Martin R. Bryce

Recent Advances in White Organic Light‐Emitting Materials and Devices (WOLEDs)

WOLEDs offer new design opportunities in practical solid-state lighting and could play a significant role in reducing global energy consumption. Obtaining white light from organic LEDs is a considerable challenge. Alongside the development of new materials with improved color stability and balanced charge transport properties, major issues involve the fabrication of large-area devices and the development of low-cost manufacturing technology. This Review will describe the types of materials (small molecules and polymers) that have been used to fabricate WOLEDs. A range of device architectures are presented and appraised.

Electron-transporting materials for organic electroluminescent and electrophosphorescent devices

One of the requirements for efficient organic electroluminescent devices (OLEDs) is balanced charge injection from the two electrodes and efficient transport of both holes and electrons within the luminescent layer in the device structure. Many of the common luminescent conjugated polymers, e.g. derivatives of poly(phenylenevinylene) and poly(fluorene), are predominantly hole transporters (i.e. p-dopable). This article gives a brief overview of organic electroluminescence and electrophosphorescence and provides a more detailed consideration of ways in which electron transport in these systems has been enhanced by the incorporation of electron-deficient (i.e. n-dopable) small molecules and polymers into the devices, either as blends or by covalent attachment of sub-units to the luminophore or as an additional electron-transporting, hole-blocking (ETHB) layer adjacent to the cathode. The chemical structures of these systems are presented and their roles are assessed. Most of these ETHB molecules are electron-deficient aromatic nitrogen-containing heterocycles, e.g. derivatives of 1,3,4-oxadiazole, pyridine, pyrimidine, pyrazine, quinoline, etc. Non-aromatic thiophene-S,S-dioxide derivatives are also discussed. The article is written from an organic chemists perspective.

Triplet Harvesting with 100% Efficiency by Way of Thermally Activated Delayed Fluorescence in Charge Transfer OLED Emitters

Organic light-emitting diodes (OLEDs) have their performance limited by the number of emissive singlet states created upon charge recombination (25%). Recently, a novel strategy has been proposed, based on thermally activated up-conversion of triplet to singlet states, yielding delayed fluorescence (TADF), which greatly enhances electroluminescence. The energy barrier for this reverse intersystem crossing mechanism is proportional to the exchange energy (ΔEST ) between the singlet and triplet states; therefore, materials with intramolecular charge transfer (ICT) states, where it is known that the exchange energy is small, are perfect candidates. However, here it is shown that triplet states can be harvested with 100% efficiency via TADF, even in materials with ΔEST of more than 20 kT (where k is the Boltzmann constant and T is the temperature) at room temperature. The key role played by lone pair electrons in achieving this high efficiency in a series of ICT molecules is elucidated. The results show the complex photophysics of efficient TADF materials and give clear guidelines for designing new emitters.

Tetrathiafulvalenes as π‐Electron Donors for Intramolecular Charge‐Transfer Materials

Although tetrathiafulvalene (TTF) and its derivatives have been extensively studied for more than 25 years as π-electron donors in intermolecular charge-transfer materials, the intriguing potential of TTF as a donor in an intramolecular sense has only recently been developed. Many versatile, functionalized TTF building blocks are now readily available, and this article will review a range of compounds in which TTF is covalently linked to an electron acceptor moiety by a variety of linking units, sometimes giving rise to an intramolecular charge-transfer (ICT) interaction, which is most frequently manifested in the optical and electrochemical properties. In this context, acceptor subunits include: tetracyano-p-quinodimethane, quinones, electron-deficient aryl groups, pyridinium and bipyridinium units, fullerenes, phthalocyanines, and mesomerically conjugated carbonyl, thiocarbonyl, ester, and related groups. This work paves the way for more systematic and detailed studies of TTF–spacer–A molecules (where A is an acceptor) in which there is increased control of the structural, electronic, optical, and magnetic properties arising from ICT interactions in the ground state, or in the excited state.

Functionalised tetrathiafulvalenes: new applications as versatile π-electron systems in materials chemistry

Not only a component of molecular conductors! Tetrathiafulvalene (TTF) and its derivatives are versatile building blocks in many areas of materials chemistry. This article reviews the current role of substituted TTFs in cation sensors, liquid crystals, intramolecular charge-transfer and nonlinear optical materials, supramolecular switches and devices, and redox polymers (main-chain, side-chain and dendritic systems).

