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Iron(II) Metallomesogens Exhibiting Coupled Spin State and Liquid Crystal Phase Transitions near Room Temperature
Author(s) -
Seredyuk Maksym,
Gaspar Ana B.,
Ksenofontov Vadim,
Galyametdinov Yury,
Kusz Joachim,
Gütlich Philipp
Publication year - 2008
Publication title -
advanced functional materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 6.069
H-Index - 322
eISSN - 1616-3028
pISSN - 1616-301X
DOI - 10.1002/adfm.200800049
Subject(s) - crystallography , triclinic crystal system , spin crossover , ligand (biochemistry) , materials science , spin states , thermotropic crystal , pyridine , octahedron , crystal structure , chemistry , liquid crystal , inorganic chemistry , medicinal chemistry , liquid crystalline , biochemistry , receptor , optoelectronics
Reaction of the ligand 2,2,2‐tris(2‐aza‐3‐((5‐akloxy)(6‐methyl)(2‐pyridyl))prop‐2‐enyl)ethane (C n ‐tameMe) with Fe(X) 2 · sH 2 O salts afforded a series of spin crossover metallomesogens with general formula [Fe(C n ‐tame)](X) 2 · sH 2 O (s ≥ 0), with n = 6, 10, 12, 14, 16, 17, 18, or 20 and X = ClO 4 − or BF 4 − . Single crystal X‐ray measurements have been performed on the [Fe(C 6 ‐tameMe)](ClO 4 ) 2 ( C 6 ‐1 ) derivative at 100 K. The complex C 6 ‐1 crystallizes in the triclinic system and adopts the P bca space group. The iron(II) ion is in a distorted octahedral environment shaped by three imine and three pyridine nitrogen atoms of the C n ‐tameMe ligand. The average Fe–N im and Fe–N py bond distance is 1.918(2) Å and 2.084(2) Å, respectively, which are characteristic for the Fe(II) ion in the LS state. Neighbor molecules are packed in a head‐to‐head fashion forming a layered microsegregated structure. Ionic layer is composed of cationic spin crossover head‐groups and perchlorate anions, whereas alkyl tails are arranged into a non‐polar hydrocarbon layer. The complex [Fe(C 18 ‐tameMe)](ClO 4 ) 2 ( C 18 ‐1 ) and the series [Fe(C n ‐tameMe)](BF 4 ) 2 ( n = 10, 12, 14, 16, 17, 18, 20) ( C n ‐2 ) series show thermally driven spin crossover and mesomorphism above 300 K. The thermotropic behavior of compounds C n ‐2 depends on the chain length defined by n . A common structural feature among all homologues of the series is a similar layered structure and adoption on melting of a smectic mesophase at ca. 350–375 K. Formation of the mesophase is due to the melting of the alkyl chains rather than a rearrangement of the ionic bilayers composed of polar SCO cations and BF 4 − or ClO 4 − anions. This gives rise to a mesophase with molten alkyl chains but with restricted movement through the ionic layer. Compounds C n ‐2 show thermochromic properties, they are dark violet in the LS state ( T < 275 K, Cr) and become red in the HS state ( T > 275 K, Cr, S X ). These bi‐functional materials combine spin state change and mesomorphic behavior in a narrow interval of temperatures, 300–375 K.