Tetrathiafulvalene and 2,2'-Bipyridine: Bridging both Worlds in the Pursuit of Novel Molecular Materials

The preparation and characterization of two families of building blocks for molecule-based magnetic and conducting materials are described in three projects. In the first project the synthesis and characterization of three bis-imine ligands LI - L3 is reported. Coordination of LI to a series of metal salts afforded the five novel coordination complexes Sn(L4)C4 (I), [Mn(L4)(u-CI)(CI)(EtOH)h (II), [CU(L4)(u-sal) h(CI04)2 (sal = salicylaldehyde anion) (III), [Fe(Ls)2]CI (IV) and [Fe(LI)h(u-O) (V). All complexes have been structurally and magnetically characterized. X-ray diffraction studies revealed that, upon coordination to Lewis acidic metal salts, the imine bonds of LI are susceptible to nucleophilic attack. As a consequence, the coordination complexes (I) - (IV) contain either the cyclised ligand L4 or hydrolysed ligand Ls. In contrast, the dimeric Fe3+ complex (V) comprises two intact ligand LI molecules. In. this complex, the ligand chelates two Fe(III) centres in a bis-bidentate manner through the lone pairs of a phenoxy oxygen and an imine nitrogen atom. Magnetic studies of complexes (II-V) indicate that the dominant interactions between neighbouring metal centres in all of the complexes are antiferromagnetic. In the second project the synthesis and characterization two families of TTF donors, namely the cyano aryl compounds (VI) - (XI) and the his-aryl TTF derivatives (XII) - (XIV) are reported. The crystal structures of compounds (VI), (VII), (IX) and (XII) exhibit regular stacks comprising of neutral donors. The UV -Vis spectra of compounds (VI) - (XIV) present an leT band, indicative of the transfer of electron density from the TTF donors to the aryl acceptor molecules. Chemical oxidation of donors (VI), (VII), (IX) and (XII) with iodine afforded a series of CT salts that where possible have been characterized by single crystal X -ray diffraction. Structural studies showed that the radical cations in these salts are organized in stacks comprising of dimers of oxidized TTF donors. All four salts behave as semiconductors, displaying room temperature conductivities ranging from 1.852 x 10-7 to 9.620 X 10-3 Scm-I. A second series of CT salts were successfully prepared via the technique of electrocrystallization. Following this methodology, single crystals of two CT salts were obtained. The single crystal X-ray structures of both salts are isostructural, displaying stacks formed by trimers of oxidized donors. Variable temperature conductivity measurements carried out on this series of CT salts reveal they also are semiconductors with conductivities ranging from 2.94 x 10-7 to 1.960 X 10-3 S em-I at room temperature. In the third project the synthesis and characterization of a series of MII(hfac)2 coordination complexes of donor ligand (XII) where M2+ = Co2+, Cu2+, Ni2+ and Zn2+ are reported. These complexes crystallize in a head-to-tail arrangement of TTF donor and bipyridine moieties, placing the metal centres and hfac ligands are located outside the stacks. Magnetic studies of the complexes (XV) - (XVIII) indicate that the bulky hfac ligands prevent neighbouring metal centres from assembling in close proximity, and thus they are magnetically isolated.

