A new strategy of platinum(II) complexation is developed to regulate the crystallinity and molecular packing of polynitrogen heterocyclic polymers, optimize the morphology of the active blends, and improve the efficiency of the resulting nonfullerene polymer solar cells (NF‐PSCs). The newly designed s‐tetrazine (s‐TZ)‐containing copolymer of PSFTZ (4,8‐bis(5‐((2‐butyloctyl)thio)‐4‐fluorothiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐alt‐3,6‐bis(4‐octylthiophen‐2‐yl)‐1,2,4,5‐tetrazine) has a strong aggregation property, which results in serious phase separation and large domains when blending with Y6 ((2,2′‐((2Z,2′Z)‐((12,13‐bis(2‐ethylhexyl)‐3,9‐diundecyl‐12,13‐dihydro‐[1,2,5]thiadiazolo[3,4‐e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2‐g]thieno[2′,3′:4,5]thieno[3,2‐b]indole‐2,10‐diyl)bis(methanylylidene))bis(5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1H‐indene‐2,1‐diylidene))dimalononitrile)), and produces a power‐conversion efficiency (PCE) of 13.03%. By adding small amount of Pt(Ph)2(DMSO)2 (Ph, phenyl and DMSO, dimethyl sulfoxide), platinum(II) complexation would occur between Pt(Ph)2(DMSO)2 and PSFTZ. The bulky benzene ring on the platinum(II) complex increases the steric hindrance along the polymer main chain, inhibits the polymer aggregation strength, regulates the phase separation, optimizes the morphology, and thus improves the efficiency to 16.35% in the resulting devices. 16.35% is the highest efficiency for single‐junction PSCs reported so far.
The origin of paired appendages was a major evolutionary innovation for vertebrates, marking the first step towards fin- (and later limb-) driven locomotion. The earliest vertebrate fossils lack paired fins but have well-developed median fins, suggesting that the mechanisms of fin development were assembled first in the midline. Here we show that shark median fin development involves the same genetic programs that operate in paired appendages. Using molecular markers for different cell types, we show that median fins arise predominantly from somitic (paraxial) mesoderm, whereas paired appendages develop from lateral plate mesoderm. Expression of Hoxd and Tbx18 genes, which specify paired limb positions, also delineates the positions of median fins. Proximodistal development of median fins occurs beneath an apical ectodermal ridge, the structure that controls outgrowth of paired appendages. Each median fin bud then acquires an anteroposteriorly-nested pattern of Hoxd expression similar to that which establishes skeletal polarity in limbs. Thus, despite their different embryonic origins, paired and median fins utilize a common suite of developmental mechanisms. We extended our analysis to lampreys, which diverged from the lineage leading to gnathostomes before the origin of paired appendages, and show that their median fins also develop from somites and express orthologous Hox and Tbx genes. Together these results suggest that the molecular mechanisms for fin development originated in somitic mesoderm of early vertebrates, and that the origin of paired appendages was associated with re-deployment of these mechanisms to lateral plate mesoderm.
Naphtho[1,2-c:5,6-c']bis[1,2,5]thiadiazole-based small molecules have been synthesized for organic solar cells. The optimized devices processed by a halogen-free solvent of CS2 exhibited a PCE of 11.53% with a small energy loss of 0.57 eV.
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