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Over a 0-7 T range, transient absorption microscopy on anthradithiophene organic crystals shows that singlet to triplet pair state conversion is anticorrelated with fluorescence yield. This shows how the dominant singlet fission charge multiplication pathway can be switched-off with increasing B-field or by changing the molecular packing motifs.

 

Quantum dot-organic semiconductor hybrid materials are gaining increasing attention as spin mixers for applications ranging from solar harvesting to spin memories. Triplet energy transfer between the inorganic quantum dot (QD) and organic semiconductor is a key step to understand in order to develop these applications. Here we report on the triplet energy transfer from PbS QDs to four energetically and structurally similar tetracene ligands. Even with similar ligands we find that the triplet energy transfer dynamics can vary significantly. For TIPS-tetracene derivatives with carboxylic acid, acetic acid and methanethiol anchoring groups on the short pro- cata side we find that triplet transfer occurs through a stepwise process, mediated via a surface state, whereas for monosubstituted TIPS-tetracene derivative 5-(4-benzoic acid)-12-triisopropylsilylethynyl tetracene (BAT) triplet transfer occurs directly, albeit slower, via a Dexter exchange mechanism. Even though triplet transfer is slower with BAT the overall yield is greater, as determined from upconverted emission using rubrene emitters. This work highlights that the surface-mediated transfer mechanism is plagued with parasitic loss pathways and that materials with direct Dexter-like triplet transfer are preferred for high-efficiency applications. 

Fluoroanthradithiophenes are well known organic semiconductors, where alkynyl substituents featuring silicon and germanium exhibit hole mobilities in excess of 5 cm 2 V −1 s −1 . A key feature to achieve these performance levels is the 2-dimensional brickwork packing of triethylsilyl and triethylgermyl side chains, which direct solid-state packing, increase molecular stability, and increase solution processability for cheap and large scale fabrication. We have recently reported side chains utilising carbon in place of the other group 14 atoms, resulting in less favourable 1-dimensional molecular packing. Here we present the synthesis of new derivatives which adopt 2-D brickwork packing without the use of silicon or germanium to determine substituent effects on charge carrier mobility. 

A carbon side-chain analogue to the high-performance organic semiconductor triethylsilylethynyl difluoroanthradithiophene has been synthesised and characterized. Atomic substitution of carbon for silicon results in subtle changes to opto-electronic properties, which are rationalised by density functional theory and balance of electron donating and withdrawing effects. Larger differences are observed in photostability and solid-state packing of the new material in comparison to known silicon and germanium derivatives. Comparison of the group 14 elements teaches us about the newly synthesised system, but also how the silylethynyl substituents used for the last two decades contribute to successful employment of functionalised polycyclic aromatic hydrocarbons as organic semiconductors.