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Supramolecular structures and columnar mesophase induction in nondiscoid pyrazoles by complexation to rhodium(I)

AuthorsGiménez, Raquel; Elduque, Anabel ; López, José A. ; Barberá, Joaquín; Cavero, Emma; Lantero, Ignacio; Oro, Luis A. ; Serrano, José Luis
Issue Date15-Nov-2006
PublisherAmerican Chemical Society
CitationInorganic Chemistry 45(25): 10363–10370 (2006)
AbstractSeveral new cis-[RhCl(CO)2(Ln)] complexes have been prepared using different polycatenar pyrazole ligands (Ln) in order to obtain columnar liquid crystalline arrangements. The topology of the ligand plays an essential role, and a mesophase is induced at room temperature from a nonmesogenic pyrazole only when it is symmetrically substituted with six decyloxy chains. The single-crystal structure of a methoxy-substituted analogue, 3,5-bis(3,4,5-trimethoxyphenyl)pyrazole, is formed by globular tetrameric structures held together by H-bonding. However, parallel dimers are present in the corresponding cis-chlorodicarbonylrhodium(I) complex, a situation that explains the induction of a columnar mesophase in the decyloxy-substituted complex. The XRD pattern of the mesophase is consistent with a hexagonal symmetry in which the columns are formed by molecules assembled in an antiparallel mode. The crystal-to-mesophase transition was also detected by spectroscopic techniques as a shift in the IR carbonyl stretching bands and the appearance of a charge-transfer band in the absorption spectrum with thermochromic behavior.
Description8 pages, 10 figures, 3 tables.
Publisher version (URL)http://dx.doi.org/10.1021/ic0614216
Appears in Collections:(ICMA) Artículos
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