The need for novel materials with luminescent properties and advanced processing features requires reliable and reproducible synthetic routes for the design of suitable materials, such as e.g. polypyridyl ruthenium(II) and iridium(III)-containing polymers. The most popular ligand for those purposes is the 4,4'-functionalized bipyridine unit. Therefore, several synthetic strategies for the derivatization of the 4,4'-dimethyl-2,2'-bipyridine are highlighted, and in particular functionalities, which enable further covalent linkage to polymeric structures, are discussed in this critical review. Subsequently, the different synthetic strategies for the preparation of polymeric metal-complexes are described, either starting from small functionalized complexes (later covalently attached to the polymer), or from macroligands (subsequently coordinated to the metal ions). The designed materials reveal good processing properties using spin coating and inkjet printing, as well as beneficial electro-optical properties for potential thin functional film applications, such as light-emitting electrochemical cells.
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http://dx.doi.org/10.1039/b610016c | DOI Listing |
Dalton Trans
January 2025
Department of Chemistry, Graduate School of Natural Science and Technology, Shimane University, 1060, Nishikawatsu, Matsue, Shimane, 690-8504, Japan.
Paddlewheel-type diruthenium(II,II) complexes are paramagnetic with two unpaired electrons ( = 1) and can be utilized as versatile building blocks for higher-order structures, such as supramolecular complexes, coordination polymers, and metal-organic frameworks, although they are generally highly air-sensitive. In this study, we developed an air-stable paddlewheel-type diruthenium(II,II) complex with two electron-withdrawing 1,8-naphthyridine-2-carboxylate (npc) ligands, [Ru(μ-npc)(OCMe)] (1). The two acetate ligands in 1 can be replaced by other carboxylate ligands; the solvothermal reactions of 1 with benzoic acid (HOCPh) yields the heteroleptic [Ru(μ-npc)(OCPh)] (2), whereas its reaction with 1,8-naphthyridine-2-carboxylic acid (Hnpc) produces the homoleptic [Ru(μ-npc)(η-npc)] (3).
View Article and Find Full Text PDFChemistry
January 2025
Brandeis University, Chemistry, 415 South Street,, Waltham, 02453, UNITED STATES OF AMERICA.
We designed and synthesized three diacetylene monomers M1-M3 having two NH2 groups. As anticipated, the NH2 groups aided the preorganization of these monomers by N-H…N hydrogen bonding. In the crystals of monomer M1 and M2, the intermolecular N-H…N hydrogen bonding preorganized the diyne units in an orientation suitable for their topochemical polymerization, but in the case of monomer M3, the distance was slightly larger than that recommended for the topochemical reaction.
View Article and Find Full Text PDFChempluschem
January 2025
Sun Yat-Sen University, School of Chemistry, CHINA.
n-butane (n-C4H10) and isobutane (i-C4H10) are important raw materials in chemical industry. The separation of the two hydrocarbon isomers via distillation is challenging and energy-consuming. Herein we report the adsorption behavior of a microporous cobalt formate framework [Co3(HCOO)6] for potential kinetic separation of butane isomers.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438, China.
In traditional atom transfer radical polymerization (ATRP), oxygen must be meticulously eliminated due to its propensity to quench radical species and halt the polymerization process. Additionally, oxygen oxidizes the lower-valent Cu catalyst, compromising its ability to activate alkyl halides and propagate polymerization. In this study, we present an oxygen-driven ATRP utilizing alkylborane compounds, a method that not only circumvents the need for stringent oxygen removal but also exploits oxygen as an essential cofactor to promote polymerization.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438, China.
The synthesis of polymers with well-defined composition, architecture, and functionality has long been a focal area of research in the field of polymer chemistry. The advancement of controlled radical polymerization (CRP) has facilitated the synthesis of precise polymers, which are endowed with new properties and functionalities, thereby exhibiting a wide range of applications. However, radical polymerization faces several challenges, such as oxygen intolerance, and common thermal initiation methods may lead to side reactions and depolymerization.
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