Novel M(II) beta-diketiminate complexes for the polymerization of lactide

Des ligands diketimines porteurs de substituants N-benzyl, N-9-anthrylmethyl et N-mesitylmethyl (nacnacBnH, nacnacAnH, and nacnacMesH) ont été synthétisés par condensation d’une amine et d’acétyl acétone ou son monoacétal d’éthylène glycol. La chlorination de la position 3 a été effectuée à l’aide de N-chlorosuccinimide conduisant à la formation des ligands ClnacnacBnH et ClnacnacAnH. Cette même position 3 a également été substituée par un groupement succinimide par lithiation du nacnacBnH, suivi de la réaction avec le N-chlorosuccinimide (3-succinimido-nacnacBnH). Les ligands N-aryl nacnacippH et nacnacNaphH (ipp = 2-isopropylphenyl, Naph = 1-naphthyl) ont été préparés selon les procédures reportées dans la littérature. La réaction de ces ligands avec Zn(TMSA)2 (TMSA = N(SiMe3)2) conduit à la formation des complexes nacnacAnZn(TMSA) et ClnacnacBnZn(TMSA). La protonation avec l’isopropanol permet l’obtention des complexes nacnacAnZnOiPr et ClnacnacBnZnOiPr. La réaction avec Mg(TMSA)2 permet quant à elle la formation des complexes nacnacAnMg(TMSA), nacnacMesMg(TMSA), ClnacnacBnMg(TMSA) et ClnacnacAnMg(TMSA). La protonation subséquente à l’aide du tert-butanol permet l’obtention du nacnacMesMgOtBu et du ClnacnacBnMgOtBu, alors que l’on observe uniquement une décomposition avec les ligands possédant des substituants N-anthrylmethyl. La réaction de ces diketimines avec Cu(OiPr)2 conduit aux dimères hétéroleptiques [nacnacBnCu(μ-OiPr)]2 et [3-Cl-nacnacBnCu(μ-OiPr)]2 lors de l’usage des ligands stériquement peu encombrés. Lors de l’utilisation de ligands plus encombrés, la stabilisation du complexe hétéroleptique par dimérisation n’est plus possible, conduisant, par un échange de ligand, à la formation des complexes homoleptiques Cu(nacnacipp)2 et Cu(nacnacNaph)2. Les complexes homoleptiques Cu(nacnacBn)2 et Cu(3-succinimido-nacnacBn)2 ont été obtenus à partir des ligands N-benzyl. Les ligands encore plus encombrés tels que nacnacAnH, nacnacMesH ou ceux comportant des substituants N-methylbenzyl ne présentent alors plus de réactivité avec le Cu(OiPr)2. La plupart des complexes ont été caractérisés par Diffraction des Rayons X. Les complexes homoleptiques ainsi que ceux de TMSA sont monomériques, alors que ceux formés à partir d’alkoxides se présentent sous forme de dimères à l’état solide. Tous les complexes d’alkoxides ainsi que les nacnacAnMg(TMSA)/BnOH et ClnacnacAnMg(TMSA)/BnOH présentent une réactivité modérée à haute en matière de polymérisation du rac-lactide (90% de conversion en 30 secondes à 3 heures). Le nacnacAnZnOiPr permet la synthèse d’un polymère hautement hétérotactique (Pr = 0.90) quand le ClnacnacBnMgOtBu/BnOH génère un polymère isotactique à -30°C (Pr = 0.43). Tous les autres catalyseurs produisent des polymères atactiques avec une légère tendance hétérotactique (Pr = 0.48 – 0.55). Les complexes hétéroleptiques [nacnacBnCu(μ-OiPr)]2 et [3-Cl-nacnacBnCu(μ-OiPr)]2 se révèlent être de très bons catalyseurs pour la polymérisation du rac-lactide présentant une conversion complète du monomère à température ambiante, en solution, en 0,5 à 5 minutes. Le [nacnacBnCu(μ-OiPr)]2 est actif en présence ou absence d’isopropanol, agissant comme agent de transfert de chaine à haute activité (k2 = 32 M–1•s–1) dans le dichlorométhane. Dans l’acétonitrile, le THF, le dichloromethane et le toluène, [nacnacBnCu(μ-OiPr)]2 conduit à une étroite polydispersité, possédant respectivement des kobs = 2.4(1), 5.3(5), 3.6-4.4 and 10(1) min–1. Aucune réaction parasite, telle qu’une trans-esterification, une épimerisation ou une décomposition du catalyseur, n’a été observée. Les complexes homoleptiques en présence d’alcool libre semblent présenter un équilibre avec une petite quantité de leurs équivalents hétéroleptiques, permettant une polymérisation complète, en moins de 60 min, à température ambiante. Tous les catalyseurs de cuivre présentent un haut contrôle de la polymérisation avec une polydispersité égale ou inférieure à 1.1. Les polymères obtenus sont essentiellement atactiques, avec une légère tendance à l’hétérotacticité à température ambiante et -17°C. Le [nacnacBnCu(μ-OiPr)]2 polymérise également la -butyrolactone (BL), l’-caprolactone (CL) et la -valerolactone (VL) avec des constantes respectivement égales à kobs = 3.0(1)•10–2, 1.2–2.7•10–2, et 0.11(1) min–1. Les homopolymères présentent une étroite polydispersité d’approximativement 1.1. Les polymérisations par addition séquentielle ont mis en évidence une trans-estérification (non observée dans les homopolymérisations) si BL ou CL sont introduits après un bloc lactide.

