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Random D-A1-D-A2 terpolymers based on benzodithiophene, thiadiazole[3,4-e]isoindole-5,7-dione and thieno[3,4-c]pyrrole-4,6-dione for efficient polymer solar cells

Recent developments on regio-regular and random terpolymers based on a donor/acceptor architecture (D1-A-D2-A or D-A1-D-A2) have shown promising results for their use as donor materials in bulk heterojunction (BHJ) polymer solar cells. New random terpolymers including benzo[1,2-b:4,5-b?]-dithiophene (BDT) as the electron-donor moiety and thiadiazolo[3,4-e]isoindole-5,7-dione (TID) and thieno[3,4-c]pyrrole-4,6-dione (TPD) as electron-accepting moieties were synthesized by Stille cross-coupling polymerization. Incremental addition of TPD (from 0 to 90%) led to the following random terpolymers: P[(BDT-TID)x-(BDT-TPD)y]n. Their electro-optical and photovoltaic properties were investigated. These high molecular weight and highly processable random terpolymers exhibited broad and strong absorption (300-800 nm), moderate bandgaps (1.52 eV to 1.64 eV) and deep-lying HOMO/LUMO energy levels (?5.6 eV and ?3.9 eV, respectively). First, the optimized inverted device ITO/ZnO/P1:PC71BM/MoO3/Ag (where P1 is a typical D/A copolymer; TID 100%; TPD 0%) showed a power conversion efficiency up to 6.36% which is higher than the PCE reported in the literature for an analog of P1 (3.42%). Then, devices based on random terpolymers (P2-P10) showed power conversion efficiencies ranging from 5.06% (for P7; 40% TID/60% TPD) up to 6.70% (for P2; 90% TID/10% TPD) when PC61PM is used as the electron acceptor. A PCE as high as 7.30%, a Voc of 0.81 V, a Jsc of 13.86 mA cm?2 and a FF of 65% were achieved for P2 when PC71PM was used. This PCE is among the highest PCE values reported for random terpolymer-based polymer solar cells.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Palladium(0)-catalysed synthesis of 2,3- and 3,4-unsaturated aryl beta-O-glycosides

Arylation of 6-O-tert-butyldiphenylsilyl-3,4-di-O-isobutyloxycarbonyl-d-glucal (3) with various phenols in the presence of a catalytic amount of palladium(0) gave the corresponding 2,3- and 3,4-unsaturated beta-O-glycosides. The reaction is stereospecific, in all cases, only the beta-anomer is formed.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Organic solvent nanofiltration and adsorbents; A hybrid approach to achieve ultra low palladium contamination of post coupling reaction products

Due to potentially toxic contamination of pharmaceutical products, effective removal of palladium from post-reaction solutions is of great importance, especially in the pharmaceutical industry. This work addresses this challenge by combining organic solvent nanofiltration (OSN) with adsorbents in a hybrid process. Post-reaction solutions resulting from acylation and Suzuki reactions were subjected to OSN, the catalyst was retained by the membrane, and the product was collected in the permeate. Palladium levels in the permeate were reduced further by using adsorbents. This technique achieved ultralow palladium concentration (<10 mg Pd kg product-1 for post-reaction solutions with toluene and ethyl acetate as solvents. The results obtained using the hybrid OSN-adsorbent process were compared to those using selected adsorbents only. When palladium was removed from a post-Suzuki reaction solution, using polystyrenebound trimercaptotriazine as the adsorbent, the hybrid process, while using 10 times less adsorbent than the adsorbent-only process, was able to reduce the product contamination to an 8.5 times lower level. It is thought that the membrane stage of this technique removes bulky ligated palladium along with palladium nanoparticles, species that are hard to remove by adsorption only. The residual palladium in the permeate stream comprises well-dissolved, smaller molecules, and these are removed very effectively by the adsorbent. This allows high-purity products to be achieved by treatment of the OSN permeate with low amounts of absorbents. Therefore, this hybrid process is recommended for separations where adsorbent-only treatment can result in significant product losses, or where strong ligand-palladium interactions compete with adsorbent active sites, keeping palladium in solution. Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Synthetic Route of 52409-22-0. In my other articles, you can also check out more blogs about 52409-22-0

Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Structure-performance relationship on the asymmetric methoxy substituents of spiro-OMeTAD for perovskite solar cells

The hole-transporting materials (HTMs) play an important role in energy conversion process of perovskite solar cells (PSCs). Here, two spiro-OMeTAD derivatives, 2,4-spiro-OMeTAD and 3,4-spiro-OMeTAD with asymmetric methoxy substituents, have been designed, synthesized and fully characterized. Optimization of the positions of the two methoxy substituents in each of the quadrants was proved to be able to adjust the electronic and optical properties of the HTMs, as investigated by cyclic voltammetry and UV/vis spectroscopy. In particular, PSC devices based on 2,4-spiro-OMeTAD exhibited highly improved photovoltaic performance showing an overall conversion efficiency of 17.2% with excellent stability, which is higher than that of the device derived from spiro-OMeTAD (15.0%) under the same conditions. Besides, 3,4-spiro-OMeTAD based PSCs only achieved a power conversion efficiency of 9.1%, demonstrating a huge influence of HTM structure on the cell performance.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Asymmetric Dearomatization/Cyclization Enables Access to Polycyclic Chemotypes

