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Abstract N‐Type thermoelectrics typically consist of small molecule dopant+polymer host. Only a few polymer dopant+polymer host systems have been reported, and these have lower thermoelectric parameters. N‐type polymers with high crystallinity and order are generally used for high‐conductivity () organic conductors. Few n‐type polymers with only short‐range lamellar stacking for high‐conductivity materials have been reported. Here, we describe an n‐type short‐range lamellar‐stacked all‐polymer thermoelectric system with highestof 78 S−1, power factor (PF) of 163 μW m−1 K−2, and maximum Figure of merit (ZT) of 0.53 at room temperature with a dopant/host ratio of 75 wt%. The minor effect of polymer dopant on the molecular arrangement of conjugated polymer PDPIN at high ratios, high doping capability, high Seebeck coefficient (S) absolute values relative to, and atypical decreased thermal conductivity () with increased doping ratio contribute to the promising performance.
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Triplet Generation Through Singlet Fission in Metal‐Organic Framework: An Alternative Route to Inefficient Singlet‐Triplet Intersystem Crossing
Abstract High quantum yield triplets, populated by initially prepared excited singlets, are desired for various energy conversion schemes in solid working compositions like porous MOFs. However, a large disparity in the distribution of the excitonic center of mass, singlet‐triplet intersystem crossing (ISC) in such assemblies is inhibited, so much so that a carboxy‐coordinated zirconium heavy metal ion cannot effectively facilitate the ISC through spin‐orbit coupling. Circumventing this sluggish ISC, singlet fission (SF) is explored as a viable route to generating triplets in solution‐stable MOFs. Efficient SF is achieved through a high degree of interchromophoric coupling that facilitates electron super‐exchange to generate triplet pairs. Here we show that a predesigned chromophoric linker with extremely poor ISC efficiency (kISC) butform triplets in MOF in contrast to the frameworks that are built from linkers with sizablekISCbut. This work opens a new photophysical and photochemical avenue in MOF chemistry and utility in energy conversion schemes.
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- Award ID(s):
- 1944903
- PAR ID:
- 10439638
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 62
- Issue:
- 38
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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