Transition Metal Complexes and Radical Anion Salts of 1,10-Phenanthroline Derivatives Annulated with a 1,2,5-Tiadiazole and 1,2,5-Tiadiazole 1,1-Dioxide Moiety: Multidimensional Crystal Structures and Various Magnetic Properties

Molecules

Yoshiaki Shuku¹ 

[1] Department of Chemistry & Research Center for Materials Science, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8602, Japan; E-Mail

关键词: spin-crossover complexes;    intermolecular interactions;    electron acceptors;    radical anion salts;   

DOI  :  10.3390/molecules19010609

来源: mdpi

【 摘 要 】

Advances in the molecular variety and the elucidation of the physical properties of 1,10-phenanthroline annulated with 1,2,5-thiadiazole and 1,2,5-thiadiazole 1,1-dioxide moieties have been achieved, and are described herein. A 1,2,5-thiadiazole compound, [1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline (tdap), was used as a ligand to create multidimensional network structures based on S•••S and S•••N intermolecular interactions. A 1,2,5-thiadiazole 1,1-dioxide compound, [1,2,5] thiadiazolo[3,4-f][1,10]phenanthroline, 1,1-dioxide (tdapO₂), was designed to create a stable radical anion, as well as good network structures. Single crystal X-ray structure analyses revealed that transition metal complexes of tdap, and radical anion salts of tdapO₂ formed multidimensional network structures, as expected. Two kinds of tdap iron complexes, namely [Fe(tdap)₂(NCS)₂] and [Fe(tdap)₂(NCS)₂]•MeCN exhibited spin crossover transitions, and their transition temperatures showed a difference of 150 K, despite their similar molecular structures. Magnetic measurements for the tdapO₂ radical anion salts revealed that the magnetic coupling constants between neighboring radical species vary from strongly antiferromagnetic (J = −320 K) to ferromagnetic (J = 24 K), reflecting the differences in their π overlap motifs.

【 授权许可】

CC BY   
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