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Readily Prepared Metallo‐Supramolecular Triple Helicates Designed to Exhibit Spin‐Crossover Behaviour
Author(s) -
Tuna Floriana,
Lees Martin R.,
Clarkson Guy J.,
Han Michael J.
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200400518
Subject(s) - spin crossover , supramolecular chemistry , hexafluorophosphate , hydrogen bond , chemistry , perchlorate , tetrafluoroborate , materials science , crystallography , ionic liquid , molecule , chemical physics , ion , crystal structure , organic chemistry , catalysis
New dinuclear supramolecular cylinders have been designed to exhibit spin‐crossover behaviour, a form of molecular bistability. This has been achieved within the framework of our imine‐based approach to supramolecular architecture by switching from pyridylimine systems to imidazolimines. Spin‐crossover behaviour is achieved while retaining the simplicity and ease‐of‐synthesis of our molecular design. The imidazole groups used also introduce additional NH groups that engage in hydrogen‐bonding to anions and solvents. In the case of the iron( II ) tetrafluoroborate complex this hydrogen bonding links supramolecular cylinders into an extended two‐dimensional array. Consistent with this, a sharper spin‐crossover transition is observed for this compound than for the corresponding hexafluorophosphate salt. More subtle anion effects are indicated in the perchlorate salt which gives a two‐step spin conversion, thereby displaying tristability.