ranging from essentially zero (Class I), to moderate (Class II), to very strong electronic coupling (Class III). The properties of Class I systems are essentially those of the separate sites. Class II systems possess new optical and electronic properties in addition to those of the separate sites. However, the interaction between the sites is sufficiently weak that Class II systems are valence trapped or charge localized and can the be described by a double-well potential. In Class III systems the interaction of the donor and acceptor sites is so great that two separate minima are no longer discernible and the energy surface features a single minimum. The electron is delocalized and the system has its own unique properties. The Robin and Day classification has enjoyed considerable success and most of the redox systems studied to date are readily assigned to Class II. However the situation becomes much more complicated when the system shows borderline Class II/III behavior. Such "almost delocalized" mixed-valence systems are difficult to characterize. In this article spectral band shapes and intensities are calculated utilizing increasingly complex models including two to four states. Free-energy surfaces are constructed for harmonic diabetic surfaces and characterized as a function of increasing electronic coupling to simulate the Class II to III transition. The properties of the charge-transfer absorption bands predicted for borderline mixed-valence systems are compared with experimental data. The treatment is restricted to symmetrical (delta G0 = 0) systems.     

Intervalence near-IR spectra of delocalized dinitroaromatic radical anions

The Class III (delocalized) intervalence radical anions of 1,4-dinitrobenzene, 2,6-dinitronaphthalene, 2,6-dinitroanthracene, 9,9-dimethyl-2,7-dinitrofluorene, 4,4'-dinitrobiphenyl, and 1,5-dinitronaphthalene show charge-transfer bands in their near-IR spectra. The dinitroaromatic radical anions have comparable but slightly larger electronic interactions (H(ab) values) through the same aromatic bridges as do the corresponding dianisylamino-substituted radical cations. H(ab) values range from 5410 cm(-)(1) (1,4- dinitrobenzene) to 3400 cm(-)(1) (9,9-dimethyl-2,7-dinitrofluorene), decreasing as the number of bonds between the nitro groups increases, except for the 1,5-dinitronaphthalene radical-anion, which has a coupling similar to that of 9,9-dimethyl-2,7-dinitrofluorene. All charge-transfer bands show vibrational fine structure. The vertical excitation energies (lambda(v)) were estimated from the vibrational components, obtained by simulation of the entire band. The large 2H(ab)/lambda(v) values confirm these radicals to be Class III delocalized mixed-valence species. Analysis using Cave and Newton's generalized Mulliken-Hush theory relating the transition dipole moment to the distance on the diabatic surfaces suggests that the electron-transfer distance on the diabatic surfaces, d(ab), is only 26-40% of the nitrogen-to-nitrogen distance, which implies that something may be wrong with our analysis.     

Direct observation of mixed-valence and radical cation dimer states of tetrathiafulvalene in solution at room temperature: association and dissociation of molecular clip dimers under oxidative control

We have observed the mixed-valence and radical cation dimer states of a glycoluril-based molecular clip with tetrathiafulvalene (TTF) sidewalls at low concentration (1 mM) at room temperature. This molecular clip has four consecutive anodic steps in its cyclic voltammogram, which suggests a sequential oxidation of these TTF sidewalls to generate species existing in several distinct charge states: neutral monomers, mixed-valence dimers, radical cation dimers, and fully oxidized tetracationic monomers. The observation of characteristic NIR spectroscopic absorption bands at approximately 1650 and 830 nm in spectroelectrochemistry experiments supports the presence of intermediary mixed-valence and radical cation dimers, respectively, during the oxidation process. The stacking of four TTF radical cations in the dimer led to the appearance of a charge-transfer band at approximately 946 nm. Nanoelectrospray ionization mass spectrometry was used to verify the tricationic state and confirm the existence of other different charged dimers during the oxidation of the molecular clip.     

