Ferrocene on Insulator: Silane Coupling to a SiO2 Surface and Influence on Electrical Transport at a Buried Interface with an Organic Semiconductor Layer.

A silane coupling-based procedure for decoration of an insulator surface containing abundant hydroxy groups by constructing redox-active self-assembled monolayers (SAMs) is described. A newly synthesized ferrocene (Fc) derivative containing a triethoxysilyl group designated FcSi was immobilized on SiO2/Si by a simple operation that involved immersing the substrate in a toluene solution of the Fc silane coupling reagent and then rinsing the resulting substrate. X-ray photoelectron spectroscopy (XPS) measurements confirmed that the Fc group was immobilized on SiO2/Si in the Fe(II) state. Cyclic voltammetry measurements showed that the Fc groups were electrically insulated from the Si electrode by the SiO2 layer. The FcSi on SiO2/Si structures were found to serve as a good scaffold for formation of organic semiconductor thin films by vacuum thermal evaporation of C8-BTBT (2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene), which is well-known as an organic field-effect transistor (OFET) material. The X-ray diffraction profile indicated that the conventional standing-up conformation of the C8-BTBT molecules perpendicular to the substrates was maintained in the thin films formed on FcSi@SiO2/Si. Further vacuum thermal evaporation of Au provided an FcSi-based OFET structure with good transfer characteristics. The FcSi-based OFET showed pronounced source-drain current hysteresis between the forward and backward scans. The degree of this hysteresis was varied reversibly via gate bias manipulation, which was presumably accompanied by trapping and detrapping of hole carriers at the Fc-decorated SiO2 surface. These findings provide new insights into application of redox-active SAMs to nonvolatile OFET memories while also creating new interfaces through junctions with functional thin films, in which the underlying redox-active SAMs play supporting roles.

Immobilizing a π-Conjugated Catecholato Framework on Surfaces of SiO2 Insulator Films via a One-Atom Anchor of a Platinum Metal Center to Modulate Organic Transistor Performance.

Chemical modification of insulating material surfaces is an important methodology to improve the performance of organic field-effect transistors (OFETs). However, few redox-active self-assembled monolayers (SAMs) have been constructed on gate insulator film surfaces, in contrast to the numerous SAMs formed on many types of conducting electrodes. In this study, we report a new approach to introduce a π-conjugated organic fragment in close proximity to an insulating material surface via a transition metal center acting as a one-atom anchor. On the basis of the reported coordination chemistry of a catecholato complex of Pt(II) in solution, we demonstrate that ligand exchange can occur on an insulating material surface, affording SAMs on the SiO2 surface derived from a newly synthesized Pt(II) complex containing a benzothienobenzothiophene (BTBT) framework in the catecholato ligand. The resultant SAMs were characterized in detail by water contact angle measurements, X-ray photoelectron spectroscopy, atomic force microscopy, and cyclic voltammetry. The SAMs served as good scaffolds of π-conjugated pillars for forming thin films of a well-known organic semiconductor C8-BTBT (2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene), accompanied by the engagements of the C8-BTBT molecules with the SAMs containing the common BTBT framework at the first layer on SiO2. OFETs containing the SAMs displayed improved performance in terms of hole mobility and onset voltage, presumably because of the unique interfacial structure between the organic semiconducting and inorganic insulating layers. These findings provide important insight into creating new elaborate interfaces through installing coordination chemistry in solution to solid surfaces, as well as OFET design by considering the compatibility between SAMs and organic semiconductors.

Benzothienobenzothiophene-Based Molecular Conductors: High Conductivity, Large Thermoelectric Power Factor, and One-Dimensional Instability.

On the basis of an excellent transistor material, [1]benzothieno[3,2-b][1]benzothiophene (BTBT), a series of highly conductive organic metals with the composition of (BTBT)2XF6 (X = P, As, Sb, and Ta) are prepared and the structural and physical properties are investigated. The room-temperature conductivity amounts to 4100 S cm(-1) in the AsF6 salt, corresponding to the drift mobility of 16 cm(2) V(-1) s(-1). Owing to the high conductivity, this salt shows a thermoelectric power factor of 55-88 µW K(-2) m(-1), which is a large value when this compound is regarded as an organic thermoelectric material. The thermoelectric power and the reflectance spectrum indicate a large bandwidth of 1.4 eV. These salts exhibit an abrupt resistivity jump under 200 K, which turns to an insulating state below 60 K. The paramagnetic spin susceptibility, and the Raman and the IR spectra suggest 4kF charge-density waves as an origin of the low-temperature insulating state.

