Insight from Electrochemical Analysis in the Radical Cation State of a Monopyrrolotetrathiafulvalene-Based [2]Rotaxane.

Mechanically interlocked molecules are a class of compounds used for controlling directional movement when barriers can be raised and lowered using external stimuli. Applied voltages can turn on redox states to alter electrostatic barriers but their use for directing motion requires knowledge of their impact on the kinetics. Herein, we make the first measurements on the movement of cyclobis(paraquat-p-phenylene) (CBPQT4+) across the radical-cation state of monopyrrolotetrathiafulvalene (MPTTF) in a [2]rotaxane using variable scan-rate electrochemistry. The [2]rotaxane is designed in a way that directs CBPQT4+ to a high-energy co-conformation upon oxidation of MPTTF to either the radical cation (MPTTF⋅+) or the dication (MPTTF2+). 1H NMR spectroscopic investigations carried out in acetonitrile at 298 K showed direct interconversion to the thermodynamically more stable ground-state co-conformation with CBPQT4+ moving across the oxidized MPTTF2+ electrostatic barrier. The electrochemical studies revealed that interconversion takes place by movement of CBPQT4+ across both the MPTTF•+ (19.3 kcal mol-1) and MPTTF2+ (18.7 kcal mol-1) barriers. The outcome of our studies shows that MPTTF has three accessible redox states that can be used to kinetically control the movement of the ring component in mechanically interlocked molecules.

Tetrathiafulvalene-Inserted Diphenoquinone: Synthesis, Structure, and Dynamic Redox Property.

A new tetrathiafulvalene (TTF) derivative is synthesized, which is substituted with two phenoxy radicals on one 1,3-dithiole ring, and may have either open-shell diradical or closed-shell extended-quinoidal ground states. X-ray single crystal analysis and NMR measurements prove that this molecule has a closed-shell extended quinoidal structure both in the solid state and in solution. DFT calculations show the donor-acceptor electronic properties of this molecule with a well-separated HOMO-LUMO distribution and a small HOMO-LUMO energy gap. Because of this donor-acceptor character, this molecule gives both the dication and the dianion species by electrochemical oxidation and reduction. Furthermore, during the redox process between the neutral and dication states, this molecule exhibits unique changes in the cyclic voltammogram upon repeating the cycles or varying the scan rate. The observed electrochemical behavior is explained by the conformational changes in the electrochemically generated species, thus indicating that this molecule is classified as a dynamic redox system.

Formation of Single Micro- and Nanowires with Extreme Aspect Ratios in Microfluidic Channels.

Shown here is the site-specific formation of single extraordinarily long metal-organic micro- and nanowires using a microfluidic device made of poly(dimethylsiloxane) (PDMS). This approach exploits two concepts, i) the diffusion of organic precursor molecules through PDMS and ii) the use of microfluidic channels as a growth template. To initiate wire formation, metal and organic precursor solutions are filled into different supply channels that are separated by PDMS. As the precursor diffuses through PDMS, and thereby infiltrates the adjacent channel, the growth of micro- and nanowires starts at the side walls of this adjacent channel. The formation yields single wires with sizes ranging from several hundreds of micrometers to millimeters at diameters of 0.5-2 µm. The principles of this formation pathway are demonstrated with the reaction of tetrathiafulvalene (TTF) and gold(III) ions that yields Au-TTF wires. The influence of various reaction parameters including the choice of solvents and the chip fabrication protocol on the reaction are evaluated. Based on these findings, a further microfluidic device design with orthogonally arranged channels is developed, and the formation of single wires in a channel-defined pattern is demonstrated. Moreover, the possibility of pulsed precursor supply allows for advanced control over the growth of the wires.

Semiconducting π-Extended Tetrathiafulvalene Derivatives.

Tetrathiafulvalene (TTF) has been one of the most studied compounds, since the discovery of electrical conductivity as a charge-transfer complex in combination with tetracyano-p-quinodimethane (TCNQ) in 1973. In 2004, TTF was realized in a new light as an innate semiconductor material, as well as conductor and superconductor material. Because of the ready modification of its core skeleton and better solubility than that of acene compounds, many TTF derivatives have been reported to attain better charge-carrier mobility for field-effect transistor devices. Considering the high charge-carrier mobility of acene and TTF derivatives, annulation of the acene and TTF moieties is expected to improve the charge-carrier mobilities. This Minireview focuses on the syntheses, crystal structures, and electronic properties of state-of-the-art π-extended TTF derivatives, based on the history of the development of TTF derivatives. The relationship between the packing structure and charge-carrier mobilities is also discussed.