Intervalence (charge-resonance) transitions in organic mixed-valence systems. Through-space versus through-bond electron transfer between bridged aromatic (redox) centers

Intervalence absorption bands appearing in the diagnostic near-IR region are consistently observed in the electronic spectra of mixed-valence systems containing a pair of aromatic redox centers (Ar(*)(+)/Ar) that are connected by two basically different types of molecular bridges. The through-space pathway for intramolecular electron transfer is dictated by an o-xylylene bridge in the mixed-valence cation radical 3(*)(+) with Ar = 2,5-dimethoxy-p-tolyl (T), in which conformational mobility allows the proximal syn disposition of planar T(*)(+)/T redox centers. Four independent experimental probes indicate the large through-space electronic interaction between such cofacial Ar(*)(+)/Ar redox centers from the measurements of (a) sizable potential splitting in the cyclic voltammogram, (b) quinonoidal distortion of T(*)(+)/T centers by X-ray crystallography, (c) "doubling" of the ESR hyperfine splittings, and (d) a pronounced intervalence charge-resonance band. The through (br)-bond pathway for intramolecular electron transfer is enforced in the mixed-valence cation radical 2a(*)(+) by the p-phenylene bridge which provides the structurally inflexible and linear connection between Ar(*)(+)/Ar redox centers. The direct comparison of intramolecular rates of electron transfer (k(ET)) between identical T(*)(+)/T centers in 3(*)(+) and 2a(*)(+)( )()indicates that through-space and through-bond mechanisms are equally effective, despite widely different separations between their redox centers. The same picture obtains for 3(*)(+) and 2a(*)(+)( )()from theoretical computations of the first-order rate constants for intramolecular electron transfer from Marcus-Hush theory using the electronic coupling elements evaluated from the diagnostic intervalence (charge-transfer) transitions. Such a strong coherence between theory and experiment also applies to the mixed-valence cation radical 7(*)(+), in which the aromatic redox S center is sterically encumbered by annulation.     

One-electron oxidation of electronically diverse manganese(III) and nickel(II) salen complexes: transition from localized to delocalized mixed-valence ligand radicals

Ligand radicals from salen complexes are unique mixed-valence compounds in which a phenoxyl radical is electronically linked to a remote phenolate via a neighboring redox-active metal ion, providing an opportunity to study electron transfer from a phenolate to a phenoxyl radical mediated by a redox-active metal ion as a bridge. We herein synthesize one-electron-oxidized products from electronically diverse manganese(III) salen complexes in which the locus of oxidation is shown to be ligand-centered, not metal-centered, affording manganese(III)-phenoxyl radical species. The key point in the present study is an unambiguous assignment of intervalence charge transfer bands by using nonsymmetrical salen complexes, which enables us to obtain otherwise inaccessible insight into the mixed-valence property. A d(4) high-spin manganese(III) ion forms a Robin-Day class II mixed-valence system, in which electron transfer is occurring between the localized phenoxyl radical and the phenolate. This is in clear contrast to a d(8) low-spin nickel(II) ion with the same salen ligand, which induces a delocalized radical (Robin-Day class III) over the two phenolate rings, as previously reported by others. The present findings point to a fascinating possibility that electron transfer could be drastically modulated by exchanging the metal ion that bridges the two redox centers.     

Molecular and electronic structures of the long-bonded pi-dimers of tetrathiafulvalene cation-radical in intermolecular electron transfer and in (solid-state) conductivity

Tetrathiafulvalene (TTF) as the prototypical electron donor for solid-state (electronics) applications is converted to the unusual cation-radical salt, TTF+* CB- (where CB- is the non-coordinating closo-dodecamethylcarboranate), for crystallographic and spectral analyses. Near-IR studies establish the spontaneous self-association of TTF+* to form the diamagnetic [TTF+,TTF+] dication and to also undergo the equally rapid cross-association with its parent donor to form the mixed-valence [TTF+*,TTF] cation-radical. The latter, most importantly, represents the first (dyad) member of a series of p-doped tetrathiafulvalene (stacked) arrays, and the thorough scrutiny of its electronic structure with the aid of Mulliken-Hush (two-state) analysis of the diagnostic (intervalence) NIR band reveals Robin-Day Class II behavior. The theoretical consequences of the unique structure of the mixed-valence [TTF+*,TTF] dyad on (a) the electron-transfer mechanism for self-exchange, (b) the molecular-orbital analysis of the Marcus reorganization energy, and (c) the ab initio computation of the coupling element or transfer integral in p-doped (solid-state) arrays are discussed.     

