Christian R. Parker

A Comprehensive Study of Extended Tetrathiafulvalene Cruciform Molecules for Molecular Electronics: Synthesis and Electrical Transport Measurements

Cruciform-like molecules with two orthogonally placed π-conjugated systems have in recent years attracted significant interest for their potential use as molecular wires in molecular electronics. Here we present synthetic protocols for a large selection of cruciform molecules based on oligo(phenyleneethynylene) (OPE) and tetrathiafulvalene (TTF) scaffolds, end-capped with acetyl-protected thiolates as electrode anchoring groups. The molecules were subjected to a comprehensive study of their conducting properties as well as their photophysical and electrochemical properties in solution. The complex nature of the molecules and their possible binding in different configurations in junctions called for different techniques of conductance measurements: (1) conducting-probe atomic force microscopy (CP-AFM) measurements on self-assembled monolayers (SAMs), (2) mechanically controlled break-junction (MCBJ) measurements, and (3) scanning tunneling microscopy break-junction (STM-BJ) measurements. The CP-AFM measurements showed structure-property relationships from SAMs of series of OPE3 and OPE5 cruciform molecules; the conductance of the SAM increased with the number of dithiafulvene (DTF) units (0, 1, 2) along the wire, and it increased when substituting two arylethynyl end groups of the OPE3 backbone with two DTF units. The MCBJ and STM-BJ studies on single molecules both showed that DTFs decreased the junction formation probability, but, in contrast, no significant influence on the single-molecule conductance was observed. We suggest that the origins of the difference between SAM and single-molecule measurements lie in the nature of the molecule-electrode interface as well as in effects arising from molecular packing in the SAMs. This comprehensive study shows that for complex molecules care should be taken when directly comparing single-molecule measurements and measurements of SAMs and solid-state devices thereof.

A New Class of Extended Tetrathiafulvalene Cruciform Molecules for Molecular Electronics with Dithiafulvene‐4,5‐Dithiolate Anchoring Groups

Cruciform motifs with two orthogonally oriented π-extended tetrathiafulvalenes and with differently protected thiolate end-groups are synthesized by stepwise coupling reactions. The molecules are subjected to single-molecule conductivity studies in a break-junction and to conducting probe atomic force microscopy studies in a self-assembled monolayer on gold.

Mixed valence radical cations and intermolecular complexes derived from indenofluorene-extended tetrathiafulvalenes

Engineering of mixed-valence (MV) radical cations and intermolecular complexes based on π-extended tetrathiafulvalenes (TTFs) is central for the development of organic conductors. On another front, redox-controlled dimerization of radical cations has recently been recognized as an important tool in supramolecular chemistry. Here we show that π-extended TTFs based on the indenofluorene core, prepared by Horner–Wadsworth–Emmons reactions, undergo reversible and stepwise one-electron oxidations and that the detectable, intermediate radical cation forms remarkably strong intermolecular MV ([neutral·cation]) and π-dimer ([cation·cation]) complexes with near-infrared radical cation absorptions. The radical cation itself seems to be a so-called Class III MV species in the Robin–Day classification. The formation of MV dimers was corroborated by ESR spectroelectrochemical studies, revealing two slightly different ESR signals upon oxidation, one assigned to the MV dimer and the other to the cation monomer. Crystals of the radical cation with different anions (PF6−, BF4−, and TaF6−) were grown by electrocrystallization. Conductance studies revealed that the salts behave as semiconductors with the hexafluorotantalate salt exhibiting the highest conductance. Using a custom-built ESR spectrometer with sub-femtomole sensitivity, the magnetic properties of one crystal were investigated. While the spin-to-spin interaction between radical cations was negligible, a high cooperativity coupling to the microwave field was observed – as a result of an exceptionally narrow spin line width and high spin density. This could have great potential for applications in quantum computation where crystalline spin ensembles are exploited for their long coherence times.

Dihydroazulene–Buckminsterfullerene Conjugates

The dihydroazulene (DHA)/vinylheptafulvene (VHF) photo/thermoswitch has recently attracted interest as a molecular switch for molecular electronics. In this field, Buckminsterfullerene, C(60), has been shown to be a useful anchoring group for adhering a molecular wire to an electrode. Here we have combined the two units with the overall aim to elucidate how C(60) influences the DHA-VHF switching events. Efficient synthetic protocols for making covalently linked DHA-C(60) conjugates were developed, using Prato, Sonogashira, Hay, and Cadiot-Chodkiewicz reactions. These syntheses provide as well a variety of potentially useful DHA and C(60) building blocks for acetylenic scaffolding. The two units were separated by bridges of various lengths, such as oligo(phenyleneethynylene) (OPE2 and OPE3) wires. The distance of separation was found to influence strongly the light-induced ring-opening reaction of DHA to its corresponding VHF. Thus, C(60) was found to significantly quench this conversion when situated closely to the DHA unit.

