Bis(Vinylenedithio)-Tetrathiafulvalene-Based Coordination Networks.

Novel coordination polymers embedding electroactive moieties present a high interest in the development of porous conducting materials. While tetrathiafulvalene (TTF) based metal-organic frameworks were reported to yield through-space conducting frameworks, the use of S-enriched scaffolds remains elusive in this field. Herein is reported the employment of bis(vinylenedithio)-tetrathiafulvalene (BVDT-TTF) functionalized with pyridine coordinating moieties in coordination polymers. Its combination with various transition metals yielded four isostructural networks, whose conductivity increased upon chemical oxidation with iodine. The oxidation was confirmed in a single-crystal to single-crystal X-ray diffraction experiment for the Cd(II) coordination polymer. Raman spectroscopy measurements and DFT calculations confirmed the oxidation state of the bulk materials, and band structure calculations assessed the ground state as an electronically localized antiferromagnetic state, while the conduction occurs in a 2D manner. These results are shedding light to comprehend how to improve through-space conductivity thanks to sulfur enriched ligands.

Mixed-Valence Conductors from Ni Bis(diselenolene) Complexes with a Thiazoline Backbone.

Highly conducting, mixed-valence, multi-component nickel bis(diselenolene) salts were obtained by electrocrystallization of the monoanionic species [Ni(Me-thiazds)2]-1 (Me-thiazds: N-methyl-1,3-thiazoline-2-thione-4,5-diselenolate), with 1:2 and 1:3 stoichiometries depending of the counter ion used (Et4N+ and nBu4N+ vs Ph4P+, respectively). This behavior strongly differs from that of the corresponding monoanionic dithiolene complexes whose oxidation afforded the single component neutral species. This provides additional rare examples of mixed-valence conducting salts of nickel diselenolene complexes, only known in two examples with the dsit (1,3-dithiole-2-thione-4,5-diselenolate) and dsise (1,3-dithiole-2-selone-4,5-diselenolate) ligands. The mixed-valence salts form highly dimerized or trimerized bi- and trimetallic units, rarely seen with such nickel complexes. Transport measurements under a high pressure (up to 10 GPa) and band structure calculations confirm the semiconducting character of [Ph4P][Ni(Me-thiazds)2]3 and the quasi metallic character of [Et4N][Ni(Me-thiazds)2]2 and [NBu4]x[Ni(Me-thiazds)2]2 salts (0 < x < 1).

Enhancing c-Si Solar Cell Efficiency in the UV Region: Photophysical Insights into the Use of Eu3+ Complexes for Down-Shifting Layer Applications.

[Eu(3DPIQC)3] (where DPIQC = 3-(diphenyl phosphoryl)-1-isoquinolinecarboxylate), a luminescent europium complex with antenna ligands, has been carefully embedded within a polyvinyl butyral (PVB) matrix and the resulting material was used to prepare films used as luminescent down-shifting layers (LDSLs) for crystalline Si-based solar cells. The films were characterized using photoluminescence spectroscopy, atomic force spectroscopy (AFM), UV-Vis spectroscopy, and fluorescence microscopy. The AFM analysis shows films with low surface roughness, while fluorescence microscopy revealed that the Eu complex embedded in PVB assumed a spheroidal configuration, a morphology especially beneficial for optical applications. The so-obtained LDSLs were utilized as energy converters in c-Si solar cells to enhance the utilization of high-energy photons, thereby improving their overall efficiency. The determination of photovoltaic parameters carried out before and after the deposition of the LDSLs on the c-Si cells confirms a positive effect on the efficiency of the cell. The Jsc increases from 121.6 mA/cm2 to 124.9 mA/cm2, and the open circuit voltage (Voc) is found to be unrelated to the complex concentration in the films. The fill factor (FF) remains constant with the Eu concentration. The EQE curves indicate an enhancement in the performance of the photovoltaic cells within the UV region of the spectrum for all coated devices. Electrochemical impedance spectroscopy (EIS) was also carried out in order to analyze the effect of the Eu complex in the charge transfer process of the devices.

Intermolecular Resonance Correlates Electron Pairs Down a Supermolecular Chain: Antiferromagnetism in K-Doped p-Terphenyl.

