Bridge-localized HOMO-binding character of divinylanthracene-bridged dinuclear ruthenium carbonyl complexes: spectroscopic, spectroelectrochemical, and computational studies

The electronic properties of four divinylanthracene-bridged diruthenium carbonyl complexes [{RuCl(CO)(PMe3)3}2(μ[BOND]CH[DOUBLE BOND]CHArCH[DOUBLE BOND]CH)] (Ar=9,10-anthracene (1), 1,5-anthracene (2), 2,6-anthracene (3), 1,8-anthracene (4)) obtained by molecular spectroscopic methods (IR, UV/Vis/near-IR, and EPR spectroscopy) and DFT calculations are reported. IR spectroelectrochemical studies have revealed that these complexes are first oxidized at the noninnocent bridging ligand, which is in line with the very small ν(C[TRIPLE BOND]O) wavenumber shift that accompanies this process and also supported by DFT calculations. Because of poor conjugation in complex 1, except oxidized 1+, the electronic absorption spectra of complexes 2+, 3+, and 4+ all display the characteristic near-IR band envelopes that have been deconvoluted into three Gaussian sub-bands. Two of the sub-bands belong mainly to metal-to-ligand charge-transfer (MLCT) transitions according to results from time-dependent DFT calculations. EPR spectroscopy of chemically generated 1+–4+ proves largely ligand-centered spin density, again in accordance with IR spectra and DFT calculations results.

Temperature- and Pressure-induced Proton Transfer in the 1:1 Adduct Formed between Squaric Acid and 4,4 '-Bipyridine

We have applied a combination of spectroscopic and diffraction methods to study the adduct formed between squaric acid and bypridine, which has been postulated to exhibit proton transfer associated with a single-crystal to single-crystal phase transition at ca. 450 K. A combination of X-ray single-crystal and very-high flux powder neutron diffraction data confirmed that a proton does transfer from the acid to the base in the high-temperature form. Powder X-ray diffraction measurements demonstrated that the transition was reversible but that a significant kinetic energy barrier must be overcome to revert to the original structure. Computational modeling is consistent with these results. Modeling also revealed that, while the proton transfer event would be strongly discouraged in the gas phase, it occurs in the solid state due to the increase in charge state of the molecular ions and their arrangement inside the lattice. The color change is attributed to a narrowing of the squaric acid to bipyridine charge-transfer energy gap. Finally, evidence for the possible existence of two further phases at high pressure is also presented.

Ultrafast excited state dynamics controlling photochemical isomerization of N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium coordinated to a {Re-1(CO)(3)(2,2 '-bipyridine)} chromophore

Two Multifunctional photoactive complexes [Re(Cl)(CO)(3)-(MeDpe(+))(2)](2+) and [Re(MeDpe(+))(CO)(3)(bpy)](2+) (MeDpe(+) = N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium, bpy = 2,2'-bipyridine) were synthesized. characterized. and their redox and photonic properties were investigated by cyclic voltammetry: ultraviolet-visible-infrared (UV/Vis/IR) spectroelectrochemistry, stationary UV/Vis and resonance Raman spectroscopy; photolysis; picosecond time-resolved absorption spectroscopy in the visible and infrared regions: and time-resolved resonance Raman spectroscopy. The first reduction step of either complex Occurs at about -1.1 V versus Fc/Fc(+) and is localized at MeDpe(+). Reduction alone does not induce a trans -> cis isomerization of MeDpe(+). [Re(Cl)(CO)(3)(MeDPe(+))(2)](2+) is photostable, while [Re(MeDpe(+))(CO)(3)(bpy)](2+) and free MeDpe(+) isomerize under near-UV irradiation. The lowest excited state of [Re(Cl)(CO)(3)(MeDPe(+))(2)](2+) has been identified as the Re(Cl)(CO)(3) -> MeDpe(+) (MLCT)-M-3 (MLCT = metal-to-ligand charge transfer), decaying directly to the ground state with lifetimes of approximate to 42 (73%) and approximate to 430ps (27%). Optical excitation of [Re(MeDpe(+))(CO)(3)(bpy)](2+) leads to population of Re(CO)(3) -> MeDpe(+) and Re(CO)(3) -> bpy (MLCT)-M-3 states, from which a MeDpe(+) localized intraligand 3 pi pi* excited state ((IL)-I-3) is populated with lifetimes of approximate to 0.6 and approximate to 10 ps, respectively. The 3IL state undergoes a approximate to 21 ps internal rotation, which eventually produces the cis isomer on a much longer timescale. The different excited-state behavior of the two complexes and the absence of thermodynamically favorable interligand electron transfer in excited [Re(MeDpe(+))(CO)(3)(bpy)](2+) reflect the fine energetic balance between excited states of different orbital origin, which can be tuned by subtle Structural variations. The complex [Re(MeDpe+)(CO)(3)(bpy)](2+) emerges as a prototypical, multifunctional species with complementary redox and photonic behavior.

