Electronic and Structural Properties of Thin Iron Oxide Films on CeO2.

Modification of CeO2 (ceria) with 3d transition metals, particularly iron, has been proven to significantly enhance its catalytic efficiency in oxidation or combustion reactions. Although this phenomenon is widely reported, the nature of the iron-ceria interaction responsible for this improvement remains debated. To address this issue, we prepared well-defined model FeOx/CeO2(111) catalytic systems and studied their structure and interfacial electronic properties using photoelectron spectroscopy, scanning tunneling microscopy, and low-energy electron diffraction, coupled with density functional theory (DFT) calculations. Our results show that under ultrahigh vacuum conditions, Fe deposition leads to the formation of small FeOx clusters on the ceria surface. Subsequent annealing results in the growth of large amorphous FeOx particles and a 2D FeOx layer. Annealing in an oxygen-rich atmosphere further oxidizes iron up to the Fe3+ state and improves the crystallinity of both the 2D layer and the 3D particles. Our DFT calculations indicate that the 2D FeOx layer interacts strongly with the ceria surface, exhibiting structural corrugations and transferred electrons between Fe2+/Fe3+ and Ce4+/Ce3+ redox pairs. The novel 2D FeOx/CeO2(111) phase may explain the enhancement of the catalytic properties of CeO2 by iron. Moreover, the corrugated 2D FeOx layer can serve as a template for the ordered nucleation of other catalytically active metals, in which the redox properties of the 2D FeOx/CeO2(111) system are exploited to modulate the charge of the supported metals.

Chemical Orderings in CuCo Nanoparticles: Topological Modeling Using DFT Calculations.

The orderings of atoms in bimetallic 1.6-2.1 nm-large CuCo nanoparticles, important as catalytic and magnetic materials, were studied using a combination of DFT calculations with a topological approach. The structure and magnetism of Cu50Co151, Cu101Co100, Cu151Co50, and Cu303Co102 nanoparticles; their resistance to disintegrating into separate Cu and Co species; as well as the exposed surface sites, were quantified and analyzed, showing a clear preference for Cu atoms to occupy surface positions while the Co atoms tended to form a compact cluster in the interior of the nanoparticles. The surface segregation of Co atoms that are encapsulated by less-active Cu atoms, induced by the adsorption of CO molecules, was already enabled at a low coverage of adsorbed CO, providing the energy required to displace the entire compact Co species inside the Cu matrices due to a notable adsorption preference of CO for the Co sites over the Cu ones. The calculated adsorption energies and vibrational frequencies of adsorbed CO should be helpful indicators for experimentally monitoring the nature of the surface sites of CuCo nanoparticles, especially in the case of active Co surface sites emerging in the presence of CO.

Mixed-ligand, radical, gold bis(dithiolene) complexes: from single-component conductors to controllable NIR-II absorbers.

Neutral radical bis(dithiolene) gold complexes [Au(dt)2]˙ are known to exhibit a strong absorption in the 1400-2000 nm NIR absorption range. Here, we demonstrate that the NIR signature of mixed-ligand bis(dithiolene) gold complexes [Au(dtA)(dtD)]˙ associating two different dithiolene, dtA and dtD, is found at higher energy, out of the range of the homoleptic analogs [Au(dtA)2]˙ and [Au(dtD)2]˙, in the looked-after NIR-II 1000-1400 nm absorption range. An efficient synthetic approach towards precursor mixed-ligand monoanionic gold bis(dithiolene) complexes [Au(dtA)(dtD)]-1 is reported. Using this strategy, no symmetrical complexes are formed and, upon electrocrystallization, no scrambling was observed in solution, allowing for the isolation of radical gold bis(dithiolene) complex such as [Au(bdt)(Et-thiazdt)]˙ (bdt: benzene-1,2-dithiolate; Et-thiazdt: N-ethyl-thiazoline-2-thione-3,4-dithiolate), which behaves as a single-component conductor. It is shown from theoretical calculations that the spin polarization induced by electron repulsions leads to a strong localization of the spin-orbitals, and provides a sound basis to understand, (i) the different ligand-based oxidation potentials, (ii) the NIR optical absorption at notably higher energies and (iii) the larger potential difference of the two redox processes than in the parent symmetric complexes. The solid-state properties of the radical complex [Au(bdt)(Et-thiazdt)]˙ are the consequence of a strongly 1D electronic structure with weakly dimerized chains and electronic localization favoring a semiconducting behavior, stable under pressures up to 18.2 GPa. Altogether, the versatility of the preparation method of [Au(dtA)(dtD)]-1 salts opens the route for a wide library of different mixed-ligand radical complexes [Au(dtA)(dtD)]˙ with simultaneously an adaptable absorption in the NIR-II range and the rich structural chemistry of single-component conductors.

