Effect of Side Chain Substituent Volume on Thermoelectric Properties of IDT-Based Conjugated Polymers

A p-type thermoelectric conjugated polymer based on indacenodithiophene and benzothiadiazole is designed and synthesized by replacing normal aliphatic side chains (P1) with conjugated aromatic benzene substituents (P2). The introduced bulky substituent on P2 is detrimental to form the intensified packing of polymers, therefore, it hinders the efficient transporting of the charge carriers, eventually resulting in a lower conductivity compared to that of the polymers bearing aliphatic side chains (P1). These results reveal that the modification of side chains on conjugated polymers is crucial to rationally designed thermoelectric polymers with high performance.

Gradient Copolymer Prepared from Alternating Ring-Opening Metathesis of Three Monomers

Bicyclo[4.2.0]oct-6-ene-7-carboxamide is a simple but highly strained olefin monomer which forms an alternating copolymer with cyclohexene in the presence of N-heterocyclic carbene-ruthenium catalyst. [4.2.0] moiety with bulky substituent on C7...

Mechanism and stereoselectivity of benzylic C–H hydroxylation by Ru–porphyrin: a computational study

Density functional theory calculations of an asymmetric benzylic C–H hydroxylation revealed the steric repulsion between the phenyl group of ethylbenzene and the bulky substituent of the D4-symmetric chiral Ru–porphyrin accounts for the stereoselectivity.

A donor design strategy for triazine-carbazole blue thermally activated delayed fluorescence materials

Enhancing the delayed emission proportion by incorporating bulky substituent at the 1-site of carbazole donors is proved to be effective and practical strategy to improve the EL performance of cyaphenine-carbazole type blue TADF emitters.

Synthesis of Monobactams via the Diastereoselective Kinugasa Reaction

The Kinugasa reaction between phthalimidoacetylene and cyclic nitrones derived from l-phenylglycine or l-serine and glyoxylic acid­, catalyzed by copper(I) chloride in the presence of triethylamine, is reported. The acetylene molecule approaches the nitrone exclusively anti to the bulky substituent next to the nitrogen atom to provide the cis-substituted β-lactam ring preferentially. The six-membered oxazinone ring can be easily opened, the phthaloyl residue can be transformed into a Boc protecting group, and substituents at the C-4 carbon atom and the nitrogen atom of the β-lactam ring can be easily removed or transformed into groups suitable for further synthesis of a variety of monobactam structures. Selected synthesized compounds were evaluated for their biological activity, showing interesting properties.

Bulky substituent and solvent-induced alternative nodes for layered Cd–isophthalate/acylhydrazone frameworks

A series of three layered cadmium–organic frameworks containing acylhydrazone and (un)substituted isophthalates have been prepared and characterised.

Steric Buttressing Changes Torquospecificity in Thermal Cyclo­butenone Rearrangements, Providing New Opportunities for 5H-Furanone Synthesis

Thermally induced rearrangements of 4-hydroxycyclo­butenones are known to provide clean and reliable access to an array of useful carbocyclic and fused heterocyclic ring systems. Rarely, such reactions have been diverted to an alternative pathway leading to furanone formation. Herein, we show that these switches in the course of the rearrangement occur when a substrate bears a bulky substituent and are due to adverse steric buttressing as the transition state for electrocyclisation is approached. We also show how the reaction provides new opportunities for furanone synthesis and how bulky proton and halogen surrogates can be used to divert classical rearrangement pathways toward furanone formation. Additionally, we show that classical rearrangement pathways can be promoted by the simple expedient of alcohol protection.

Synthesis of new pyrrolidine-based organocatalysts and study of their use in the asymmetric Michael addition of aldehydes to nitroolefins

New pyrrolidine-based organocatalysts with a bulky substituent at C2 were synthesized from chiral imines derived from (R)-glyceraldehyde acetonide by diastereoselective allylation followed by a sequential hydrozirconation/iodination reaction. The new compounds were found to be effective organocatalysts for the Michael addition of aldehydes to nitroolefins and enantioselectivities up to 85% ee were achieved.