Synthesis, structure, solution chemistry and the electronic effect of para substituents on the vanadium center in a family of mixed-ligand [(VO)-O-V(ONO)(ON)] compexes

Four tridentate dibasic ONO donor hydrazone ligands derived from the condensation of benzoylhydrazine with either 2-hydroxyacetophenone or its para substituted derivatives (H2L1-4, general abbreviation H2L) have been used as primary ligands and 8-hydroxyquinoline (Hhq, a bidentate monobasic ON donor species) has been used as auxiliary ligand. The reaction of [(VO)-O-IV(acac)21 with H2L in methanol followed by the addition of Hhq in equimolar ratio under aerobic condition afforded the mixed-ligand oxovanadium(V) complexes of the type [(VO)-O-V(L)(hq)] (1-4) in excellent yield. The X-ray structure of the compound [(VO)-O-V(L-4)(hq)] (4) indicates that the H2L4 ligand is bonded with vanadium meridionally in a tridentate dinegative fashion through its deprotonated phenolic-O, deprotonated enolic-O and imine-N atoms. The V-O bond length order is: oxo < phenolato < enolato. H-1 NMR spectra of 4 in CDCl3 solution indicates that it's solid-state structure is retained in solution. Complexes are diamagnetic and exhibit only ligand to metal charge transfer (LMCT) transition band near 530 nm in CH2Cl2 solution in addition to intra-ligand pi-pi* transition band near 335 rim and they display quasi-reversible one electron reduction peak near -0.10 V versus SCE in CH2Cl2 solution. lambda(max) (for LMCT transition) and the reduction peak potential (E-p(c)) values of the complexes are found to be linearly related with the Hammett (sigma) constants of the substituents in the aryloxy ring of the hydrazone ligands. lambda(max) and E-p(c) values show large dependence d lambda(max)/d sigma = 32.54 nm and dE(p)(c)/d sigma = 0.19 V, respectively, on the Hammett constant. (c) 2006 Elsevier B.V. All rights reserved.

Design, synthesis and computational modelling of aromatic tweezer-molecules as models for chain-folding polymer blends

Novel 'tweezer-type' complexes that exploit the interactions between pi-electron-rich pyrenyl groups and pi-electron deficient diimide units have been designed and synthesised. The component molecules leading to complex formation were accessed readily from commercially available starting materials through short and efficient syntheses. Analysis of the resulting complexes, using the visible charge-transfer band, revealed association constants that increased sequentially from 130 to 11,000 M-1 as increasing numbers of pi-pi-stacking interactions were introduced into the systems. Computational modelling was used to analyse the structures of these complexes, revealing low-energy chain-folded conformations for both components, which readily allow close, multiple pi-pi-stacking and hydrogen bonding to be achieved. In this paper, we give details of our initial studies of these complexes and outline how their behaviour could provide a basis for designing self-healing polymer blends for use in adaptive coating systems. (C) 2008 Elsevier Ltd. All rights reserved.

Facile photoinduced charge separation through a cyanoacetylide bridge in a heterobimetallic Fe(II)-Re(I) complex

Photoinduced Fe-to-bpy charge transfer in [{Cp(dppe)Fe}-(mu-C CC N){Re(CO)(3)(bpy)}]PF6 has been observed by ps-TRIR spectroscopy, supported by UV-Vis/IR spectroelectrochemistry and DFT calculations.