Synthesis, characterization, and photophysical properties of a series of supramolecular mixed-valence compounds

The synthesis and characterization of 10 cyano-bridged trinuclear mixed-valence compounds of the form [(NH3)5M-NC-FeII(CN)4-CN-M'(NH3)5]n+ (M = RuIII, OsIII, CrIII, or PtIV; n = 2, 3, or 4) is reported. The electronic spectra of these supramolecular compounds exhibit a single intervalent (IT) absorption band for each nondegenerate Fe-->M/M' transition. The redox potential of the Fe(II) center is shifted more positive with the addition of each coordinated metal complex, while the redox potentials of the pendant metals vary only slightly from their dinuclear counterparts. As a result, the Fe-->M IT bands are blue-shifted from those in the corresponding dinuclear mixed-valence compounds. The energies of these IT bands show a linear correlation with the ground-state thermodynamic driving force, as predicted by classical electron transfer theory. Estimates of the degree of electronic coupling (Hab) between the metal centers using a theoretical analysis of the IT band shapes indicate that most of these values are similar to those for the corresponding dinuclear species. Notable exceptions occur for the Fe-->M IT transitions in Os-Fe-M (M = Cr or Pt). The enhanced electronic coupling in these two species can be explained as a result of excited state mixing between electron transfer and/or ligand-based charge transfer states and an intensity-borrowing mechanism. Additionally, the possibility of electronic coupling between the remote metal centers in the Ru-Fe-Ru species is discussed in order to explain the observation of two closely spaced redox waves for the degenerate Ru(III) acceptors.     

DFT description of the magnetic properties and electron localization in dinuclear di-mu-oxo-bridged manganese complexes

Density functional theory (DFT) was applied to describe the magnetic and electron-transfer properties of dinuclear systems containing the [MnO2Mn]n+ core, with n=0,1,2,3,4. The calculation of the potential energy surfaces (PESs) of the mixed-valence species (n=1,3) allowed the classification of these systems according to the extent of valence localization as Class II compounds, in the Robin-Day classification scheme. The fundamental frequencies corresponding to the asymmetric breathing vibration were also computed.     

Multifunctional ferrocene-ruthenocene dyads linked by single or double aza-containing bridges displaying metal-metal interactions and cation recognition properties

The synthesis, electrochemical, electronic, and cation sensing properties of the ruthenocene-terminated 2-aza-1,3-butadiene 2, linear ferrocene-ruthenocene dyads 3 and 5, and the new structural motifs diaza[4.4]ruthenocenophane 7 and mixed ferrocene and ruthenocene metallocenophanes 8 and 10 are presented. The properties of these compounds have been systematically varied by introducing the ferrocene and ruthenocene moieties at the 1- or 4-position of the unsymmetrical 2-aza-1,3-butadiene bridge. Spectroelectrochemical studies of compounds 3 and 8, in which the ruthenocene unit appended at the 1-position of the bridge exhibits a rather unusual electrochemical behavior, revealed the presence of low-energy bands in the near-infrared (NIR) region in the partially oxidized forms, at 1070 and 1163 nm, respectively, which indicate the existence of intramolecular charge transfer between the iron and the ruthenium centers. The electrochemical and intermetallic charge-transfer (MMCT) studies (HAB, lambda and alpha parameters) indicate that the 3*+ and 8*+ systems belong to the Class II classification for a mixed-valence compound. In addition, the low-energy (LE) band of the absorption spectra of all compounds prepared, except compound 10, are red-shifted by complexation with divalent Mg2+, Zn2+, Cd2+, Hg2+, and Ni2+ metal ions. For open dyads, biruthenocene compound 2 exhibited the higher red-shift by 92 nm, whereas for closed compounds the [4.4]ruthenocenoferrocenophane 8 displayed a remarkable red-shift by about 180 nm for Zn2+, Cd2+, Hg2+, and Ni2+ metal ions and by about 146 nm for Mg2+ cation. The changes in the absorption spectra are accompanied by dramatic color changes which allow the potential for "naked eye" detection. The experimental data and conclusions are supported by DFT computations.     

