Spin-Crossover Anticooperativity Induced by Weak Intermolecular Interactionsстатья
Статья опубликована в высокорейтинговом журнале
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Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 2 декабря 2016 г.
Аннотация:As a rule, rational design of cooperative spin-crossover (SCO) molecular switches is largely based on consideration of sizes and structures of individual building blocks, whereas a meticulous analysis of crystal packing, including the weakest intermolecular interactions, is often assumed to play a secondary role or is even fully neglected. By investigating cobalt(11) clathrochelates, which do not change the molecular volume upon SCO, we showed that even weak (1.2 kcal/mol) pi center dot center dot center dot Cl intermolecular interactions can cause a pronounced anticooperativity of SCO, being more gradual in the solid state than in solution. Our results clearly demonstrate that the "chemical pressure" concept is not as general as it is thought to be, and the successful design of molecular switches requires in-depth analysis of intermolecular interactions, however weak they seem.