Enantioenriched, polycyclic compounds were obtained from a simple acylphloroglucinol scaffold. Highly enantioselective dearomatization was accomplished using a Trost ligand?palladium(0) complex. A computational DFT model was developed to rationalize observed enantioselectivities and revealed a key reactant-ligand hydrogen bonding interaction. Dearomatized products were used in visible light-mediated photocycloadditions and oxidative free radical cyclizations to obtain novel polycyclic chemotypes including tricyclo[4.3.1.01,4]decan-10-ones, bicyclo[3.2.1]octan-8-ones and highly substituted cycloheptanones.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Trineopentylphosphine: A conformationally flexible ligand for the coupling of sterically demanding substrates in the Buchwald-Hartwig amination and suzuki-miyaura reaction

Trineopentylphosphine (TNpP) in combination with palladium provides a highly effective catalyst for the Buchwald-Hartwig coupling of sterically demanding aryl bromides and chlorides with sterically hindered aniline derivatives. Excellent yields are obtained even when both substrates include 2,6-diisopropyl substituents. Notably, the reaction rate is inversely related to the steric demand of the substrates. X-ray crystallographic structures of Pd(TNpP)2, [Pd(4-t-Bu-C6H4)(TNpP)(mu-Br)] 2, and [Pd(2-Me-C6H4)(TNpP)(mu-Br)] 2 are reported. These structures suggest that the conformational flexibility of the TNpP ligand plays a key role in allowing the catalyst to couple hindered substrates. The Pd/TNpP system also shows good activity for the Suzuki coupling of hindered aryl bromides.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Regioisomerism of an alkyl-substituted bithiophene comonomer in (3: E,8 E)-3,8-bis(2-oxoindolin-3-ylidene)naphtho-[1,2- b:5,6- b ?]difuran-2,7(3 H,8 H)-dione (INDF)-based D-A polymers for organic thin film transistors

Two donor-acceptor (D-A) polymers based on (3E,8E)-3,8-bis(2-oxoindolin-3-ylidene)naphtha-[1,2-b:5,6-b?]difuran 2,7(3H,8H)-dione (INDF) and substituted regioisomeric bithiophene (BT) units with different side chain positions (head-to-head, HH, and tail-to-tail, TT) were synthesized. PINDFBT-(HH) achieved electron (mue) and hole (muh) mobilities as high as 0.33 cm2 V-1 s-1 and 0.15 cm2 V-1 s-1, respectively, while PINDFBT-(TT) showed an order of magnitude lower mobilities with mue of 0.07 cm2 V-1 s-1 and muh of 0.02 cm2 V-1 s-1. The distinctly different electrical performance of these two polymers originates from their different side chain placements on the bithiophene units and consequently different electronic structures, backbone coplanarity, chain packing, and thin film morphology. Our results showed that a bithiophene unit with an HH substitution pattern is much more favoured in terms of the charge transport property of the polymers.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Low-Cost N,N?-Bicarbazole-Based Dopant-Free Hole-Transporting Materials for Large-Area Perovskite Solar Cells

Despite the recent unprecedented development of efficient dopant-free hole transporting materials (HTMs) for high-performance perovskite solar cells (PSCs) on small-area devices (?0.1 cm2), low-cost dopant-free HTMs for large-area PSCs (?1 cm2) with high power conversion efficiencies (PCEs) have rarely been reported. Herein, two novel HTMs, 3,3?,6,6? (or 2,2?,7,7?)-tetrakis(N,N?-di-p-methoxyphenylamine)-N,N?-bicarbazole (3,6 BCz-OMeTAD or 2,7 BCz-OMeTAD), are synthesized via an extremely simple route from very cheap raw materials. Owing to their excellent film-forming abilities and matching energy levels, 3,6 BCz-OMeTAD and 2,7 BCz-OMeTAD can be successfully employed as a perfect ultrathin (?30 nm) hole transporting layer in large-area PSCs up to 1 cm2. The 3,6 BCz-OMeTAD and 2,7 BCz-OMeTAD based large-area PSCs show highest PCEs up to 17.0% and 17.6%, respectively. More importantly, high performance large-area PSCs based on 2,7 BCz-OMeTAD retain 90% of the initial efficiency after 2000 h storage in an ambient environment without encapsulation.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Bromomethyllithium-mediated chemoselective homologation of disulfides to dithioacetals

An efficient, chemoselective homologation of disulfides and diselenides to the corresponding dithio- and diselenoacetals has been developed via the addition of bromomethyllithium. Chemoselectivity is fully preserved in the presence of concomitant electrophilic sites decorating the substrates. The synthetic potential of selected dithioacetals has been evaluated in Feringa-Fananas-Mastral-type Pd-catalyzed coupling with an organolithium and in the unusual 1,4-addition to a Weinreb amide.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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PYRIMIDINE DERIVATIVES AS CORTICOTROPIN RELEASING FACTOR INHIBITORS

The present invention relates to novel heterocyclic antagonists of Formula (I) and pharmaceutical compositions comprising said antagonists of the corticotropin releasing factor receptor (“CRF receptor”) useful for the treatment of depression, anxiety, affective disorders, feeding disorders, post-traumatic stress disorder, headache, drug addiction, inflammatory disorders, drug or alcohol withdrawal symptoms and other conditions the treatment of which can be effected by the antagonism of the CRF-1 receptor. ”

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method