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.

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).

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.

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.

New insights into the structural properties of κ-(BEDT-TTF)2Ag2(CN)3 spin liquid.

Here, the first accurate study is presented of the room-temperature and 100 K structures of one of the first organic spin liquids, κ-(BEDT-TTF)2Ag2(CN)3. It is shown that the monoclinic structure determined previously is only the average one. It is shown that the exact structure presents triclinic symmetry with two non-equivalent dimers in the unit cell. But surprisingly this does not lead to a sizeable charge disproportionation between dimers. The difference from the analogue compound κ-(BEDT-TTF)2Cu2(CN)3 which also presents a spin liquid phase is discussed in detail. The data provided here show the importance of the anionic layer and in particular the transition metal position in the process of symmetry breaking. The possible impact of the symmetry breaking, albeit weak, on the spin-liquid mechanism and the influence of various disorders on the physical properties of this system is also discussed.

Crystallization Induced Enhanced Emission in Two New Zn(II) and Cd(II) Supramolecular Coordination Complexes with the 1-(3,4-Dimethylphenyl)-5-Methyl-1H-1,2,3-Triazole-4-Carboxylate Ligand.

Two new d10 metal supramolecular metal-organic frameworks (SMOFs) with general formula [ML2(H2O)2]n (M = Zn, Cd) have been synthetized using the sodium salt of the anionic 1-(3,4-dimethylphenyl)-5-methyl-1H-1,2,3-triazole-4-carboxylate ligand (Na+L-). Both SMOFs have been structurally characterized by single-crystal X-ray diffraction analysis and IR spectroscopy. The compounds are isostructural and form supramolecular aggregates via hydrogen bonds with the presence of less common dihydrogen bonds. Interestingly, they show ionic conductivity and porosity. The luminescent properties have been also studied by means of the excitation and emission spectra. Periodic DFT and molecular TD-DFT calculations have been used to unravel the emergence of luminescence in the otherwise non-emitting 1-(3,4-dimethylphenyl)-5-methyl-1H-1,2,3-triazole-4-carboxylate ligand once incorporated in the SMOFs. Our results also illustrate the importance of considering the dielectric environment in the crystal when performing excited state calculations for isolated fragments to capture the correct electronic character of the low-lying states, a practice which is not commonly adopted in the community.

In Search of Chiral Molecular Superconductors: κ-[(S,S)-DM-BEDT-TTF]2 ClO4 Revisited.

The relationship between chirality and superconductivity is an intriguing question. The two enantiomeric crystalline radical cation salts κ-[(S,S)-DM-BEDT-TTF]2 ClO4 and κ-[(R,R)-DM-BEDT-TTF]2 ClO4 , showing κ-type arrangement of the organic layers, are investigated in search for superconducting chiral molecular materials following a 1992 report indicating the occurrence of a superconducting transition in the former compound. While the initial interpretation is presently challenged through in-depth temperature and pressure dependent single crystal resistivity measurements combined with band structure calculations, the two chiral conductors show metal like behavior with room temperature conductivities of 10-30 S cm-1 at ambient pressure and stabilization of the metallic state down to the lowest temperatures under moderate pressures. Moreover, their structural and theoretical investigations reveal an original feature, namely the existence of two different κ layers with 1D and 2D electronic dimensionality, respectively, as a consequence of an interlayer charge transfer. The resistivity drop observed for one sample below 1 K and insensitive to magnetic field, possibly results from mixing in-plane and out-of-plane contributions to the measured resistance and suggests current induced charge order melting. This feature contradicts the occurrence of superconductivity in these chiral molecular conductors and leaves open the discovery of the first chiral molecular superconductors.

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.

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.

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.

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.

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.

Evaluation of novel platinum(ii) based AIE compound-encapsulated mesoporous silica nanoparticles for cancer theranostic application.