Structure and properties of Dinuclear [RuII([n]aneS4)] complexes of 3,6-Bis(2-pyridyl)-1,2,4,5-tetrazine

The synthesis of dinuclear [Ru(II)([n]aneS(4))] (where n = 12, 14) complexes of the bridging ligand 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine are reported. The X-ray structures of both of the new complexes are compared to a newly obtained structure for a dinuclear [Ru(II)([9]aneS(3))]-based analogue, whose synthesis has previously been reported. A comparison of the electrochemistry of the three complexes reveals that the first oxidation of the [Ru(II)([n]aneS(4))]-based systems is a ligand-based couple, indicating that the formation of the radical anion form of the bridging ligand is stabilized by metal center coordination. Spectroelectrochemistry studies on the mixed-valence form of the new complexes suggest that they are Robin and Day Class II systems. The electrochemical and electronic properties of these complexes is rationalized by a consideration of the pi-bonding properties of thiacrown ligands.     

Dinuclear cyano-bridged CoIII-FeII complexes as precursors for molecular mixed-valence complexes of higher nuclearity

The preparation and characterization of a series of trinuclear mixed-valence cyano-bridged Co(III)-Fe(II)-Co(III) compounds derived from known dinuclear [[L(n)Co(III)(mu-NC)]Fe(II)(CN)(5)](-) complexes (L(n)() = N(5) or N(3)S(2) n-membered pendant amine macrocycle) are presented. All of the new trinuclear complexes were fully characterized spectroscopically (UV-vis, IR, and (13)C NMR). Complexes exhibiting a trans and cis arrangement of the Co-Fe-Co units around the [Fe(CN)(6)](4-) center are described (i.e., cis/trans-[{L(n)Co(III)(mu-NC)](2)Fe(II)(CN)(4)](2+)), and some of their structures are determined by X-ray crystallography. Electrochemical experiments revealed an expected anodic shift of the Fe(III/II) redox potential upon addition of a tripositively charged [Co(III)L(n)] moiety. The Co(III/II) redox potentials do not change greatly from the di- to the trinuclear complex, but rather behave in a fully independent and noncooperative way. In this respect, the energies and extinction coefficients of the MMCT bands agree with the formal existence of two mixed-valence Fe(II)-CN-Co(III) units per molecule. Solvatochromic experiments also indicated that the MMCT band of these compounds behaves as expected for a class II mixed-valence complex. Nevertheless, its extinction coefficient is dramatically increased upon increasing the solvent donor number.     

Current trends and future challenges in the experimental, theoretical and computational analysis of intervalence charge transfer (IVCT) transitions

Mixed-valence chemistry has a long and rich history which is characterised by a strong interplay of experimental, theoretical and computational studies. The intervalence charge transfer (IVCT) transitions generated in dinuclear mixed-valence species (particularly of ruthenium and osmium) have received considerable attention in this context, as they provide a powerful and sensitive probe of the factors which govern electronic delocalisation and the activation barrier to intramolecular electron transfer. This tutorial review discusses classical, semi-classical and quantum mechanical theoretical treatments which have been developed over the past 35 years for the analysis of IVCT absorption bands. Particular attention is drawn to the applicability of these models for the analysis of mixed-valence complexes which lie between the fully localised (Class II) and delocalised (Class III) limits in the "localised-to-delocalised" (Class II-III) regime. A clear understanding of the complex interplay of inter- and intramolecular factors which influence the IVCT process is crucial for the design of experimental studies to probe the localised-to-delocalised regime and in guidance of the development of appropriate theoretical models.     