Recent interest in potassium-doped p-terphenyl has been fueled by reports of superconductivity at Tc values surprisingly high for organic compounds. Despite these interesting properties, studies of the structure-function relationships within these materials have been scarce. Here, we isolate a phase-pure crystal of potassium-doped p-terphenyl: [K(222)]2[p-terphenyl3]. Emerging antiferromagnetism in the anisotropic structure is studied in depth by magnetometry and electron spin resonance. Combining these experimental results with density functional theory calculations, we describe the antiferromagnetic coupling in this system that occurs in all 3 crystallographic directions. The strongest coupling was found along the ends of the terphenyls, where the additional electron on neighboring p-terphenyls antiferromagnetically couple. This delocalized bonding interaction is reminiscent of the doubly degenerate resonance structure depiction of polyacetylene. These findings hint toward magnetic fluctuation-induced superconductivity in potassium-doped p-terphenyl, which has a close analogy with high Tc cuprate superconductors. The new approach described here is very versatile as shown by the preparation of two additional salts through systematic changing of the building blocks.

Engineering Polar Oxynitrides: Hexagonal Perovskite BaWON2.

Non-centrosymmetric polar compounds have important technological properties. Reported perovskite oxynitrides show centrosymmetric structures, and for some of them high permittivities have been observed and ascribed to local dipoles induced by partial order of nitride and oxide. Reported here is the first hexagonal perovskite oxynitride BaWON2 , which shows a polar 6H polytype. Synchrotron X-ray and neutron powder diffraction, and annular bright-field in scanning transmission electron microscopy indicate that it crystalizes in the non-centrosymmetric space group P63 mc, with a total order of nitride and oxide at two distinct coordination environments in cubic and hexagonal packed BaX3 layers. A synergetic second-order Jahn-Teller effect, supported by first principle calculations, anion order, and electrostatic repulsions between W6+ cations, induce large distortions at two inequivalent face-sharing octahedra that lead to long-range ordered dipoles and spontaneous polarization along the c axis. The new oxynitride is a semiconductor with a band gap of 1.1 eV and a large permittivity.

Effects of Temperature on the Shape and Symmetry of Molecules and Solids.

Despite its undeniable problems from a philosophical point of view, the concept of molecular structure, with attributes such as shape and symmetry, directly borrowed from the description of macroscopic objects, is nowadays central to most of the chemical sciences. Descriptions such as "the tetrahedral carbon atom" or "octahedral coordination complexes" are widely used as much in elementary textbooks as in the most up-to-date research articles. The definition of molecular shape is, however, not as simple as it might seem at first sight. Molecules don't behave as macroscopic objects do, and the arrangement of atoms within a molecule changes continuously due to the incessant motion of its constituent particles, nuclei, and electrons. How are molecular shape and symmetry affected by this thermal motion? In this Minireview, we introduce the language of continuous symmetry measures as a new tool to quantitatively describe the effects of temperature on molecular shape and symmetry, enriching in this way the set of molecular descriptors that might be used in the establishment of new empirical structure-property relations, of great interest in concomitant areas such as medicinal chemistry or materials science.

Charge Delocalization, Oxidation States, and Silver Mobility in the Mixed Silver-Copper Oxide AgCuO2 ¤.

The electronic structure of AgCuO2, and more specifically the possible charge delocalization and its implications for the transport properties, has been the object of debate. Here the problem is faced by means of first-principles density functional theory calculations of the electron and phonon band structures as well as molecular dynamics simulations for different temperatures. It is found that both Cu and Ag exhibit noninteger oxidation states, in agreement with previous spectroscopic studies. The robust CuO2 chains impose a relatively short contact distance to the silver atoms, which are forced to partially use their d z2 orbitals to build a band. This band is partially emptied through overlap with a band of the CuO2 chain, which should be empty if copper were in a Cu3+ oxidation state. In that way, although structural correlations could roughly be consistent with an Ag+Cu3+O2 formulation, the appropriate oxidation states for the silver and copper atoms become Ag(1+δ)+ and Cu(3-δ)+, and as a consequence, the stoichiometric material should be metallic. The study of the electronic structure suggests that Ag atoms form relatively stable chains that can easily slide despite the linear coordination with oxygen atoms of the CuO2 chains. Phonon dispersion calculations and molecular dynamics simulations confirm the stability of the structure although pointing out that sliding of the silver chains is an easy motion that does not lead to substantial modifications of the electronic structure around the Fermi level and, thus, should not alter the good conductivity of the system. However, this sliding of the silver atoms from the equilibrium position explains the observed large thermal factors.

Conformational analysis of enantiomerization coupled to internal rotation in triptycyl-n-helicenes.