Redox-Driven Transformation of a Discrete Molecular Cage into an Infinite 3D Coordination Polymer.

Two M12 L6 redox-active self-assembled cages constructed from an electron-rich ligand based on the extended tetrathiafulvalene framework (exTTF) and metal complexes with a linear geometry (PdII and AgI ) are depicted. Remarkably, based on a combination of specific structural and electronic features, the polycationic self-assembled AgI coordination cage undergoes a supramolecular transformation upon oxidation into a three-dimensional coordination polymer, that is characterized by X-ray crystallography. This redox-controlled change of the molecular organization results from the drastic conformational modifications accompanying oxidation of the exTTF moiety.

P-Type Low-Molecular-Weight Hydrogelators.

As the use of low-molecular-weight gelators (LMWGs) as components in single and multicomponent systems for optoelectronic and solar cell applications increases, so does the need for more functional gelators. There are relatively few examples of p-type gelators that can be used in such systems. Here, the synthesis and characterization of three amino-acid-functionalized p-type gelators based on terthiophene, tetrathiafulvalene, and oligo(phenylenevinylene) are described. The cores of these molecules are already used as electron donors in optoelectronic applications. These newly designed molecules can gel water to form highly organized structures, which can be dried into thin films that show p-type behavior.

Photo- and Electronically Switchable Spin-Crossover Iron(II) Metal-Organic Frameworks Based on a Tetrathiafulvalene Ligand.

A major challenge is the development of multifunctional metal-organic frameworks (MOFs), wherein magnetic and electronic functionality can be controlled simultaneously. Herein, we rationally construct two 3D MOFs by introducing the redox active ligand tetra(4-pyridyl)tetrathiafulvalene (TTF(py)4 ) and spin-crossover FeII centers. The materials exhibit redox activity, in addition to thermally and photo-induced spin crossover (SCO). A crystal-to-crystal transformation induced by I2 doping has also been observed and the resulting intercalated structure determined. The conductivity could be significantly enhanced (up to 3 orders of magnitude) by modulating the electronic state of the framework via oxidative doping; SCO behavior was also modified and the photo-magnetic behavior was switched off. This work provides a new strategy to tune the spin state and conductivity of framework materials through guest-induced redox-state switching.

NHC-CAAC Heterodimers with Three Stable Oxidation States.

The synthesis of N-heterocyclic carbene (NHC)-cyclic (alkyl)(amino) carbene (CAAC) heterodimers is presented. As the free carbenes do not react together in solution, the synthetic approach involves the addition of a free NHC to a cyclic iminium salt, which results in the formation of the protonated heterodimer. Subsequent deprotonation leads to the isolation of the corresponding mixed Wanzlick dimers. One- and two-electron oxidations of these triazaolefins result in the formation of stable cationic radicals and bis(cations), respectively, which have been isolated and fully characterized. Cyclic voltammetry, UV/Vis spectroscopy, spin density, and DFT calculations suggest that these heterodimers feature complementary electronic properties to tetrathiafulvalenes (TTFs).

Regioselective synthesis of chiral dimethyl-bis(ethylenedithio)tetrathiafulvalene sulfones.

Enantiopure (R,R) and (S,S)-dimethyl-bis(ethylenedithio)tetrathiafulvalene monosulfones have been synthesized by the aerial oxidation of the chiral dithiolates generated from the propionitrile-protected precursors. Both enantiomers crystallize in the orthorhombic chiral space group P212121. They show a boat-type conformation of the TTF moiety, a rather rigid dithiin sulfone ring and the methyl groups in a bisequatorial conformation. Cyclic voltammetry measurements indicate fully reversible oxidation in radical cation and dication species.

[2.2]Paracyclophane derivatives containing tetrathiafulvalene moieties.

The synthesis of [2.2]paracyclophane derivatives containing tetrathiafulvalene units has been accomplished by the coupling reaction of 4-([2.2]paracyclophan-4-yl)-1,3-dithiol-2-thione in the presence of trimethylphosphite. The 1,3-dithiol-2-thione derivative was in turn synthesized by the regioselective bromination of 4-acetyl[2.2]paracyclophane, then through the corresponding dithiocarbamates and 1,3-dithiolium salts.

Copper ion salts of arylthiotetrathiafulvalenes: synthesis, structure diversity and magnetic properties.