Single Molecular Conductance of Tolanes: Experimental and Theoretical Study on the Junction Evolution Dependent on the Anchoring Group

Employing a scanning tunneling microscopy based beak junction technique and mechanically controlled break junction experiments, we investigated tolane (diphenylacetylene)-type single molecular junctions having four different anchoring groups (SH, pyridyl (PY), NH(2), and CN) at a solid/liquid interface. The combination of current-distance and current-voltage measurements and their quantitative statistical analysis revealed the following sequence for junction formation probability and stability: PY > SH > NH(2) > CN. For all single molecular junctions investigated, we observed the evolution through multiple junction configurations, with a particularly well-defined binding geometry for PY. The comparison of density functional theory type model calculations and molecular dynamics simulations with the experimental results revealed structure and mechanistic details of the evolution of the different types of (single) molecular junctions upon stretching quantitatively.

Current trends in tetrathiafulvalene chemistry: towards increased dimensionality

Some of the current directions in research on conducting and superconducting charge-transfer salts based upon tetrathiafulvalene (TTF)π-electron donor molecules are reviewed. Particular emphasis is placed upon new donor molecules, which have been studied with the aim of increasing the dimensionality in the solid state, thereby gaining control over the intermolecular architecture and long-range electron delocalization. Important structural features of the π-donor in this respect are: close intermolecular sulfur—sulfur contacts, attachment of hydrogen-bonding substituents, and extended π-conjugation. The electronic and structural properties of selected TTF derivatives and their salts are discussed. Synthetic schemes are also presented.

Single-Molecule Conductance of Functionalized Oligoynes: Length Dependence and Junction Evolution

We report a combined experimental and theoretical investigation of the length dependence and anchor group dependence of the electrical conductance of a series of oligoyne molecular wires in single-molecule junctions with gold contacts. Experimentally, we focus on the synthesis and properties of diaryloligoynes with n = 1, 2, and 4 triple bonds and the anchor dihydrobenzo[b]thiophene (BT). For comparison, we also explored the aurophilic anchor group cyano (CN), amino (NH2), thiol (SH), and 4-pyridyl (PY). Scanning tunneling microscopy break junction (STM-BJ) and mechanically controllable break junction (MCBJ) techniques are employed to investigate single-molecule conductance characteristics. The BT moiety is superior as compared to traditional anchoring groups investigated so far. BT-terminated oligoynes display a 100% probability of junction formation and possess conductance values which are the highest of the oligoynes studied and, moreover, are higher than other conjugated molecular wires of similar length. Density functional theory (DFT)-based calculations are reported for oligoynes with n = 1-4 triple bonds. Complete conductance traces and conductance distributions are computed for each family of molecules. The sliding of the anchor groups leads to oscillations in both the electrical conductance and the binding energies of the studied molecular wires. In agreement with experimental results, BT-terminated oligoynes are predicted to have a high electrical conductance. The experimental attenuation constants βH range between 1.7 nm(-1) (CN) and 3.2 nm(-1) (SH) and show the following trend: βH(CN) < βH(NH2) < βH(BT) < βH(PY) ≈ βH(SH). DFT-based calculations yield lower values, which range between 0.4 nm(-1) (CN) and 2.2 nm(-1) (PY).

Electrical conductance of conjugated oligomers at the single molecule level.

We determine and compare, at the single molecule level and under identical environmental conditions, the electrical conductance of four conjugated phenylene oligomers comprising terminal sulfur anchor groups with simple structural and conjugation variations. The comparison shows that the conductance of oligo(phenylene vinylene) (OPV) is slightly higher than that of oligo(phenylene ethynylene) (OPE). We find that solubilizing side groups do neither prevent the molecules from being anchored within a break junction nor noticeably influence the conductance value.

White polymeric light-emitting diode based on a fluorene polymer∕Ir complex blend system

Efficient white-polymeric light-emitting diodes (PLED) were fabricated as a single active layer containing blue-emitting poly(9,9-bis(2-ethylhexyl)fluorene-2,7-diyl) endcapped with bis(4-methylphenyl)phenylamine; (PF2∕6am4), and yellow-orange-emitting iridium [tri-fluorenyl] pyridine complex [Ir(Fl3Py)3]. The fluorene-like ligands in the blended device prevent phase segregation and also enhance energy transfer from the polymer host to the guest due to efficient overlap of wave function (Dexter process) and host singlet emission and guest absorption bands (Forster process) which reduces the loading level required to produce white emission. The two emitted colors complement each other and doping levels of 2%–3% produce white emission. Above a certain current density, depending on the doping level, the device Commission Internationale de L’Eclairage (CIE) coordinates become bias independent and a stabilized white emission can be obtained. A white-emitting PLED (coordinates 0.348, 0.367) of peak external quan...