We present a computational study of a reduced potential energy surface (PES) to describe enantiomerization and internal rotation in three triptycyl-n-helicene molecules, centering the discussion on the issue of a proper reaction coordinate choice. To reflect the full symmetry of both strongly coupled enantiomerization and rotation processes, two non-fixed combinations of dihedral angles must be used, implying serious computational problems that required the development of a complex general algorithm. The characteristic points on each PES are analyzed, the intrinsic reaction coordinates are calculated, and finally they are projected on the reduced PES. Unlike what was previously found for triptycyl-3-helicene, the surfaces for triptycyl-4-helicene and triptycyl-5-helicene contain valley-ridge-inflection (VRI) points. The reaction paths on the reduced surfaces are analyzed to understand the dynamical behaviour of these molecules and to evaluate the possibility of a molecule of this family exhibiting a Brownian ratchet behaviour.

Electronic engineering of a tetrathiafulvalene charge-transfer salt via reduced symmetry induced by combined substituents.

A 1 : 1 metallic charge-transfer salt is obtained by cosublimation of (Z,E)-(SMe)2Me2TTF and TCNQ. X-ray diffraction studies confirm the formation of segregated stacks comprising donor and acceptor molecules in [(E)-(SMe)2Me2TTF](TCNQ). The crystal packing features lateral SS interactions between TTF stacks, which is in sharp contrast to that in (TTF)(TCNQ). Structural analysis and theoretical studies afford a partial charge-transfer (ρ ≈ 0.52), leading to a system with the electronic structure close to quarter-filled. Resistivity measurements reveal that this material behaves as a metal down to 56 K and 22 K at 1 bar and 14.9 kbar, respectively. The thermopower is negative in the metallic regime, indicating the dominant role of the acceptor stacks for the observed conducting behavior. Analysis of single-crystal EPR spectra shows the remaining spin susceptibility at 4.3 K, suggesting the importance of the Hubbard U correction. These results highlight the judicious engineering of electronic and geometrical effects on the TTF core; the combined use of methyl and thiomethyl groups has decreased the TCNQ bandwidth while maintaining the segregated stacks, converting the metal to insulator (M-I) transition to more 4kF like. In addition, the enhanced SS contacts between the TTF stacks lead to more rapidly decreasing M-I transition temperature under various pressures.

Conducting Anilate-Based Mixed-Valence Fe(II)Fe(III) Coordination Polymer: Small-Polaron Hopping Model for Oxalate-Type Fe(II)Fe(III) 2D Networks.

The mixed-valence FeIIFeIII 2D coordination polymer formulated as [TAG][FeIIFeIII(ClCNAn)3]·(solvate) 1 (TAG = tris(amino)-guanidinium, ClCNAn2- = chlorocyanoanilate dianionic ligand) crystallized in the polar trigonal space group P3. In the solid-state structure, determined both at 150 and at 10 K, anionic 2D honeycomb layers [FeIIFeIII(ClCNAn)3]- establish in the ab plane, with an intralayer metal-metal distance of 7.860 Å, alternating with cationic layers of TAG. The similar Fe-O distances suggest electron delocalization and an average oxidation state of +2.5 for each Fe center. The cation imposes its C3 symmetry to the structure and engages in intermolecular N-H···Cl hydrogen bonding with the ligand. Magnetic susceptibility characterization indicates magnetic ordering below 4 K and the presence of a hysteresis loop at 2 K with a coercive field of 60 Oe. Mössbauer measurements are in agreement with the existence of Fe(+2.5) ions at RT and statistic charge localization at 10 K. The compound shows semiconducting behavior with the in-plane conductivity of 2 × 10-3 S/cm, 3 orders of magnitude higher than the perpendicular one. A small-polaron hopping model has been applied to a series of oxalate-type FeIIFeIII 2D coordination polymers, providing a clear explanation on the much higher conductivity of the anilate-based systems than the oxalate ones.

Localization versus Delocalization in Chiral Single Component Conductors of Gold Bis(dithiolene) Complexes.

The first examples of chiral single component conductors are reported. Both (S,S) and (R,R) enantiomers of 5,6-dimethyl-5,6-dihydro-1,4-dithiin-2,3-dithiolate (dm-dddt) ligand have been used to prepare anionic metal bis(dithiolene) complexes formulated as ([(n-Bu)4N][M(dm-dddt)2] (M = Au, Ni), which are isostructural according to single crystal X-ray analysis. Single crystal transport measurements indicate semiconducting behavior for the anionic radical Ni complexes, with low room temperature conductivity values and high activation energies. Electrocrystallization experiments provided neutral [M(dm-dddt)2] (M = Au, Ni) complexes. The neutral radical gold compounds show intermolecular S···S interactions in the solid state giving rise to layers interconnected through weak C-H···S hydrogen bonds. The most peculiar structural feature concerns a dissymmetry between the two dithiolene moieties, while the nickel counterpart is symmetric. Single crystal resistivity measurements show thermally activated behavior for the open-shell gold complexes, with room temperature conductivity values of 0.02-0.04 S·cm(-1) and activation energies strongly influenced by hydrostatic pressure. A thorough theoretical study on nickel anion radical and gold neutral radical bis(dithiolene) complexes applied to the chiral complexes [M(dm-dddt)2] (M = Au, Ni(-)) and to a series of previously reported compounds addressed the issue of symmetry versus asymmetry from an electronic coupling perspective between the two dithiolene ligands. It results that neutral gold complexes with dithiolene ligands without extended delocalization are Class II mixed-valent compounds in the Robin and Day classification, presenting an inherent tendency toward asymmetric structures, which can be however modulated by the intermolecular organization in the solid state.