The combination of CuBr2 and arylthio-substituted tetrathiafulvalene derivatives (1-7) results in a series of charge-transfer (CT) complexes. Crystallographic studies indicate that the anions in the complexes, which are derived from CuBr2, show diverse configurations including linear [Cu(I)Br2](-), tetrahedral [Cu(II)Br4](2-), planar [Cu(II)2Br6](2-), and coexistence of planar [Cu(II)Br4](2-) and tetrahedral [Cu(II)Br3](-) ions. On the other hand, the TTFs show either radical cation or dication states that depend on their redox potentials. The central TTF framework on most of TTFs is nearly planar despite the charge on them, whereas the two dithiole rings on molecule 4 in complex 4·CuBr4 are significantly twisted with a dihedral angle of 38.3°. The magnetic properties of the complexes were elucidated. The temperature-dependent magnetic susceptibility of complex 5·Cu2Br6 shows the singlet-triplet transition with coupling constant J = -248 K, and that of 3·(CuBr4)0.5·CuBr3·THF shows the abrupt change at 270 K caused by the modulation of intermolecular interactions. The thermo variation of magnetic susceptibility for the other complexes follows the Curie-Weiss law, indicating the weak antiferromagnetic interaction at low temperature.

Mono- and bis(pyrrolo)tetrathiafulvalene derivatives tethered to C60: synthesis, photophysical studies, and self-assembled monolayers.

A series of mono- (MPTTF) and bis(pyrrolo)tetrathiafulvalene (BPTTF) derivatives tethered to one or two C60 moieties was synthesized and characterized. The synthetic strategy for these dumbbell-shaped compounds was based on a 1,3-dipolar cycloaddition reaction between aldehyde-functionalized MPTTF/BPTTF derivatives, two different tailor-made amino acids, and C60. Electronic communication between the MPTTF/BPTTF units and the C60 moieties was studied by a variety of techniques including cyclic voltammetry and absorption spectroscopy. These solution-based studies indicated no observable electronic communication between the MPTTF/BPTTF units and the C60 moieties. In addition, femtosecond and nanosecond transient absorption spectroscopy revealed, rather surprisingly, that no charge transfer from the MPTTF/BPTTF units to the C60 moieties takes place on excitation of the fullerene moiety. Finally, it was shown that the MPTTF-C60 and C60-BPTTF-C60 dyad and triad molecules formed self-assembled monolayers on a Au(111) surface by anchoring to C60.

Ethylenedithio-tetrathiafulvalene-helicenes: electroactive helical precursors with switchable chiroptical properties.

Electroactive fused ethylenedithio-tetrathiafulvalene-[4]helicene and -[6]helicenes have been synthesized through a strategy that involved the preparation of 2,3-dibromo-helicene derivatives as intermediates. The dihedral angles between the terminal helicenes, as determined by single-crystal X-ray analysis, are 22.7° and 50.7° for the [4]helicene and [6]helicene, respectively. Their solid-state architectures show interplay between S⋅⋅⋅S and π⋅⋅⋅π intermolecular interactions. The chiroptical properties of the enantiopure EDT-TTF-[6]helicene derivatives have been investigated and supported by TDDFT calculations. Remarkable redox switching of the circular dichroism (CD) signal between the neutral and radical-cation species has been achieved.

Tetramethyl-bis(ethylenedithio)-tetrathiafulvalene (TM-BEDT-TTF) revisited: crystal structures, chiroptical properties, theoretical calculations, and a complete series of conducting radical cation salts.

The (S,S,S,S) and (R,R,R,R) enantiomers of tetramethyl-bis(ethylenedithio)-tetrathiafulvalene (TM-BEDT-TTF) show equatorial conformation for the four methyl groups in the solid state, according to the single-crystal X-ray analyses. Theoretical calculations at the Density Functional Theory (DFT) and time-dependent (TD) DFT levels indicate higher gas phase stability for the axial conformer than the equatorial one by 1.25 kcal ∙ mole⁻¹ and allow the assignment of the UV-vis and circular dichroism transitions. A complete series of radical cation salts of 1:1 stoichiometry with the triiodide anion I3⁻ was obtained by electrocrystallization of both enantiopure and racemic forms of the donor. In the packing the donors are organized in dimers that further interact through S ∙ ∙ ∙ S intermolecular contacts and the triiodide anions lie parallel to pairs of oxidized donors. The conductivity of the racemate, which adopts the same, but disordered, structural type, is considerably lower, with much higher activation energy.

Synthesis and electrochemical proprieties of novel unsymmetrical bis-tetrathiafulvalenes and electrical conductivity of their charge transfer complexes with tetracyanoquinodimethane (TCNQ).