Relativistic ab initio calculations for ion-atom collisions

Within the independent particle model we solve the time-dependent single-particle equation using ab initio SCF-DIRAC-FOCK-SLATER wavefunctions as a basis. To reinstate the many-particle aspect of the collision system we use the inclusive probability formalism to answer experimental questions. As an example we show an application to the case of S{^15+} on Ar where experimental data on the K-K charge transfer are available for a wide range of impact energies from 4.7 to 90 MeV. Our molecular adiabatic calculations and the evaluation using the inclusive probability formalism show good results in the low energy range from 4.7 to 16 MeV impact energy.

Application of inclusive probability theory to heavy ion-atom collisions

Using the independent particle model as our basis we present a scheme to reduce the complexity and computational effort to calculate inclusive probabilities in many-electron collision system. As an example we present an application to K - K charge transfer in collisions of 2.6 MeV Ne{^9+} on Ne. We are able to give impact parameter-dependent probabilities for many-particle states which could lead to KLL-Auger electrons after collision and we compare with experimental values.

Estimates of electronic coupling for excess electron transfer in DNA

Electronic coupling Vda is one of the key parameters that determine the rate of charge transfer through DNA. While there have been several computational studies of Vda for hole transfer, estimates of electronic couplings for excess electron transfer (ET) in DNA remain unavailable. In the paper, an efficient strategy is established for calculating the ET matrix elements between base pairs in a π stack. Two approaches are considered. First, we employ the diabatic-state (DS) method in which donor and acceptor are represented with radical anions of the canonical base pairs adenine-thymine (AT) and guanine-cytosine (GC). In this approach, similar values of Vda are obtained with the standard 6-31 G* and extended 6-31++ G* basis sets. Second, the electronic couplings are derived from lowest unoccupied molecular orbitals (LUMOs) of neutral systems by using the generalized Mulliken-Hush or fragment charge methods. Because the radical-anion states of AT and GC are well reproduced by LUMOs of the neutral base pairs calculated without diffuse functions, the estimated values of Vda are in good agreement with the couplings obtained for radical-anion states using the DS method. However, when the calculation of a neutral stack is carried out with diffuse functions, LUMOs of the system exhibit the dipole-bound character and cannot be used for estimating electronic couplings. Our calculations suggest that the ET matrix elements Vda for models containing intrastrand thymine and cytosine bases are essentially larger than the couplings in complexes with interstrand pyrimidine bases. The matrix elements for excess electron transfer are found to be considerably smaller than the corresponding values for hole transfer and to be very responsive to structural changes in a DNA stack

Intramolecular proton transfer in [Ph2B-OH2](+). Participation of a phenyl group

Ab initio calculations at the HF/6-31+G* level on [Ph2B-OH2](+) show that in the gas phase the structure with the proton attached to an ipso C is lower in energy than the one with the proton on the oxygen atom by 8.40 kcal mol(-1). The transition states and reaction paths for intramolecular proton transfer in [Ph2B-OH2](+) have also been studied.