Exploring the electronic structure of an organic semiconductor based on a compactly fused electron donor-acceptor molecule.

A Mott-type semiconductor based on a compactly fused and partially oxidized electron donor-acceptor (D-A) molecule was recently prepared and identified to exhibit a large room-temperature conductivity of 2 S cm(-1) . In a marked contrast to the organic conductors characterized by relatively well decoupled and segregated uniform stacks of D and A moieties, the formally half-oxidized tetrathiafulvalene donors of the actual compound are organized in columnar π stacks only, whereby the coplanar electron-acceptor units, namely benzothiadiazole, are closely annulated along their ridges. Herein, we present a theoretical study that explores the electronic structure of this novel type of organic semiconductor. The highly symmetric-solid state material behaves as a one-dimensional electronic system with strong antiferromagnetic interactions (coupling constant>200 cm(-1) ). The unique shape and local dipole of this redox-active fused electron D-A molecule lays the basis for further investigations of the collective electronic structure, mainly in the function of different counterions embedded in the crystalline lattice.

Links between the Crystal and Electronic Structure in the New Family of Unconventional Superconductors A2Cr3As3 (A = K, Rb, Cs).

The electronic structure of a new family of superconductors is examined through density functional theory calculations. In contrast with other quasi-1D superconductors, these phases exhibit a relatively complex electronic structure and the Fermi surface contains both 1D and 3D components. It is shown that cations have an almost nil influence on the electronic structure. The absence of a structural Peierls modulation is discussed, and the differences with the structurally related M2Mo6Se6 (M = Tl, In, ...) superconductors are stressed. The large electron mass renormalization and the lack of clear correlation between N(EF) and Tc suggest the existence of strong electron correlations and an unconventional origin of the superconductivity.

Electronic Structure and Magnetic Properties of CuFeS2.

Chalcopyrite (CuFeS2) is an antiferromagnetic semiconductor with unusual magnetic and electrical properties, which are still not clearly understood. Neutron diffraction experiments reveal a phase transition at ∼50 K that has been attributed to an unexpected appearance of magnetic moments on Cu ions, having a paramagnetic arrangement down to 50 K and then ordering to an antiferromagnetic state at lower temperatures. In this study we use DFT-based computational methods to investigate the electronic structure and magnetic properties of CuFeS2 in order to obtain a reliable source of information for the interpretation of the observed magnetic behavior, and in particular to shed some light on the magnetic behavior of copper atoms in this compound. We have calculated the electronic structure of the ground and low-energy magnetically excited states and deduced a set of exchange coupling constants that are used afterward in classical Monte Carlo simulations to obtain magnetic susceptibility data, which compare successfully with our experimental results above ∼170 K. From our results it can be inferred that copper atoms remain in a diamagnetic state in this temperature range, although spin delocalization from neighboring iron atoms results in a non-negligible spin density on the copper atoms at high temperatures.

Distortions of π-coordinated arenes with anionic character.

A qualitative analysis of the distortions that operate on the π system of bridging arenes with anionic character is presented and substantiated by computational studies at the density functional B3LYP and CASSCF levels. The observed effects of bonding to two metal atoms and of the negative charge are an expansion of the arene ring due to the partial occupation of π* orbitals, an elongation or compression distortion accompanied by a loss of the equivalence of carbon-carbon bonds due to a Jahn-Teller distortion of the arene dianions, and a ring puckering due to a second-order Jahn-Teller distortion that may appear independently of the existence of the first-order effect. The workings of the orbital mixing produced by these distortions have been revealed in a straightforward way by a pseudosymmetry analysis of the HOMOs of the distorted conformations. The systems studied include Li(I) and Y(III) adducts of benzene, as well as trimethylsilyl-substituted derivatives in the former case. An analysis of the structural data of a variety of purported di- and tetraanionic arene ligands coordinated to transition metals in several bridging modes has reproduced the main geometrical trends found in the computational study for the benzene and trimethylsilyl-substituted benzene dianions, allowing a classification of the variety of structural motifs found in the literature.

