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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. 

Abstract A three‐component synthesis methodology is described for the formation of covalent organic frameworks (COFs) containing extended aromatics. Notably, this approach enables synthesis of the building blocks and COF along parallel reaction landscapes, on a similar timeframe. The use of fragmental building block components, namely pyrene dione diboronic acid as aggregation‐inducing COF precursor and the diamineso‐phenylenediamine (Ph), 2,3‐diaminonaphthalene (Naph), or (1R,2R)‐(+)‐1,2‐diphenylethylenediamine (2Ph) as extending functionalization units in conjunction with 2,3,6,7,10,11‐hexahydroxytriphenylene, resulted in the formation of the corresponding pyrene‐fused azaacene, i.e., Aza‐COF series with full conversion of the dione moiety, long‐range order, and high surface area. In addition, the novel three‐component synthesis was successfully applied to produce highly crystalline, oriented thin films of the Aza‐COFs with nanostructured surfaces on various substrates. The Aza‐COFs exhibit light absorption maxima in the blue spectral region, and each Aza‐COF presents a distinct photoluminescence profile. Transient absorption measurements of Aza‐Ph‐ and Aza‐Naph‐COFs suggest ultrafast relaxation dynamics of excited‐states within these COFs.