The synthesis and properties of a series of bis-tetrathiafulvalenes (bis-TTFs) containing nitrophenyl, aminophenyl or dimethylaminophenyl is reported. The synthesis was carried out by using routes involving Wittig-type, cross-coupling, reduction and alkylation reactions. The electron donor ability of these new compounds has been measured by cyclic voltammetry (CV). Charge transfer complexes with tetracyanoquinodimethane (TCNQ) were prepared by chemical redox reactions. The complexes have been proven to give conducting materials.

Activating both Halogen and Chalcogen Bonding Interactions in Cation Radical Salts of Iodinated Tetrathiafulavalene Derivatives.

Halogen bonding (XB) interactions are investigated in cation radical salts of bis(methylthio)-5,5'-diiodotetrathiafulvalene (1). Electrocrystallization of 1 in the presence of Bu4 NCl affords a 1 : 1 salt formulated as (E-1)Cl. Particularly strong I⋅⋅⋅Cl- XB interactions are observed around the Cl- anion with the distances at 78 % the sum of the van der Waals radii, a consequence of the XB charge activation in the cation radical. Moreover, the Cl- environment is complemented by two extra S⋅⋅⋅Cl- chalcogen bonding (ChB) interactions, an original feature among reported halide salts of TTF derivatives. Electrostatic potential calculations on the cation radical further demonstrate the efficient activation of the S atoms of the 1,3-dithiole rings (Vs,max =87.2 kcal/mol), as strong as with the iodine atoms (Vs,max =87.9 kcal/mol). The radical cations form weakly dimerized stacks, as confirmed by the variable-temperature magnetic susceptibility and the weak conductivity (4.8×10-5  S cm-1 ).

Organic semiconductors for organic field-effect transistors.

The advantages of organic field-effect transistors (OFETs), such as low cost, flexibility and large-area fabrication, have recently attracted much attention due to their electronic applications. Practical transistors require high mobility, large on/off ratio, low threshold voltage and high stability. Development of new organic semiconductors is key to achieving these parameters. Recently, organic semiconductors have been synthesized showing comparable mobilities to amorphous-silicon-based FETs. These materials make OFETs more attractive and their applications have been attempted. New organic semiconductors resulting in high-performance FET devices are described here and the relationship between transistor characteristics and chemical structure is discussed.

Carbon Nanotubes Conjugated with Triazole-Based Tetrathiafulvalene-Type Receptors for C60 Recognition.

Fullerene receptors prepared by a twofold CuI -catalyzed azide-alkyne cycloaddition reaction with π-extended tetrathiafulvalene (exTTF) have been covalently linked to single-walled carbon nanotubes and multi-walled carbon nanotubes. The nanoconjugates obtained were characterized by several analytical, spectroscopic and microscopic techniques (TEM, FTIR, Raman, TGA and XPS), and evaluated as C60 receptors by using UV-Vis spectroscopy. The complexation between the exTTF-triazole receptor in the free state and C60 was also studied by UV-Vis and 1 H NMR titrations, and compared with analogous triazole-based tweezer-type receptors containing the electron-acceptor 11,11,12,12-tetracyano-9,10-anthraquinodimethane and benzene rings instead of exTTF motifs, providing in all cases very similar values for the association constant (log Ka ≈3.0-3.1). Theoretical density functional theory calculations demonstrated that the enhanced interaction between the host and the guest upon increasing the size of the π-conjugated arms of the tweezer is compensated by an increase in the energy penalty needed to distort the geometry of the host to wrap C60 .

Tetrathiafulvalene Belts with Large Cavities.

The latest member of the cyclophane family, the macrotricyclic tetrathiafulvalene (TTF) "belt", is now available. A general synthetic strategy for the construction of tetraconnected belt-type TTFs (shown schematically) has been developed, made possible by the use of a TTF with two different protecting groups. In the solid-state structure of one of the three TTF-belts prepared two chloroform molecules reside inside the spacious cavity.

Tetrathiafulvaleno-Annelated Porphyrins.

Two efficient synthetic routes to the first tetrathiafulvaleno-annelated porphyrins are reported. These novel porphyrin systems (see picture; Pe=pentyl) have been characterized by using a variety of techniques including EPR spectroscopy, cyclic voltammetry, and mass spectrometry. Langmuir-Blodgett films obtained from the porphyrins were used to carry out structural studies by using X-ray diffraction and atomic force microscopy.