Induced-fit binding of π-electron donor substrates to macrocyclic aromatic ether-imide-sulfones: a versatile approach to molecular assembly

Novel macrocyclic receptors which bind electron-donor aromatic substrates via π-stacking donor- acceptor interactions are obtained by cyclo-imidization of an amine-functionalized arylether-sulfone with pyromellitic- and 1,4,5,8-naphthalene-tetracarboxylic dianhydrides. These macrocycles complex with a wide variety of π-donor substrates including tetrathiafulvalene, naphthalene, anthracene, pyrene, perylene, and functional derivatives of these polycyclic hydrocarbons. The resulting supramolecular assemblies range from simple 1:1 complexes, to [2]- and [3]-pseudorotaxanes, and even (as a result of crystallographic disorder) an apparent polyrotaxane. Direct, five-component self-assembly of a metal-centred [3]pseudorotaxane is also observed, on complexation of a macrocyclic ether-imide with 8-hydroxyquinoline in the presence of palladium(II) ions. Binding studies in solution were carried out by 1H NMR and UV-visible spectroscopy, and the stoichiometries of binding were confirmed by Job plots based on charge-transfer absorption bands. The highest association constants are found for strong π-donor guests with large surface-areas, notably perylene and 1-hydroxypyrene, for which Ka values of 1.4 x 103 and 2.3 x 103 M-1 respectively are found. Single crystal X-ray analyses of the receptors and their derived complexes reveal large, induced-fit distortions of the macrocyclic frameworks as a result of complexation. These structures provide compelling evidence for the existence of strong, attractive forces between the electronically-complementary aromatic π-systems of host and guest.

The synthesis, structure, and electrochemical properties of Fe(C CC N)(dppe)Cp and related compounds

The cyanoacetylide complex Fe(CCCN)(dppe)Cp (3) is readily obtained from sequential reaction of Fe(CCSiMe3)(dppe)Cp with methyllithium and phenyl cyanate. Complex 3 is a good metalloligand, and coordination to the metal fragments [RhCl(CO)(2)], [Ru(PPh3)(2)Cp](+), and [Ru(dppe)Cp*](+) affords the corresponding cyanoaceylide-bridged heterobimetallic complexes. In the case of the 36-electron complexes [Cp(dppe)Fe-CCCN-MLn](n+), spectroscopic and structural data are consistent with a degree of charge transfer from the iron centre to the rhodium or ruthenium centre via the C3N bridge, giving rise to a polarized ground state. Electrochemical and spectroelectrochemical methods reveal significant interactions between the metal centres in the oxidized (35 electron) derivatives, [Cp(dppe)Fe-CCCN-MLn]((n+1)+).

Electronic properties of 4,4 ',5,5 '-tetramethyl-2,2 '-biphosphinine (tmbp) in the redox series fac-[Mn(Br)(CO)(3)(tmbp)], [Mn(CO)(3)(tmbp)](2), and [Mn(CO)(3)(tmbp)](-): crystallographic, spectroelectrochemical, and DFT computational study

Stepwise electrochemical reduction of the complex fac-[Mn(Br)(CO)(3)(tmbp)] (tmbp = 4,4',5,5'-tetramethyl-2,2'-biphosphinine) produces the dimer [Mn(CO)(3)(tmbp)](2) and the five-coordinate anion [Mn(CO)(3)(tmbp)](-). All three members of the redox series have been characterized by single-crystal X-ray diffraction. The crystallographic data provide valuable insight into the localization of the added electrons on the (carbonyl)manganese and tmbp centers. In particular, the formulation of the two-electron-reduced anion as [Mn-0(CO)(3)(tmbp(-))](-) also agrees with the analysis of its IR nu(CO) wavenumbers and with the results of density functional theoretical (DFT) MO calculations on this compound. The strongly delocalized pi-bonding in the anion stabilizes its five-coordinate geometry and results in the appearance of several mixed Mn-to-tmbp charge-transfer/IL(tmbp) transitions in the near-UV-vis spectral region. A thorough voltammetric and UV-vis/IR spectroelectrochemical study of the reduction path provided evidence for a direct formation of [Mn(CO)(3)(tmbp)](-) via a two-electron ECE mechanism involving the [Mn(CO)(3)(tmbp)](.) radical transient. At ambient temperature [Mn(CO)(3)(tmbp)](-) reacts rapidly with nonreduced fac-[Mn(Br)(CO)(3)(tmbp)] to produce [Mn(CO)(3)(tmbp)](2). Comparison with the analogous 2,2'-bipyridine complexes has revealed striking similarity in the bonding properties and reactivity, despite the stronger pi-acceptor character of the tmbp ligand.