Electrochemically controlled hydrogen bonding. o-Quinones as simple redox-dependent receptors for arylureas

9,10-Phenanthrenequinone and acenaphthenequinone are shown to act as simple redox-dependent receptors toward aromatic ureas in CH(2)Cl(2) and DMF. Reduction of the o-quinones to their radical anions greatly increases the strength of hydrogen bonding between the quinone carbonyl oxygens and the urea N-hydrogens. This is detected by large positive shifts in the redox potential of the quinones with no change in electrochemical reversibility upon addition of urea guests. Cyclic voltammetric studies with a variety of possible guests show that the effect is quite selective. Only guests with two strong hydrogen donors, such as O-H bonds or amide N-H bonds, that are capable of simultaneously interacting with both carbonyl oxygens give large shifts in the redox potential of the quinones. The electronic character and conformational preference of the guest are also shown to significantly affect the magnitude of the observed potential shift. In the presence of strong proton donors the electrochemistry of the quinone becomes irreversible indicating that proton transfer has taken place. Experiments with compounds of different acidity show that the pK(a) of the protonated quinone radical is about 15 on the DMSO scale, >4 pK(a) units smaller than that of 1,3-diphenylurea. This is further proof that hydrogen bonding and not proton transfer is responsible for the large potential shifts observed with this and similar guests.     

Direct measurement of excited-state intervalence transfer in [(tpy)Ru(III)(tppz(*-))Ru(II)(tpy)](4+) by time-resolved near-infrared spectroscopy

Extension of time-resolved infrared (TRIR) measurements into the near-infrared region has allowed the first direct measurement of a mixed-valence band in the metal-to-ligand charge transfer (MLCT) excited state of a symmetrical ligand-bridged complex. Visible laser flash excitation of [(tpy)Ru(tppz)Ru(tpy)]4+ (tppz is 2,3,5,6-tetrakis(2-pyridyl)pyrazine; tpy is 2,2':6',6' '-terpyridine) produces the mixed-valence, MLCT excited state [(tpy)RuIII(tppz*-)RuII(tpy)]4+* with the excited electron localized on the bridging tppz ligand. A mixed-valence band appears at numax = 6300 cm-1 with a bandwidth-at-half- maximum, Deltanu1/2 = 1070 cm-1. In the analogous ground-state complex, [(tpy)Ru(tppz)Ru(tpy)]5+, a mixed-valence band appears at numax = 6550 cm-1 with Deltanu1/2 = 970 cm-1 which allows a comparison to be made of electronic coupling across tppz0 and tppz*- as bridging ligands.     

Neutral organic mixed-valence compounds: synthesis and all-optical evaluation of electron-transfer parameters

In this paper we present the synthesis as well as a detailed study of the electrochemical and photophysical properties of a series of neutral organic mixed-valence (MV) compounds, 1-7, in which different amine donor centers are connected to perchlorinated triarylmethyl radical units by various spacers. We show that this new class of compounds are excellent model systems for the investigation of electron transfer due to their uncharged character and, consequently, their excellent solubility, particularly in nonpolar solvents. A detailed band shape analysis of the intervalence charge-transfer (IV-CT) bands in the context of Jortner's theory allowed the electron-transfer parameters (inner vibrational reorganization energy lambdav, outer solvent reorganization energy lambdao, and the difference in the free energy between the diabatic ground and excited states, DeltaG degrees degrees , as well as the averaged molecular vibrational mode v) to be extracted independently. In this way we were able to analyze the solvatochromic behavior of the IV-CT bands by evaluating the contribution of each parameter. By comparison of different compounds, we were also able to assign specific molecular moieties to changes in vv. For this class of molecules, we also demonstrate that the adiabatic dipole moment difference Deltamicroab and, consequently, the electronic coupling V12 can be evaluated directly from the absorption spectra by a new variant of the solvatochromic method. Furthermore, an investigation of the electrochemistry of compounds 1-7 by cyclic voltammetry as well as spectroelectrochemistry shows that, not only in the neutral MV compounds but also in their oxidized forms, a charge transfer can be optically induced but with exchanged donor-acceptor functionalities of the redox centers.     

