The Interplay of Strongly and Weakly Exchange-Coupled Triplet Pairs in Intramolecular Singlet Fission.

Singlet fission (SF) and triplet-triplet annihilation upconversion (TTA-UC) nominally enable the interconversion of higher-energy singlet states with two lower-energy triplet states and vice versa, with both processes having envisaged application for enhanced solar power devices. The mechanism of SF/TTA-UC involves a complex array of different multiexcitonic triplet-pair states that are coupled by the exchange interaction to varying extents. In this work a family of bounded intramolecular SF materials, based upon the chromophore 1,6-diphenyl-1,3,5-hexatriene, were designed and synthesized.

Reducing undesired solubility of squarephaneic tetraimide for use as an organic battery electrode material.

Locally aromatic alkyl--substituted squarephaneic tetraimide (SqTI) conjugated macrocycles are four-electron reducible, owing to global aromaticity and presumed global Baird aromaticity of the dianion and tetraanion states, respectively. However, their good solubility inhibits their application as a battery electrode material. By applying sidechain removal as a strategy to reduce SqTI solubility, we report the development of its unsubstituted derivative SqTI-H, which was obtained directly from squarephaneic tetraanhydride by facile treatment with hexamethyldisilazane and MeOH.

A convenient synthesis of ferrocene-(ethynylphenyl)thioacetates.

Ferrocene is popular within the field of molecular electronics due to its well-defined electronic properties. However, where the conductance of highly-conjugated oligophenylethylenes has been widely studied, work on analogous ferrocenyl systems has been relatively rare, possibly due to difficulties associated with the synthesis of molecules containing terminal thioacetates, which are often used to bind molecules to metallic electrodes. Herein, a widely applicable synthetic methodology is demonstrated which can be used to synthesize a variety of conjugated ferrocene-alkyne systems terminated with thioacetates, including symmetric, asymmetric and multi-ferrocene systems.

Functionalisation of conjugated macrocycles with type I and II concealed antiaromaticity cross-coupling reactions.

Conjugated macrocycles can exhibit concealed antiaromaticity; that is, despite not being antiaromatic, under specific circumstances, they can display properties typically observed in antiaromatic molecules due to their formal macrocyclic 4 π-electron system. Paracyclophanetetraene (PCT) and its derivatives are prime examples of macrocycles exhibiting this behaviour. In redox reactions and upon photoexcitation, they have been shown to behave like antiaromatic molecules (requiring type I and II concealed antiaromaticity, respectively), with such phenomena showing potential for use in battery electrode materials and other electronic applications.

Quantum Interference and Contact Effects in the Thermoelectric Performance of Anthracene-Based Molecules.

We report on the single-molecule electronic and thermoelectric properties of strategically chosen anthracene-based molecules with anchor groups capable of binding to noble metal substrates, such as gold and platinum. Specifically, we study the effect of different anchor groups, as well as quantum interference, on the electric conductance and the thermopower of gold/single-molecule/gold junctions and generally find good agreement between theory and experiments. All molecular junctions display transport characteristics consistent with coherent transport and a Fermi alignment approximately in the middle of the highest occupied molecular orbital/lowest unoccupied molecular orbital gap.

Assembly, structure and thermoelectric properties of 1,1'-dialkynylferrocene 'hinges'.

Dialkynylferrocenes exhibit attractive electronic and rotational features that make them ideal candidates for use in molecular electronic applications. However previous works have primarily focussed on single-molecule studies, with limited opportunities to translate these features into devices. In this report, we utilise a variety of techniques to examine both the geometric and electronic structure of a range of 1,1'-dialkynylferrocene molecules, as either single-molecules, or as self-assembled monolayers.

Multi-component self-assembled molecular-electronic films: towards new high-performance thermoelectric systems.

The thermoelectric properties of parallel arrays of organic molecules on a surface offer the potential for large-area, flexible, solution processed, energy harvesting thin-films, whose room-temperature transport properties are controlled by quantum interference (QI). Recently, it has been demonstrated that constructive QI (CQI) can be translated from single molecules to self-assembled monolayers (SAMs), boosting both electrical conductivities and Seebeck coefficients. However, these CQI-enhanced systems are limited by rigid coupling of the component molecules to metallic electrodes, preventing the introduction of additional layers which would be advantageous for their further development.

Optimised power harvesting by controlling the pressure applied to molecular junctions.

A major potential advantage of creating thermoelectric devices using self-assembled molecular layers is their mechanical flexibility. Previous reports have discussed the advantage of this flexibility from the perspective of facile skin attachment and the ability to avoid mechanical deformation. In this work, we demonstrate that the thermoelectric properties of such molecular devices can be controlled by taking advantage of their mechanical flexibility.

Tuning the thermoelectrical properties of anthracene-based self-assembled monolayers.

It is known that the electrical conductance of single molecules can be controlled in a deterministic manner by chemically varying their anchor groups to external electrodes. Here, by employing synthetic methodologies to vary the terminal anchor groups around aromatic anthracene cores, and by forming self-assembled monolayers (SAMs) of the resulting molecules, we demonstrate that this method of control can be translated into cross-plane SAM-on-gold molecular films. The cross-plane conductance of SAMs formed from anthracene-based molecules with four different combinations of anchors are measured to differ by a factor of approximately 3 in agreement with theoretical predictions.

Scale-Up of Room-Temperature Constructive Quantum Interference from Single Molecules to Self-Assembled Molecular-Electronic Films.

The realization of self-assembled molecular-electronic films, whose room-temperature transport properties are controlled by quantum interference (QI), is an essential step in the scale-up of QI effects from single molecules to parallel arrays of molecules. Recently, the effect of QI (DQI) on the electrical conductance of self-assembled monolayers (SAMs) has been investigated. Here, through a combined experimental and theoretical investigation, we demonstrate chemical control of different forms of QI (CQI) in cross-plane transport through SAMs and assess its influence on cross-plane thermoelectricity in SAMs.