A new emissive Ru(II)N5O core

From the reaction of cis-Ru(1,10-phenanthroline)(2)Cl(2 center dot)2H(2)O with 2-picolinic acid in 1:1 molar ratio in degassed methanol-water mixture, [Ru(1,10-phenanthroline)(2)(2-picolinate)]PF6 center dot H2O (1) has been isolated as a red compound by adding excess of NH4PF6. Single crystal X-ray crystallography shows that the metal in 1 has an octahedral N5O coordination sphere. Complex 1 displays (MLCT)-M-1 bands in the 400-500 nm region in acetonitrile. Upon excitation at 435 nm, complex 1 gives rise to a broad emission band at 675 nm in acetonitrile at room temperature with a quantum yield of 0.0022. The energy of the MLCT state in 1 is estimated as 1.99 eV. Since, from cyclic voltammetry, the ground state potential of the Ru(II/III) couple in 1 is found to be 1.01 V vs NHE, the potential of the same couple in the excited state is calculated as -0.98 V vs NHE. The emissive state in 1 seems to be the triplet Ru(II) -> 1, 10-phenanthroline charge transfer state.

Influence of the solvent on the self-assembly of a modified amyloid beta peptide fragment. II. NMR and computer simulation investigation

The conformation of a model peptide AAKLVFF based on a fragment of the amyloid beta peptide A beta 16-20, KLVFF, is investigated in methanol and water via solution NMR experiments and Molecular dynamics computer simulations. In previous work, we have shown that AAKLVFF forms peptide nanotubes in methanol and twisted fibrils in water. Chemical shift measurements were used to investigate the solubility of the peptide as a function of concentration in methanol and water. This enabled the determination of critical aggregation concentrations, The Solubility was lower in water. In dilute solution, diffusion coefficients revealed the presence of intermediate aggregates in concentrated solution, coexisting with NMR-silent larger aggregates, presumed to be beta-sheets. In water, diffusion coefficients did not change appreciably with concentration, indicating the presence mainly of monomers, coexisting with larger aggregates in more concentrated solution. Concentration-dependent chemical shift measurements indicated a folded conformation for the monomers/intermediate aggregates in dilute methanol, with unfolding at higher concentration. In water, an antiparallel arrangement of strands was indicated by certain ROESY peak correlations. The temperature-dependent solubility of AAKLVFF in methanol was well described by a van't Hoff analysis, providing a solubilization enthalpy and entropy. This pointed to the importance of solvophobic interactions in the self-assembly process. Molecular dynamics Simulations constrained by NOE values from NMR suggested disordered reverse turn structures for the monomer, with an antiparallel twisted conformation for dimers. To model the beta-sheet structures formed at higher concentration, possible model arrangements of strands into beta-sheets with parallel and antiparallel configurations and different stacking sequences were used as the basis for MD simulations; two particular arrangements of antiparallel beta-sheets were found to be stable, one being linear and twisted and the other twisted in two directions. These structures Were used to simulate Circular dichroism spectra. The roles of aromatic stacking interactions and charge transfer effects were also examined. Simulated spectra were found to be similar to those observed experimentally.(in water or methanol) which show a maximum at 215 or 218 nm due to pi-pi* interactions, when allowance is made for a 15-18 nm red-shift that may be due to light scattering effects.