Arylamine-substituted oligo(ladder-type pentaphenylene)s: electronic communication between bridged redox centers

Novel bis(arylamine-substituted) oligo(ladder-type pentaphenylene)s 1-3, with bridge lengths estimated to be 2.2, 4.2, and 6.3 nm, respectively, have been developed, and the model compound 4 with a mono-arylamine substituent was also synthesized. Their absorption spectra in different solvents are almost identical, while distinct bathochromic shifts of the photoluminescence (PL) spectra were observed with increasing solvent polarity due to the polarized excited states. The cyclic voltammetry (CV) and differential pulse voltammetry (DPV) spectra display a two-step oxidation of the bridged diamines in compound 1, which suggests that the electron and charge delocalize in mixed-valence (MV) cation 1+* and that both redox centers can communicate through the pentaphenylene bridge. Only unresolved curves in CV and DPV spectra were observed in the first two oxidation processes of diamines 2 and 3, indicating that the bridges are too long for efficient delocalization over the entire molecules and the radical cations localize at each arylamine center. This finding was further supported by chemical oxidation with SbCl5 and studies of the corresponding UV-vis-NIR absorption spectra of compounds 1-4. A significant intervalence charge-transfer (IVCT) band around 5283 cm-1 (1893 nm) was observed in 1+*. This is the first report of such a highly intense IVCT band in the NIR region with intensity similar to that of the visible band of the radicals, enabling further analysis of the CT process and the coupling matrix element V, classifying 1+* as a class II derivative (V = 1.6 kcal/mol). This study may offer an effective way to improve the understanding of charge transfer and charge-carrier transport in various conjugated oligomers or polymers and facilitate their ongoing exploration in optoelectronic applications.     

Electronic structure and nature of the ground state of the mixed-valence binuclear tetra(mu-1,8-naphthyridine-N,N')-bis(halogenonickel) tetraphenylborate complexes: experimental and DFT characterization

The ground state electronic structure of the mixed-valence systems [Ni(2)(napy)(4)X(2)](BPh(4)) (napy=1,8-naphthyridine; X=Cl, Br, I) was studied with combined experimental (X-ray diffraction, temperature dependence of the magnetic susceptibility, and high-field EPR spectroscopy) and theoretical (DFT) methods. The zero-field splitting (zfs) ground S=3/2 spin state is axial with /D/ approximately 3 cm(-1). The iodide derivative was found to be isostructural with the previously reported bromide complex, but not isomorphous. The compound crystallizes in the monoclinic system, space group P2(1)/n, with a=17.240(5), b=26.200(5), c=11.340(5) A, beta=101.320(5) degrees. DFT calculations were performed on the S=3/2 state to characterize the ground state potential energy surface as a function of the nuclear displacements. The molecules can thus be classified as Class III mixed-valence compounds with a computed delocalization parameter, B=3716, 3583, and 3261 cm(-1) for the Cl, Br, and I derivatives, respectively.     

Simultaneous bridge-localized and mixed-valence character in diruthenium radical cations featuring diethynylaromatic bridging ligands

A series of bimetallic ruthenium complexes [{Ru(dppe)Cp*}(2)(μ-C≡CArC≡C)] featuring diethynylaromatic bridging ligands (Ar = 1,4-phenylene, 1,4-naphthylene, 9,10-anthrylene) have been prepared and some representative molecular structures determined. A combination of UV-vis-NIR and IR spectroelectrochemical methods and density functional theory (DFT) have been used to demonstrate that one-electron oxidation of compounds [{Ru(dppe)Cp*}(2)(μ-C≡CArC≡C)](HC≡CArC≡CH = 1,4-diethynylbenzene; 1,4-diethynyl-2,5-dimethoxybenzene; 1,4-diethynylnaphthalene; 9,10-diethynylanthracene) yields solutions containing radical cations that exhibit characteristics of both oxidation of the diethynylaromatic portion of the bridge, and a mixed-valence state. The simultaneous population of bridge-oxidized and mixed-valence states is likely related to a number of factors, including orientation of the plane of the aromatic portion of the bridging ligand with respect to the metal d-orbitals of appropriate π-symmetry.