The conductance of a family of biphenyl-dithiol derivatives with conformationally fixed torsion angle was measured using the scanning tunneling microscopy (STM)-break-junction method. We found that it depends on the torsion angle phi between two phenyl rings; twisting the biphenyl system from flat (phi = 0 degrees ) to perpendicular (phi = 90 degrees ) decreased the conductance by a factor of 30. Detailed calculations of transport based on density functional theory and a two level model (TLM) support the experimentally obtained cos(2) phi correlation between the junction conductance G and the torsion angle phi. The TLM describes the pair of hybridizing highest occupied molecular orbital (HOMO) states on the phenyl rings and illustrates that the pi-pi coupling dominates the transport under "off-resonance" conditions where the HOMO levels are well separated from the Femi energy.

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Ni-rich LiNi x Co y Mn z O2 (NCM) cathode materials have great potential for application in next-generation lithium-ion batteries owing to their high specific capacity. However, they are subjected to severe structural changes upon (de)­lithiation, which adversely affects the cycling stability. Herein, we investigate changes in crystal and electronic structure of NCM811 (80% Ni) at high states of charge by a combination of operando X-ray diffraction (XRD), operando hard X-ray absorption spectroscopy (hXAS), ex situ soft X-ray absorption spectroscopy (sXAS), and density functional theory (DFT) calculations and correlate the results with data from galvanostatic cycling in coin cells. XRD reveals a large decrease in unit cell volume from 101.38(1) to 94.26(2) Å3 due to collapse of the interlayer spacing when x(Li) < 0.5 (decrease in c-axis from 14.469(1) Å at x(Li) = 0.6 to 13.732(2) Å at x(Li) = 0.25). hXAS shows that the shrinkage of the transition metal–oxygen layer mainly originates from nickel oxidation. sXAS, together with DFT-based Bader charge analysis, indicates that the shrinkage of the interlayer, which is occupied by lithium, is induced by charge transfer between O 2p and partially filled Ni eg orbitals (resulting in decrease of oxygen–oxygen repulsion). Overall, the results demonstrate that high-voltage operation of NCM811 cathodes is inevitably accompanied by charge-transfer-induced lattice collapse.

Disordered organic materials have a wide range of interesting applications, such as organic light emitting diodes, organic photovoltaics, and thin film electronics. To model electronic transport through such materials it is essential to describe the energy distribution of the available electronic states of the carriers in the material. Here, we present a self-consistent, linear-scaling first-principles approach to model environmental effects on the electronic properties of disordered molecular systems. We apply our parameter free approach to calculate the energy disorder distribution of localized charge states in a full polaron model for two widely used benchmark-systems (tris(8-hydroxyquinolinato)aluminum (Alq3) and N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4,4'-diamine (α-NPD)) and accurately reproduce the experimental charge carrier mobility over a range of 4 orders of magnitude. The method can be generalized to determine electronic and optical properties of more complex systems, e.g. guest-host morphologies, organic-organic interfaces, and thus offers the potential to significantly contribute to de novo materials design.

Proton conducting nanoporous materials attract substantial attention with respect to applications in fuel cells, supercapacitors, chemical sensors, and information processing devices inspired by biological systems. Here, a crystalline, nanoporous material which offers dynamic remote-control over the proton conduction is presented. This is realized by using surface-mounted metal-organic frameworks (SURMOFs) with azobenzene side groups that can undergo light-induced reversible isomerization between the stable trans and cis states. The trans-cis photoisomerization results in the modulation of the interaction between MOF and guest molecules, 1,4-butanediol and 1,2,3-triazole; enabling the switching between the states with significantly increased (trans) and reduced (cis) conductivity. Quantum chemical calculations show that the trans-to-cis isomerization results in the formation of stronger hydrogen bridges of the guest molecules with the azo groups, causing stronger bonding of the guest molecules and, as a result, smaller proton conductivity. It is foreseen that photoswitchable proton-conducting materials may find its application in advanced, remote-controllable chemical sensors, and a variety of devices based on the conductivity of protons or other charged molecules, which can be interfaced with biological systems.

We report on theoretical and experimental work involving a particular molecular switch, an [Fecomplex, that utilizes a spin transition ("crossover"). The hallmark of this transition is a change of the spin of the metal ion, S Fe = 0 to S Fe = 2, at fixed oxidation state of the Fe ion. Combining density functional theory and first principles calculations, we demonstrate that within a single molecule this transition can be triggered by charging the ligands. In this process the total spin of the molecule, combining metal ion and ligands, crosses over from S = 0 to S = 1. Three-terminal transport through a single molecule shows indications of this transition induced by electric gating. Such an electric field control of the spin transition allows for a local, fast, and direct manipulation of molecular spins, an important prerequisite for molecular spintronics.

Future prospects of the organic light emitting diode (OLED) technology rely on the development of new organic semiconductors with optical and electronic properties outperforming those of presently available materials. Computational materials design is becoming a widely used tool to complement and accelerate experimental efforts. Computational tools were also shown to contribute to the understanding of experimentally observed phenomena. Impurities and charge traps are omnipresent in most currently available organic semiconductors and limit the charge transport and thus the efficiency of the devices. The microscopic cause as well as the chemical nature of these traps is presently not well understood. Using a multiscale model we characterize the influence of impurities on the density of states and charge transport in small-molecule amorphous organic semiconductors. We use the model to quantitatively describe the influence of water molecules and water-oxygen complexes on the electron and hole mobility by influencing the shape of the density of states and at the same time acting as explicit charge traps within the energy gap. Our results show that deep trap states introduced by molecular oxygen mainly determine the electron mobility in widely used materials such as α-NPD. TOC

A mononuclear ruthenium(II) polypyridyl complex with an enlarged terpyridyl coordination cage was synthesized by the formal introduction of a carbon bridge between the coordinating pyridine rings. Structurally, the ruthenium(II) complex shows an almost perfect octahedral N6 coordination around the central Ru(II) metal ion. The investigation of the photophysical properties reveals a triplet metal-to-ligand charge transfer emission with an unprecedented quantum yield of 13% and a lifetime of 1.36 mus at room temperature and in the presence of air oxygen. An exceptional small energy gap between light absorption and light emission, or Stokes shift, was detected. Additionally, time-dependent density functional theory calculations were carried out in order to characterize the ground state and both the singlet and triplet excited states. The exceptional properties of the new compound open the perspective of exploiting terpyridyl-like ruthenium complexes in photochemical devices under ambient conditions.