Nature of holes, oxidation states, and hypervalency in covellite (CuS).

The electronic structure of covellite (CuS) is analyzed on the basis of density functional theory calculations. The nature of holes in the valence band, as well as the so far much debated question of the appropriate oxidation formalism for this conductor, is discussed. The role of S-S bonds and the anomalous coordination of one type of sulfur atom (hypervalency) are considered. It is suggested that the low-temperature transition is mostly a symmetry-lowering process slightly stabilizing the Cu-S network.

Stereochemistry of complexes with double and triple metal-ligand bonds: a continuous shape measures analysis.

To each coordination polyhedron we can associate a normalized coordination polyhedron that retains the angular orientation of the central atom-ligand bonds but has all the vertices at the same distance from the center. The use of shape measures of these normalized coordination polyhedra provides a simple and efficient way of discriminating angular and bond distance distortions from an ideal polyhedron. In this paper we explore the applications of such an approach to analyses of several stereochemical problems. Among others, we discuss how to discern the off-center displacement of the metal from metal-ligand bond shortening distortions in families of square planar biscarbene and octahedral dioxo complexes. The normalized polyhedron approach is also shown to be very useful to understand stereochemical trends with the help of shape maps, minimal distortion pathways, and ligand association/dissociation pathways, illustrated by the Berry and anti Berry distortions of triple-bonded [X≡ML4] complexes, the square pyramidal geometries of Mo coordination polyhedra in oxido-reductases, the coordination geometries of actinyl complexes, and the tetrahedricity of heavy atom-substituted carbon centers.

A fullerene-carbene adduct as a crystalline molecular rotor: remarkable behavior of a spherically-shaped rotator.

A new fullerene structure was recently obtained from the reaction of a Lewis basic N-heterocyclic carbene (NHC) and the Lewis acidic C60. The molecular features of the zwitterionic adduct can be described as a molecular rotor with the fullerene cage acting as the rotator that spins about one distinct axis given by its C-C single bond linkage with the imidazolium heterocycle stator. A detailed structural analysis of the compound by means of single-crystal X-ray diffraction (XRD) revealed significant differences in the packing motifs of solvent-free and solvent-containing crystals. Variable temperature single-crystal XRD experiments (80 K ≤ T ≤ 480 K) carried out to investigate the rotational dynamics of the fullerene group in the higher quality solvent-free structure revealed atomic displacement parameters consistent with fast rotation of the highly symmetric fullerene in the solid state, whereas the imidazolium unit remains in a fixed position and therefore represents the stator. DFT and semiempirical calculations were applied to get insight into the profile of the rotational potential of the fullerene unit, particularly considering interactions with the neighboring molecules in the crystal lattice. The results indicate that the crystal environment leads to the presence of one lowest energy minimum that is connected to seven others that are slightly higher in energy through rotational barriers of approximately 1.5-2.5 kcal mol(-1).

Optical properties of 4-bromobenzaldehyde derivatives in chloroform solution.

In this work we give a deeper insight into the electronic structure of a series of purely organic molecules that were recently employed as building blocks in crystals with very efficient phosphorescent emission. With this purpose, the low-lying excited states of a series of 4-bromobenzaldehyde derivatives in chloroform solution are explored by means of time-dependent density functional theory (TDDFT) calculations, together with the absorption, fluorescence, and phosphorescence experimental spectra. The optical properties of the studied molecular models are extensively discussed, in terms of the frontier molecular orbitals involved in the relevant electronic transitions, the recorded and simulated absorption profiles, and the molecular geometries and transition energies of the emitting states. The calculations eventually help in the assignment of the character of the lowest lying singlet and triplet emitting states for these compounds.

Pseudosymmetry analysis of molecular orbitals.

We introduce a pseudosymmetry analysis of molecular orbitals by means of the newly proposed irreducible representation measures. To do that we define first what we consider as molecular pseudosymmetry and the relationships of this concept with those of approximate symmetry and quasisymmetry. We develop a general algorithm to quantify the pseudosymmetry content of a given object within the framework of the finite group algebra. The obtained mathematical expressions are able to decompose molecular orbitals by means of the irreducible representations of any reference symmetry point group. The implementation and usefulness of the pseudosymmetry analysis of molecular orbitals is demonstrated in the study of σ and π orbitals in planar and nonplanar polycyclic aromatic hydrocarbons and the t2 g and eg character of the d-orbitals in the [FeH6](3-) anion in its high spin state along the Bailar twist pathway.