A mononuclear CoII single‐molecule magnet suitable for click chemistry was investigated. [M(oda)(aterpy)] complexes (oda2– = oxodiacetate, aterpy = 4′‐azido‐2,2′:6′,2″‐terpyridine) with M = MnII, ZnII, and CoII were synthesized as azide‐functionalized building blocks for the copper‐catalyzed azide–alkyne cycloaddition reaction. The required structural integrity of the complexes in solution was proven in great detail by using ESI‐MS and NMR spectroscopy. For the six‐coordinate [Co(oda)(aterpy)] complex, single‐molecule magnet behavior was confirmed with an effective energy barrier of 4.2 cm–1.
CuAAC click reactions were used for the first time to assemble click-functionalized magnetic molecules into extended molecular arrangements in a deliberate manner.
A series of fused dihydrodibenzobarrelene (dibenzobicyclo[2.2.2]octadiene) and lactone rings were prepared from dialkyl fumarates and 9‐anthracenemethanol. These products were prepared via a one‐pot synthesis in which a Diels‐Alder reaction occurred followed by an intramolecular transesterification to form the lactone ring. A key feature of this synthetic methodology is the straightforward purification of the reaction products, in most cases without the need for chromatography. The ease of work‐up along with the simple setup of the reaction (no catalysts or other reagents needed) make this methodology a convenient and potentially scalable route to complex, multicyclic structures. Molecular modeling of the transition structures for Diels‐Alder reaction suggested that transesterification could precede cycloaddition, but NMR in situ studies confirmed the opposite occurrence. Product formed exclusively in the trans configuration for all alkyl fumarates used.
We are reporting new dimeric units of basic carboxylates bearing the {Fe(III)(2)M(II)O} motif for M = Co and Ni, covalently bound through the tetradentate bridging (LL) 2,2'-azopyiridine (azpy) and 2,3-di(2-pyridyl)quinoxaline ligands (dpq). We structurally characterized the hexanuclear clusters, and their magnetic properties have been fully analyzed. DFT calculations have been performed as a supplementary tool. All results evidence a weak antiferromagnetic interaction through the bridging ligands between isolated spin ground states arising from intra-Fe(2)MO core exchange couplings. Together with the pioneer 2,2'-bipyrimidine bridged systems, the new complexes reported constitute a family of complexes where the exchange interaction can be tuned by the selection of the bridging LL type ligand.
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