Thermo-responsive poly(methyl methacrylate)-block-poly(N-isopropylacrylamide) block copolymers synthesized by RAFT polymerization: micellization and gelation

RAFT polymerization was used to prepare PMMA-b-PNIPAM copolymers. Two different chain transfer agents, tBDB and MCPDB, were used to mediate the sequential polymerizations. Micellar solutions and gels were prepared from the resulting copolymers in aqueous solution. When heated above T-c of PNIPAM (about 31 degrees C), DLS revealed that PNIPAM coronas collapsed, resulting in aggregation of the original micelles. The micellar gels underwent syneresis above T-c as water was expelled from the ordered gel structure, the lattice periodicity of which was determined by SANS. A large decrease in lattice spacing was observed above T-c. The gel became more viscoelastic at high temperature, as revealed by shear rheometry which showed a large increase in G".

Charge transfer in Cr adsorption and reaction at the rutile TiO2(110) surface

The rutile TiO2(110) surface has been doped with sub-monolayer metallic Cr, which oxidises and donates charge to specific surface Ti ions. X-Ray and ultra violet photoemission spectroscopy and first principles density functional theory with Hubbard U are used to assign the oxidation states of Cr and surface Ti and we find that Cr2+ forms on bridging oxygen ions and a 5-fold coordinated surface Ti atom is reduced to Ti3+ and the Cr ions readily react with oxygen (to Cr3+), which leads to depletion of surface Ti3+ 3d electrons.

Critical Mass: Sermon for the Church of the Atom (part of A Theatre to Address at Arnolfini, Bristol and Late at Tate Britain)

A Theatre to Address explores the work of contemporary artists who use text as both a visual and sonic form. In this programme, text appears not primarily as a means of communication, but as something which has shape and structure of its own. The Reading Room will also be displaying work that looks at text as concrete or visual poetry, and the script in artists' practice. Clare Gasson presents a new work The traveller - walking walking walking through ... that explores the connection between the text, the rhythm and the action. Maryam Jafri presents a performance-lecture Death With Friends, a body of visual and textual material that forms the basis for her new film of the same name. Pil and Galia Kollectiv present a radical worship for the apocalypse, featuring a sermon for the Church of the Atom with live music by Gelbart.

Electronic charge transfer between ceria surfaces and gold adatoms: a GGA+U investigation

We use density functional theory calculations with Hubbard corrections (DFT+U) to investigate electronic aspects of the interaction between ceria surfaces and gold atoms. Our results show that Au adatoms at the (111) surface of ceria can adopt Au0, Au+ or Au� electronic configurations depending on the adsorption site. The strongest adsorption sites are on top of the surface oxygen and in a bridge position between two surface oxygen atoms, and in both cases charge transfer from the gold atom to one of the Ce cations at the surface is involved. Adsorption at other sites, including the hollow sites of the surface, and an O–Ce bridging site, is weaker and does not involve charge transfer. Adsorption at an oxygen vacancy site is very strong and involves the formation of an Au� anion. We argue that the ability of gold atoms to stabilise oxygen vacancies at the ceria surface by moving into the vacancy site and attracting the excess electrons of the defect could be responsible for the enhanced reducibility of ceria surfaces in the presence of gold. Finally, we rationalise the differences in charge transfer behaviour from site to site in terms of the electrostatic potential at the surface and the coordination of the species.

RuII(α-diimine) or RuIII(α-diimine·–)? Structural, spectroscopic, and theoretical evidence for the stabilization of a prominent metal-to-Ligand charge- transfer excited-state configuration in the ground state

The new compounds [Ru(R-DAB)(acac)2] (R-DAB = 1,4-diorganyl- 1,4-diazabuta-1,3-diene; R = tert-butyl, 4-methoxyphenyl, 2,6-dimethylphenyl; acac– = 2,4-pentanedionate) exhibit intrachelate ring bond lengths 1.297transfer absorption band in the visible region and by DFT calculations. Oxidation of the compounds occurs mainly at the R-DAB·– radical ligand to produce UV/Vis/NIR and electron paramagnetic resonance (EPR) spectroelectrochemically detectable RuIII species, whereas the reduction proceeds less reversibly and yields predominantly (R-DAB)-ligand-based spin for the 4-methoxyphenyl derivative, measured at low temperature. The results are discussed with respect to metal-to-ligand chargetransfer (MLCT) excited states of conventional (α-diimine)- ruthenium(II) complexes and in view of other (α-diimine)- metal complexes with ambiguous oxidation-state assignments.