Advanced biomedical research has established that cancer is a multifactorial disorder which is highly heterogeneous in nature and responds differently to different treatment modalities, due to which constant monitoring of therapy response is becoming extremely important. To accomplish this, different theranostic formulations have been evaluated. However, most of them are found to suffer from several limitations extending from poor resolution, radiation damage, to high costs. In order to develop a better theranostic modality, we have designed and synthesized a novel platinum(ii)-based 'aggregation induced emission' (AIE) molecule (named BMPP-Pt) which showed strong intra-cellular fluorescence and also simultaneously exhibited potent cytotoxic activity. Due to this dual functionality, we wanted to explore the possibility of using this compound as a single molecule based theranostic modality. This compound was characterized using elemental analysis, NMR and IR spectroscopy, mass spectrometry and single crystal X-ray structure determination. BMPP-Pt was found to exhibit a high AIE property with emission maxima at 497 nm. For more efficient cancer cell targeting, BMPP-Pt was encapsulated into mesoporous silica nanoparticles (Pt-MSNPs) and the MSNPs were further surface modified with an anti-EpCAM aptamer (Pt-MSNP-E). Pt-MSNPs exhibited higher intracellular fluorescence compared to free BMPP-Pt, though both of them induced a similar degree of cell death via the apoptosis pathway, possibly via cell cycle arrest in the G1 phase. Anti-EpCAM aptamer modification was found to increase both cytotoxicity and intracellular fluorescence compared to unmodified MSNPs. Our study showed that EpCAM functionalized BMPP-Pt loaded MSNPs can efficiently internalize and induce apoptosis of cancer cells as well as show strong intracellular fluorescence. This study provides clues towards the development of a potential single compound based theranostic modality in future.

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.

Self-Assembly of Discrete Metallocycles versus Coordination Polymers Based on Cu(I) and Ag(I) Ions and Flexible Ligands: Structural Diversification and Luminescent Properties.

Three new Ag(I) and one Cu(I) coordination compounds with two different positional isomers, propane-1,3-diyl bis(pyridine-4-carboxylate) (L1) and propane-1,3-diyl bis(pyridine-3-carboxylate) (L2), of a bis-(pyridyl-carboxylate) ligand have been synthesized. X-ray diffraction analysis revealed that the self-assembly of L1 with AgCF3SO3 and AgClO4 salts leads to the formation of discrete binuclear metallocycles {Ag(L1)CF3SO3}2 (1) and {Ag(L1)ClO4}2 (2), respectively. However, self-assembly of the other ligand, L2, with AgCF3SO3 and CuCl salts, results in a 1-D zig-zag chain {Ag(L2)CF3SO3}∞ (3) and a 1-D double-stranded helical chain {Cu2Cl2(L2)2}∞ (4) coordination polymers, respectively. Solid emission spectra recorded at room temperature show interesting luminescence properties for all four compounds in the range from 438 to 550 nm, especially for compound 4 that was found to change its emission color when the wavelength of the excitation radiation is switched from 332 to 436 nm.

Structural and electronic control of the metal to insulator transition and local orderings in the θ-(BEDT-TTF)2X organic conductors.

A first-principles density functional theory (DFT) study of [Formula: see text]-(BEDT-TTF)2X molecular conductors with X = I3, CsCo(SCN)4 (ambient pressure, 7.5 kbar and 10 kbar), CsZn(SCN)4, TlCo(SCN)4, RbCo(SCN)4 and RbZn(SCN)4 (220 K and 90 K) is reported. It is shown that these salts exhibit three different types of band structure each of them associated with a different physical behavior. In contrast with previous proposals it is found that the key electronic parameter behind the differences in the band structures is the intrastack transfer integral, t c . A new mechanism for the metal to insulator transition in the [Formula: see text]-(BEDT-TTF)2MM'(SCN)4 ([Formula: see text], Tl; [Formula: see text], Co) salts is proposed, where an order-disorder structural transition of the ethylenedithio groups doubling the periodicity along the stack direction drives the system into an electronically pseudo-1D system along the interstack direction that is subject to a 4k F charge localization of holes. The structural rearrangement is such that the holes are not distributed equally between the two donors; the larger hole density is associated with the B donors which establish the strongest hydrogen bonds with the anion layers. A detailed microscopic description of how disorder of the ethylenedithio groups, the θ dihedral angle and the electronic structure intermingle and lead to the unusual phase diagram of these salts is presented. In this framework the role of pressure and uniaxial strain in controlling the physical behavior of these salts is discussed.