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Thus far, there is still no study systematically investigating the influence of asymmetric side-chain design on a polymer’s stretchability and its associated stretchable device applications. Herein, three kinds of asymmetric side chains consisting of carbosilane side chain (Si-C8), siloxane-Terminated side chain (SiO-C8), and decyltetradecane side chain (DT) are engineered in isoindigo-bithiophene (PII2T, P1-P3) and isoindigo-difluorobithiophene (PII2TF, P4-P6) conjugated polymers, and their structure-stretchability correlation is explored in field-effect transistor characterization. It is revealed that owing to the geometric difference between the side chains, different asymmetric side-chain combinations impose distinct influences on the molecular stacking and orientation of the derived polymers. Surprisingly, the combination of asymmetric side chains and backbone fluorination is shown to deliver the best stretchability and mechanical durability of the derived polymer. Consequently, P6 consisting of asymmetric Si-C8/DT side chains and fluorinated backbone possesses the best mobility preservation of 81% at 100% strain with the stretching force perpendicular to the charge-Transporting direction. Moreover, it presents 90% mobility retention after 400 stretching-releasing cycles with 60% strain, greatly exceeding the value (36%) of the non-fluorinated counterpart (P3). Our results suggest that the rational design of asymmetric side chains and backbone fluorination provides an efficient way to enhance the intrinsic stretchability of conjugated polymers.

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

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Although the palladium-catalyzed Suzuki-Miyaura cross-coupling of aryl esters has received significant attention, there is a lack of methods that utilize cheap and readily accessible Pd-phosphane catalysts, and can be routinely carried out with high cross-coupling selectivity. Herein, we report the first general method for the cross-coupling of pentafluorophenyl esters (pentafluorophenyl = pfp) by selective C?O acyl cleavage. The reaction proceeds efficiently using Pd(0)/phosphane catalyst systems. The unique characteristics of pentafluorophenyl esters are reflected in the fully selective cross-coupling vs. phenolic esters. Of broad synthetic interest, this report establishes pentafluorophenyl esters as new, highly reactive, bench-stable, economical, ester-based, electrophilic acylative reagents via acyl-metal intermediates. Mechanistic studies strongly support a unified reactivity scale of acyl electrophiles by C(O)?X (X = N, O) activation. The reactivity of pfp esters can be correlated with barriers to isomerization around the C(acyl)?O bond.

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

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Self-assembly of three-dimensional (3-D) architecture using terpyridine (tpy)-based building blocks is challenging and seldom addressed due the fixed geometry (around 180) of tpy-M(ii)-tpy (M = Ru, Fe, Zn, and Cd) connectivity. Here we describe the self-assembly of 3-D giant metallo-supramolecular cubes using three-armed terpyridine ligands constructed on adamantane with molecular weight up to 18 k and edge length at ?4.9 nm, which is significantly larger than the sizes of previous metallo-supramolecular cubes. Instead of using metal center as vertices in the commonly used synthetic strategy of 3-D molecular coordination ensembles, these cages [M 12L8] bear 8 ligands as vertices with 12 metal ions on the edges. With a suitable edge length, the giant cubes appear to be the sole product after self-assembly from a variety of possible architectures. The 3-D metallo-supramolecules were characterized and supported by NMR, DOSY, ESI-MS, travelling wave ion mobility-MS and AFM. The Royal Society of Chemistry 2014.

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

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A new series of n-type D-A terpolymers (P(NDI2HD-T-S)) was synthesized from an electron-deficient naphthalene diimide (NDI)-based unit in conjugation with two electron-rich thiophene (T) and selenophene (S) units, and their performances as electron acceptors in all-polymer solar cells (all-PSCs) were compared. The crystallinity of the P(NDI2HD-T-S) terpolymers can be systematically controlled by tuning the T/S molar ratios (T/S=100/0, 80/20, 50/50, 20/80 and 0/100) in the polymer backbone. An increase in the S content induced a significant enhancement in the crystallinity of the terpolymers. Therefore, the incorporation of more S units enhanced the structural ordering of the terpolymers and the electron mobility in the all-PSCs. The power conversion efficiency of the all-PSCs based on a P(NDI2HD-T-S) terpolymer acceptor and a PTB7 polymer donor increased from 2.50 to 3.60% as the S content increased, which was primarily due to the enhanced short-circuit current. To understand the effects of the T/S compositions on the photovoltaic performances, we investigated their influence on the optical, electrical and structural properties of the n-type D-A terpolymers.

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

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Desmosine, a crosslinking pyridinium amino acid found in elastin, is a useful biomarker for the diagnosis of diseases related to elastin degradation, such as chronic obstructive pulmonary disease (COPD). In order to achieve the precise quantitation of this compound using isotope dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis, isotopically-labeled internal standards including deuterated desmosine are required. We report herein the synthesis of multi-deuterated desmosine (d3?9) as a potential internal standard. This synthesis involves the preparation of an alkyne via a Sonogashira cross-coupling, followed by deuterogenation of the triple bond to incorporate deuterium atoms into the substrate.

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

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2,3-Disubstituted benzo[b]furans are prepared in one step from commercially available phenols and readily accessible unactivated internal alkynes (see scheme). This Pd-catalyzed oxidative annulation has a broad substrate scope and allows access to a wide range of benzo[b]furans. Copyright

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

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An efficient synthesis of substituted 1,4-diazepines is developed. The accessible intermediates have been obtained via Pd-catalyzed amination. The subsequent hydrogenation and intramolecular condensation sequences could be conducted successively in one pot without special operation. The mild and general strategy enables the synthesis of various substituted 1,4-diazepines in high yields.

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

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Cooperative catalysis enables the direct enantioselective alpha-allylation of linear prochiral esters using Si-substituted allyl electrophiles. The Si-substituent directs the regioselectivity of enantioselective bond formation and provides products containing synthetically versatile pentafluorophenyl ester and vinylsilane moieties. Critical to the efficacy of this process was the recognition that the ancillary ligand on palladium could be altered to prevent formation of a deleterious ether by-product, whilst retaining enantioselectivity through the Lewis base catalyst. Flexibility such as this is unique to cooperative catalysis events and provides efficient access to an array of enantioenriched products that are orthogonally functionalized and easily modified.

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

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Novel aryl silicon and aryl germanium host materials are described. These compounds improve OLED device performance when used as hosts in the emissive layer of the OLED.

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

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The utility of the thio acid-azide coupling reaction to afford amides is explored in imidazole-containing substrates for application in the total synthesis of examples of oroidin alkaloids. Good yields of the expected amides are obtained in both monomeric and dimeric substrates. Bis azides react preferentially at the 2-azido position but hydrosulfenylation and reduction interfere. 2-Thiophenyl and 2-oxo groups were evaluated as 2-amino surrogates, the thioether delivered the expected amide, whereas 2-imidazolone gave a mixture of the expected amide and the hydrosulfenylation product.

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