Tracking molecular resonance forms of donor–acceptor push–pull molecules by single-molecule conductance experiments

The ability of molecules to change colour on account of changes in solvent polarity is known as solvatochromism and used spectroscopically to characterize charge-transfer transitions in donor–acceptor molecules. Here we report that donor–acceptor-substituted molecular wires also exhibit distinct properties in single-molecule electronics under the influence of a bias voltage, but in absence of solvent. Two oligo(phenyleneethynylene) wires with donor–acceptor substitution on the central ring (cruciform-like) exhibit remarkably broad conductance peaks measured by the mechanically controlled break-junction technique with gold contacts, in contrast to the sharp peak of simpler molecules. From a theoretical analysis, we explain this by different degrees of charge delocalization and hence cross-conjugation at the central ring. Thus, small variations in the local environment promote the quinoid resonance form (off), the linearly conjugated (on) or any form in between. This shows how the conductance of donor–acceptor cruciforms is tuned by small changes in the environment.

On the bromination of the dihydroazulene/vinylheptafulvene photo-/thermoswitch.

Summary Background: The dihydroazulene (DHA)/vinylheptafulvene (VHF) system (with two cyano groups at C1) functions as a photo-/thermoswitch. Direct ionic bromination of DHA has previously furnished a regioselective route to a 7,8-dibromide, which by elimination was converted to a 7-bromo-substituted DHA. This compound has served as a central building block for functionalization of the DHA by palladium-catalyzed cross-coupling reactions. The current work explores another bromination protocol for achieving the isomeric 3-bromo-DHA and also explores the outcome of additional bromination of this compound as well as of the known 7-bromo-DHA. Results: Radical bromination on two different VHFs by using N-bromosuccinimide/benzoyl peroxide and light, followed by a ring-closure reaction generated the corresponding 3-bromo-DHAs, as confirmed in one case by X-ray crystallography. According to a 1H NMR spectroscopic study, the ring closure of the brominated VHF seemed to occur readily under the reaction conditions. A subsequent bromination–elimination protocol provided a 3,7-dibromo-DHA. In contrast, treating the known 7-bromo-DHA with bromine generated a very labile species that was converted to a new 3,7-dibromoazulene, i.e., the fully unsaturated species. Azulenes were also found to form from brominated compounds when left standing for a long time in the solid state. Kinetics measurements reveal that the 3-bromo substituent enhances the rate of the thermal conversion of the VHF to DHA, which is opposite to the effect exerted by a bromo substituent in the seven-membered ring. Conclusion: Two general procedures for functionalizing the DHA core with a bromo substituent (at positions 3 and 7, respectively) are now available with the DHA as starting material.

Multistate Switches: Ruthenium Alkynyl-Dihydroazulene/Vinylheptafulvene Conjugates.

Multimode molecular switches incorporating distinct and independently addressable functional components have potential applications as advanced switches and logic gates for molecular electronics and memory storage devices. Herein, we describe the synthesis and characterization of four switches based on the dihydroazulene/vinylheptafulvene (DHA/VHF) photo/thermoswitch pair functionalized with the ruthenium-based Cp*(dppe)Ru ([Ru*]) metal complex (dppe=1,2-bis(diphenylphosphino)ethane; Cp*=pentamethylcyclopentadienyl). The [Ru*]-DHA conjugates can potentially exist in six different states accessible by alternation between DHA/VHF, Ru(II) /Ru(III) , and alkynyl/vinylidene, which can be individually stimulated by using light/heat, oxidation/reduction, and acid/base. Access to the full range of states was found to be strongly dependent on the electronic communication between the metal center and the organic photoswitch in these [Ru*]-DHA conjugates. Detailed electrochemical, spectroscopic (UV/Vis, IR, NMR), and X-ray crystallographic studies indeed reveal significant electronic interactions between the two moieties. When in direct conjugation, the ruthenium metal center was found to quench the photochemical ring-opening of DHA, which in one case could be restored by protonation or oxidation, allowing conversion to the VHF state.

Diindenothienoacene–tetrathiafulvalene redox systems

Extended tetrathiafulvalenes with central diindenothienoacene cores were prepared and studied for their redox and spectroelectrochemical properties, which depended strongly on the orientation of the thiophene rings. The cations undergo remarkably strong associations, rendering them attractive as redox-controllable tectons in supramolecular chemistry, and in one case crystals were grown by electrocrystallization.

Interactions between tetrathiafulvalene units in dimeric structures – the influence of cyclic cores

Summary A selection of cyclic and acyclic acetylenic scaffolds bearing two tetrathiafulvalene (TTF) units was prepared by different metal-catalyzed coupling reactions. The bridge separating the two TTF units was systematically changed from linearly conjugated ethyne, butadiyne and tetraethynylethene (trans-substituted) units to a cross-conjugated tetraethynylethene unit, placed in either acyclic or cyclic arrangements. The cyclic structures correspond to so-called radiaannulenes having both endo- and exocyclic double bonds. Interactions between two redox-active TTF units in these molecules were investigated by cyclic voltammetry, UV–vis–NIR and EPR absorption spectroscopical methods of the electrochemically generated oxidized species. The electron-accepting properties of the acetylenic cores were also investigated electrochemically.

The gilded edge in acetylenic scaffolding: pd-catalyzed cross-coupling reactions of phosphine-gold(I) oligoynyl complexes.

Stable bis(gold(I) alkynyl) complexes of tetraethynylethene (TEE) derivatives were readily prepared and employed in Sonogashira-like palladium-catalyzed phosphine-gold(I) halide elimination reactions with aryl iodides and redox-active tetrathiafulvalene (TTF) mono- and bisiodides. This presents a particularly convenient method for the preparation of symmetrical and asymmetrical tetrathiafulvalene (TTF)-fused radiaannulenes in good yields.