Structure and spectroelectrochemical response of arene− ruthenium and arene−osmium complexes with potentially hemilabile noninnocent ligands

Nine of the compounds [M(L2−)(p-cymene)] (M = Ru, Os, L2− = 4,6-di-tert-butyl-N-aryl-o-amidophenolate) were prepared and structurally characterized (Ru complexes) as coordinatively unsaturated, formally 16 valence electron species. On L2−-ligand based oxidation to EPR-active iminosemiquinone radical complexes, the compounds seek to bind a donor atom (if available) from the N-aryl substituent, as structurally certified for thioether and selenoether functions, or from the donor solvent. Simulated cyclic voltammograms and spectroelectrochemistry at ambient and low temperatures in combination with DFT results confirm a square scheme behavior (ECEC mechanism) involving the Ln ligand as the main electron transfer site and the metal with fractional (δ) oxidation as the center for redox-activated coordination. Attempts to crystallize [Ru(Cym)(QSMe)](PF6) produced single crystals of [RuIII(QSMe •−)2](PF6) after apparent dissociation of the arene ligand.

EPR in the Characterization of the Shade Effect on Translucence, Remaining Free Radicals, and Polymerization Depth of Commercially Available Resin Composites

The aim of this study was to assess the relation between the number of free radicals generated and the polymerization depth in two different commercial brands of resin composites with different colors and translucence. Electron paramagnetic resonance quantified the radical populations through relative intensity (I (r)) of free radicals generated, and radical decay was monitored. Sample translucence and the classical polymerization depth were measured. The analysis indicated that resin with more color pigments (MA4, I (r) = 0.73 a.u) or more opacity components (ODA2, I (r) = 0.84 a.u) generated smaller populations of free radicals and have the lower polymerization depth than clearer (M, I (r) = 1.20 a.u and MA2, I (r) = 1.02) or more translucent (OEA2, I (r) = 1.00 a.u) composites for the same light-curing time. It seems that irradiation doses have to be adequate to more colored and less translucent resins.

Detailed analysis of the charge transfer complex N,N-dimethylaniline-SO(2) by Raman spectroscopy and density functional theory calculations

Although the amine sulfur dioxide chemistry was well characterized in the past both experimentally and theoretically, no systematic Raman spectroscopic study describes the interaction between N,N-dimethylaniline (DMA) and sulfur dioxide (SO(2)). The formation of a deep red oil by the reaction of SO(2) with DMA is an evidence of the charge transfer (CT) nature of the DMA-SO(2) interaction. The DMA -SO(2) normal Raman spectrum shows the appearance of two intense bands at 1110 and 1151 cm(-1), which are enhanced when resonance is approached. These bands are assigned to nu(s)(SO(2)) and nu(phi-N) vibrational modes, respectively, confirming the interaction between SO(2) and the amine via the nitrogen atom. The dimethyl group steric effect favors the interaction of SO(2) with the ring pi electrons, which gives rise to a pi-pi* low-energy CT electronic transition, as confirmed by time-dependent density functional theory (TDDFT) calculations. In addition, the calculated Raman DMA-SO(2) spectrum at the B3LYP/6-311++g(3df,3pd) level shows good agreement with the experimental results (vibrational wavenumbers and relative intensities), allowing a complete assignment of the vibrational modes. A better understanding of the intermolecular interactions in this model system can be extremely useful in designing new materials to absorb, detect, or even quantify SO(2). Copyright (C) 2009 John Wiley & Sons, Ltd.