Yan Geng

Contrast formation in Kelvin probe force microscopy of single π-conjugated molecules.

We report the contrast formation in the local contact potential difference (LCPD) measured by Kelvin probe force microscopy (KPFM) on single charge-transfer complexes (CTCs) on a NaCl bilayer on Cu(111). At different tip heights, we found quantitatively different LCPD contrasts that characterize different properties of the molecule. In the small distance regime, the tip penetrates the electron density of the molecule, and the contrast is related to the size and topography of the electron shell of the molecule. For larger distances, the LCPD contrast corresponds to the electrostatic field above the molecule. However, in the medium-distance regime, that is, for tip heights similar to the size of the molecule, the nonspherical distribution of π- and σ-electrons often conceals the effect of the partial charges within the molecule. Only for large distances does the LCPD map converge toward the simple field of a dipole for a polar molecule.

Electronic tuning effects via π-linkers in tetrathiafulvalene-based dyes

Four new tetrathiafulvalene (TTF)-based dyes featured with a donor–bridge–acceptor (D–π–A) structure were synthesized and characterized. All of them undergo two reversible oxidations to form stable radical cation and dication species. The electronic interactions between the TTF donor and the cyanoacrylic acid acceptor through the different π-linkers have been demonstrated by the presence of a photo-induced intramolecular charge-transfer (ICT) absorption band in the visible region. A red shift of the ICT state can be finely tuned by the degree of aromaticity and extended conjugation of π-bridges. To some extent, the oxidation potentials of these dyes are affected by the nature of π-bridges. They have been applied in organic dye-sensitized solar cells, showing relatively low power conversion efficiencies of up to 0.87% due to substantial charge recombination losses.

A Compact Tetrathiafulvalene–Benzothiadiazole Dyad and Its Highly Symmetrical Charge‐Transfer Salt: Ordered Donor π‐Stacks Closely Bound to Their Acceptors

A compact and planar donor-acceptor molecule 1 comprising tetrathiafulvalene (TTF) and benzothiadiazole (BTD) units has been synthesised and experimentally characterised by structural, optical, and electrochemical methods. Solution-processed and thermally evaporated thin films of 1 have also been explored as active materials in organic field-effect transistors (OFETs). For these devices, hole field-effect mobilities of μFE = (1.3±0.5)×10(-3) and (2.7±0.4)×10(-3)  cm(2)  V s(-1) were determined for the solution-processed and thermally evaporated thin films, respectively. An intense intramolecular charge-transfer (ICT) transition at around 495 nm dominates the optical absorption spectrum of the neutral dyad, which also shows a weak emission from its ICT state. The iodine-induced oxidation of 1 leads to a partially oxidised crystalline charge-transfer (CT) salt {(1)2I3}, and eventually also to a fully oxidised compound {1I3}⋅1/2I2. Single crystals of the former CT compound, exhibiting a highly symmetrical crystal structure, reveal a fairly good room temperature electrical conductivity of the order of 2 S cm(-1). The one-dimensional spin system bears compactly bonded BTD acceptors (spatial localisation of the LUMO) along its ridge.

HOMO Stabilisation in π‐Extended Dibenzotetrathiafulvalene Derivatives for Their Application in Organic Field‐Effect Transistors

Three new organic semiconductors, in which either two methoxy units are directly linked to a dibenzotetrathiafulvalene (DB-TTF) central core and a 2,1,3-chalcogendiazole is fused on the one side, or four methoxy groups are linked to the DB-TTF, have been synthesised as active materials for organic field-effect transistors (OFETs). Their electrochemical behaviour, electronic absorption and fluorescence emission as well as photoinduced intramolecular charge transfer were studied. The electron-withdrawing 2,1,3-chalcogendiazole unit significantly affects the electronic properties of these semiconductors, lowering both the HOMO and LUMO energy levels and hence increasing the stability of the semiconducting material. The solution-processed single-crystal transistors exhibit high performance with a hole mobility up to 0.04 cm(2)  V(-1)  s(-1) as well as good ambient stability.

A quinoxaline-fused tetrathiafulvalene derivative and its semiconducting charge-transfer salt: synthesis, crystal structures and physical properties

A quinoxaline-fused tetrathiafulvalene (TTF) derivative 1 has been synthesized to form a compact and planar π-conjugated donor–acceptor (D–π–A) ensemble, and its single crystal structure has been determined by X-ray diffraction. The inherent redox activity of 1 has been probed by cyclic voltammetry, and UV-vis spectroscopy revealed the typical broad and intense intramolecular charge-transfer (ICT) absorption occurring for such compactly fused D–π–A molecules. Reaction with iodine led to a 2 : 1 semiconducting charge-transfer salt {(1)2I3}, whose single crystal structure investigation, however, underlined the occurrence of a pronounced charge localization in the organic lattice. Consequently, the electrical conductivity of {(1)2I3}, measured by the four contact method on single crystals, gave only a limited value of about 1 × 10−4 Ω−1 cm−1, and the activation energy was determined to be on the order of 470–480 meV.

Donor–Acceptor Properties of a Single-Molecule Altered by On-Surface Complex Formation

Electron donor-acceptor molecules are of outstanding interest in molecular electronics and organic solar cells for their intramolecular charge transfer controlled via electrical or optical excitation. The preservation of their electronic character in the ground state upon adsorption on a surface is cardinal for their implementation in such single-molecule devices. Here, we investigate by atomic force microscopy and scanning tunneling microscopy a prototypical system consisting of a π-conjugated tetrathiafulvalene-fused dipyridophenazine molecule adsorbed on thin NaCl films on Cu(111). Depending on the adsorption site, the molecule is found either in a nearly undisturbed free state or in a bound state. In the latter case, the molecule adopts a specific adsorption site, leading to the formation of a chelate complex with a single Na+ alkali cation pulled out from the insulating film. Although expected to be electronically decoupled, the charge distribution of the complex is drastically modified, leading to the loss of the intrinsic donor-acceptor character. The chelate complex formation is reversible with respect to lateral manipulations, enabling tunable donor-acceptor molecular switches activated by on-surface coordination.

Anthanthrene dye-sensitized solar cells: influence of the number of anchoring groups and substitution motif

Four new dye molecules comprising an anthanthrene core, thiophene-cyanoacrylic acid electron acceptor and triphenylamine (TPA) electron donor units were prepared. Thereby, the substitution pattern at the anthanthrene core has been varied systematically. The molecules were fully characterized using optical spectroscopy and cyclic voltammetry, and their electronic structures and excitation energies were calculated by DFT and TDDFT methods. The photovoltaic properties of dye-sensitized solar cells based on these molecules were investigated. In comparison to symmetric dyes, the introduction of the organic donor TPA in asymmetric dyes leads to a remarkable improvement of the solar energy conversion efficiencies due to higher Voc and Jsc values of devices, giving rise to the best overall efficiency of 5.27%.

A highly sensitive TTF-functionalised probe for the determination of physiological thiols and its application in tumor cells

A tetrathiafulvalene (TTF)-fused piazselenole as a novel redox-active probe for highly sensitive determination of physiological thiols by electrochemical detection has been synthesised and successfully tested in intracellular non-protein thiol detection, reaching a detection limit of 10−10 M.

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.