A highly conducting organic metal derived from an organic-transistor material: benzothienobenzothiophene.

BTBT ([1]benzothieno[3,2-b][1]benzothiophene) is an organic semiconductor that realizes high mobility in organic transistors. Here we report that the charge-transfer (CT) salt, (BTBT)2PF6, shows a high room-temperature conductivity of 1500 S cm(-1). This compound exhibits a resistivity jump around 150 K, but when it is covered with Apiezon N grease the resistivity jump is suppressed, and the metallic conductivity is maintained down to 60 K. Owing to the very high conductivity, the ESR signal shows a significantly asymmetric Dysonian lineshape (A/B ≅ 3) even at room temperature. Since most organic conductors are based on strong electron donors, it is remarkable that such a weak electron donor as BTBT realizes a stable and highly conducting organic metal.

Chiral metal down to 4.2 K - a BDH-TTP radical-cation salt with spiroboronate anion B(2-chloromandelate)2.

We report the first example of a chiral BDH-TTP radical-cation salt. Chirality is induced in the structure via the use of a chiral spiroboronate anion where three stereocentres are present, one on each chiral ligand and one on the boron centre. Despite starting from a labile racemic mixture of BS and BR enantiomers, only one enantiomer is present in the crystal lattice. The anions pack in a novel double anion layer which is the thickest anion layer found in a BDH-TTP salt. This material is chiral and shows metallic behaviour down to at least 4.2 K.

New π-extended catecholato complexes of Pt(ii) and Pd(ii) containing a benzothienobenzothiophene (BTBT) moiety: synthesis, electrochemical behavior and charge transfer properties.

Benzothienobenzothiophene (BTBT) and derivatives have received increasing attention as organic field-effect transistor materials and molecular conductors. This report presents the first synthesis of metal complexes involving a BTBT moiety, which was achieved by complexation of 2,2'-bipyridyl complexes of Pt(ii) and Pd(ii) with dihydroxy-substituted BTBT (1) as a new π-extended catecholato ligand (tBu2Bpy = 4,4'-di-tert-butyl-2,2'-dipyridyl). The resulting complexes M(tBu2Bpy)(O2BTBT) (M = Pt (3Pt) and Pd (3Pd)) were characterized by UV-vis spectroscopy, density functional theory (DFT) calculations, and cyclic voltammetry. The electron donating ability of BTBT was substantially enhanced upon including two oxygen substituents followed by metal coordination. This enabled chemical oxidation of 3Pt and 3Pd with a mild chemical oxidant (ferrocenium hexafluorophosphate) and formation of the one-electron-oxidized state. While 3Pt and 3Pd exhibited an absorption band originating from a catecholate → Bpy ligand-to-ligand charge transfer transition typical of this class of catecholato complexes, the radical cations exhibited a unique π-π* intramolecular charge transfer (ICT) transition absorption in which the π and π* orbitals were the newly incorporated benzothienothiophene-based donor and semiquinonato-based acceptor, respectively. The BTBT+ skeleton was electronically divided into two sites by the present chemical modification. The ICT properties of the complexes were found to be modulated by varying the metal ions. These findings offer a new approach to molecular design for (semi)conducting materials using optical properties.

Enantiopure and racemic radical-cation salts of B(malate)2(-) anions with BEDT-TTF.

We have synthesized the first examples of radical-cation salts of BEDT-TTF with chiral borate anions, [B(malate)2](-), prepared from either enantiopure or racemic bidentate malate ligands. In the former case only one of two diastereoisomers of the borate anion is incorporated, while for the hydrated racemic salt one racemic pair of borate anions containing a R and a S malate ligand is incorporated. Their conducting and magnetic properties are reported. The tight-binding band calculation indicates that the chiral salt has an effective half-filled flat band, which is likely to be caused by the chiral structural feature.