Non-stoichiometric oxide and metal interfaces and reactions

We have employed a combination of experimental surface science techniques and density functional calculations to study the reduction of TiO2(110) surfaces through the doping with submonolayer transition metals. We concentrate on the role of Ti adatoms in self doping of rutile and contrast the behaviour to that of Cr. DFT+U calculations enable identification of probable adsorption structures and their spectroscopic characteristics. Adsorption of both metals leads to a broken symmetry and an asymmetric charge transfer localised around the defect site of a mixed localised/delocalised character. Charge transfer creates defect states with Ti 3d character in the band gap at similar to 1-eV binding energy. Cr adsorption, however, leads to a very large shift in the valence-band edge to higher binding energy and the creation of Cr 3d states at 2.8-eV binding energy. Low-temperature oxidation lifts the Ti-derived band-gap states and modifies the intensity of the Cr features, indicative of a change of oxidation state from Cr3+ to Cr4+. Higher temperature processing leads to a loss of Cr from the surface region, indicative of its substitution into the bulk.

Spectroscopy of ultrathin epitaxial rutile TiO[sub 2](110) films grown on W(100)

Epitaxial ultrathin titanium dioxide films of 0.3 to similar to 7 nm thickness on a metal single crystal substrate have been investigated by high resolution vibrational and electron spectroscopies. The data complement previous morphological data provided by scanned probe microscopy and low energy electron diffraction to provide very complete characterization of this system. The thicker films display electronic structure consistent with a stoichiometric TiO2 phase. The thinner films appear nonstoichiometric due to band bending and charge transfer from the metal substrate, while work function measurements also show a marked thickness dependence. The vibrational spectroscopy shows three clear phonon bands at 368, 438, and 829 cm(-1) (at 273 K), which confirms a rutile structure. The phonon band intensity scales linearly with film thickness and shift slightly to lower frequencies with increasing temperature, in accord with results for single crystals. (c) 2007 American Institute of Physics.

Luminescence of a new Ru(II) polypyridine complex controlled by a redox-responsive protonable anthra[1,10]phenanthrolinequinone

Redox-controlled luminescence quenching is presented for a new Ru(II)-bipyridine complex [Ru(bpy)(2)(1)](2+) where ligand 1 is an anthra[1,10] phenanthrolinequinone. The complex emits from a short-lived metal-to-ligand charge transfer, (MLCT)-M-3 state (tau = 5.5 ns in deaerated acetonitrile) with a low luminescence quantum yield (5 x 10(-4)). The emission intensity becomes significantly enhanced when the switchable anthraquinone unit is reduced to corresponding hydroquinone. On the contrary, chemical one-electron reduction of the anthraquinone moiety to semiquinone in aprotic tetrahydrofuran results in total quenching of the emission.

Synthesis, spectroscopy and spectroelectrochemistry of chlorocarbonyl {1,2-bis[(2,6-diisopropylphenyl)imino]-acenaphthene-kappa(2)-N,N '}rhodium (I)

Reaction of the dinuclear complex [{Rh(CO)(2)}(2) (mu-Cl)(2)]with an alpha-diimine ligand, 1,2- bis[(2,6-diisopropylphenyl) imino] acenaphthene (iPr(2)Ph-bian), produces square-planar [RhCl(CO)(iPr(2)Ph-bian)]. For the first time, 2: 1 and 1: 1 alpha-diimine/dimer reactions yielded the same product. The rigidity of iPr(2)Ph-bian together with its flexible electronic properties and steric requirements of the 2,6-diisopropyl substituents on the benzene rings allow rapid closure of a chelate bond and replacement of a CO ligand instead of chloride. A resonance Raman study of [RhCl(CO)(iPr(2)Ph-bian)] has revealed a predominant Rh-to-bian charge transfer (MLCT) character of electronic transitions in the visible spectral region. The stabilisation of [RhCl(CO)(iPr(2)Ph-bian)] in lower oxidation states by the pi-acceptor iPr(2)Ph-bian ligand was investigated in situ by UV-VIS, IR and EPR spectroelectrochemistry at variable temperatures. The construction of the novel UV-VIS-NIR-IR low-temperature OTTLE cell used in these studies is described in the last part of the paper.