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Robust Direct (Hetero)arylation Polymerization in Biphasic Conditions

The synthesis of conjugated polymers from direct (hetero)arylation polymerization (DHAP) has been achieved for the first time using biphasic water/toluene conditions. This protocol is robust enough to form polymers even when air is introduced in the system. General reactivity is demonstrated for a single set of polymerization conditions with thienyl- or phenyl-based substrates, whether they are electron-rich or electron-poor. Complete characterization from differential scanning calorimetry and 1H NMR and UV-vis-NIR spectroscopies is presented, demonstrating this DHAP protocol offers comparable or better properties than the very best values published thus far. High molecular weights are obtained, showcasing the perfect equilibrium of reactivity and selectivity attained with this method. Moreover, this efficient and versatile methodology, which also uses low-cost, “wet” reagents, is scalable and done at ambient pressure.

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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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Torsional Bias as a Strategy to Tune Singlet-Triplet Gaps in Organic Diradicals

Quinoidal compounds with proaromatic structures possess differing degrees of diradical character, where the open-shell diradical resonance form has restored aromaticity throughout the compound. Methods to tune the diradical character of these compounds have traditionally focused on altering the length and the molecular composition of the pi-conjugated backbones. However, other molecular design strategies to tune the singlet-triplet gap of pi-conjugated quinoidal molecules have not been extensively explored. We previously reported a strikingly small energy gap between the quinoidal and diradical states of a quinoidal small molecule containing methano[10]annulene (TMTQ) that was dictated in large part by the unusual aromaticity of the central annulene ring. Here, we report on two alkylated derivatives of TMTQ that present substantially different torsional biases to the planarity of the TMTQ pi-system. Using a combination of electronic and vibrational spectroscopies, magnetic measurements, and quantum chemical calculations, we demonstrate here how a steric effect rather than pi-electron compositional molecular engineering can dramatically narrow the singlet-triplet gap of a quinoidal compound to as small as -0.52 kcal/mol, determined experimentally. This study offers important insight for the continued development of open-shell diradical molecules that need not rely exclusively on the design of synthesis of new and complex pi-conjugated systems.

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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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HETEROCYCLIC NUCLEAR HORMONE RECEPTOR MODULATORS

Provided are fused bicyclic compounds of Formula (I) effective to modulate the glucocorticoid receptor, wherein X, Y, Z, M, Q, L, J, G, E, A, Ring 1 and 2 are defined as in the description. Also provided herein are a pharmaceutical composition thereof, and uses in the manufacture of a medicament for treating corresponding disease thereof.

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

Final Thoughts on Chemistry for Pd2(DBA)3

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Pure and complex nanostructures using poly[bis(triiso-propylsilylethynyl) benzodithiophene-bis(decyltetradecyl-thien) naphthobisthiadiazole], carbon nanotubes and reduced graphene oxide for high-performance polymer solar cells

Crystallization of poly[bis(triiso-propylsilylethynyl) benzodithiophene-bis(decyltetradecyl-thien) naphthobisthiadiazole] (PBDT-TIPS-DTNT-DT) was investigated in supramolecules based on carbon nanotubes (CNTs) and reduced graphene oxide (rGO) and their grafted derivatives. The principal peaks of PBDT-TIPS-DTNT-DT crystals were in the range 3.50?3.75. By grafting the surface of the carbonic materials, the assembling of polymer chains decreased because of hindrance of poly(3-dodecylthiophene) (PDDT) grafts against pi-stacking. The diameters of CNT/polymer and CNT-g-PDDT/polymer supramolecules were 160 and 100 nm. The rGO/polymer supramolecules had the highest melting point (Tm = 282 C) and fusion enthalpy (DeltaHm = 25.98 J g?1), reflecting the largest crystallites and the most ordered constituents. Nano-hybrids based on grafted rGO (276 C and 28.26 J g?1), CNT (275 C and 27.32 J g?1) and grafted CNT (268 C and 22.17 J g?1) were also analyzed. Tm and DeltaHm values were significantly less in corresponding melt-grown systems. The nanostructures were incorporated in active layers of PBDT-TIPS-DTNT-DT:phenyl-C71-butyric acid methyl ester (PC71BM) solar cells to improve the photovoltaic features. The best results were detected for PBDT-TIPS-DTNT-DT:PC71BM:rGO/polymer systems having Jsc = 13.11 mA cm?2, fill factor 60% and Voc = 0.71 V with an efficacy of 5.58%. On grafting the rGO and CNT, efficiency reductions were 12.01% (5.58%?4.91%) and 9.34% (4.07%?3.69%), respectively.

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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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Sidechain engineering in anthracene derivatives: Towards photofunctional liquid crystals

A series of anthracene derivatives were synthesised to explore how their sidechain configurations influenced their phase behaviour and thereby guiding the design of photofunctional liquid crystalline materials. In the case of 9,10-diphenylanthracene derivatives, longer and more alkyl sidechains resulted in lower melting temperatures, yet liquid crystallinity was not observed. A novel room-temperature molecular liquid was synthesised based on 9,10-diphenylanthracene, the optical properties of which may be exploited in photonic applications. Liquid crystallinity was observed in one of the derivatives of 9,10-bis(phenylethynyl)anthracene, forming a nematic phase at around 210C. These results highlight the potential opportunities for photofunctional materials with enhanced properties if liquid crystalline anthracenes can be found with lower phase transition temperatures.

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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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PdII complexes of [44]-and [46]decaphyrins: The largest hueckel aromatic and antiaromatic, and Moebius aromatic macrocycles

Reductive metalation of [44]decaphyrin with [Pd2-(dba)3] provided a Hueckel aromatic [46]decaphyrin PdII complex, which was readily oxidized upon treatment with DDQ to produce a Hueckel antiaromatic [44]decaphyrin PdII complex. In CH2Cl2 solution the latter complex underwent slow tautomerization to a Moebius aromatic [44]decaphyrin PdII complex which exists as a mixture of conformers in dynamic equilibrium. To the best of our knowledge, these three PdII complexes represent the largest Hueckel aromatic, Hueckel antiaromatic, and Moebius aromatic complexes to date.

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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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Palladium catalyzed cyclizations of oxime esters with 1,2-disubstituted alkenes: Synthesis of dihydropyrroles

Pd-catalyzed cyclizations of oxime esters with 1,2-dialkylated alkenes provide an entry to chiral dihydropyrroles. Substrate and catalyst controlled strategies for selective product formation (vs alternative pyrroles) are outlined.

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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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One-Step Construction of Fluorenone-Based Donor-Acceptor-Type Conjugated Polymers via Direct Arylation Polymerization for Cell-Imaging Applications

Direct arylation polymerization (DARP) is a novel approach to obtain conjugated polymers (CPs) through the straightforward C-H activation of monomer building blocks. In this work, a convenient DARP method with high efficiency and excellent regioselectivity is developed to synthesize a series of donor-acceptor (D-A)-type CPs composed of electron-acceptor moiety fluorenones (FOs) and various electron-donor moieties. CPs with different band gaps are obtained in good yields and display large Stokes shifts up to 295 nm. Two ionic CPs, PFOP-NEt3(+) and PFOP-COO(-), were prepared in a polar solvent system to improve the water solubility and biocompatibility using the proposed DARP method. Detailed photophysical studies of these two CPs suggest that both solvation and hydrogen bonds play important roles in determining the polymers’ spectroscopic properties. Further studies of the cationic polymer PFOP-NEt3(+) in cell imaging demonstrate its potential application in labeling cell membranes and lysosomes given its low cytotoxicity, excellent photostability, and specific subcellular localization.

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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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Non-halogenated solvent-processed ternary-blend solar cells: Via alkyl-side-chain engineering of a non-fullerene acceptor and their application in large-area devices

Solution processability is one of the advantages of organic solar cells (OSCs). However, most high-efficiency OSCs are prepared using hazardous chlorinated solvents for the deposition of photoactive layers. The replacement of non-halogenated solvents with eco-friendly green solvents for photoactive materials is urgently required. Herein, we have developed a novel asymmetric T2-OEHRH, which is modified from the symmetric T2-ORH. The introduction of asymmetric alkyl side chains onto rhodanine end groups can effectively suppress excessive self-aggregation/crystallization and substantially improve solubility without sacrificing optoelectrical properties. Therefore, ternary-blend OSCs based on PTB7-Th:EH-IDTBR:T2-OEHRH processed using a non-halogenated solvent system exhibit a uniform and favorable morphology and give a high power conversion efficiency (PCE) of 12.10%. More importantly, we demonstrate an impressive PCE of 9.32% for large-area NFA-OSCs (substrate size = 100 cm2 and aperture size = 55.5 cm2) prepared via D-bar coating in air. To our knowledge, this PCE is the highest reported to date for NFA-based large-area OSC modules processed from a non-halogenated solvent. This asymmetric alkyl-chain engineering strategy can be exploited to develop high-performance large-area NFA-OSCs with eco-friendly solvent processing.

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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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Composition and organic optoelectric device and display device

Disclosed are a composition including a first host compound including moieties represented by the Chemical Formulae 1 to 3 that are sequentially bonded with each other and a second host compound including at least one carbazole group with a substituent having hole characteristics, and an organic optoelectric device and a display device to which the composition is applied. In the Chemical Formulae 1 to 3, X1, X2, R1 to R4 and L are the same as described in the detailed description.

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