Thermal spin-crossover in the [M(3)Zn(6)Cl(6)L(12)] (M = Zn, Fe(II); L = 5,6-dimethoxy-1,2,3-benzotriazolate) system: structural, electrochemical, Mössbauer, and UV-Vis spectroscopic studies.
Fusion of pentanuclear Kuratowski-type coordination units leads to homo- and heterononanuclear coordination compounds, two of which are presented, having structural formulae [Zn(9)Cl(6)(OMe(2)bta)(12)]·DMF (1), and [Fe(II)(3)Zn(6)Cl(6)(OMe(2)bta)(12)]·DMF (2), respectively; (OMe(2)btaH = 5,6-dimethoxy-1,2,3-benzotriazole; DMF = N,N'-dimethylformamide). Single crystal X-ray structure analyses reveal the presence of {M(3)Zn(6)L(12)}(6+) cores (M = Zn or Fe(II); L = 5,6-dimethoxy-1,2,3-benzotriazolate) in which the M(II) ions are bridged by μ(3)-OMe(2)bta ligands. In both compounds, the six peripheral Zn ions are tetracoordinated, whereas the remaining three metal ions M are hexacoordinated. The charge of each {M(3)Zn(6)L(12)}(6+) moiety is balanced by six chloride anions that are monodentately bound to the peripheral Zn ions. Based on differences in experimental Fe-N-donor bond lengths (deduced from single crystal data of 2 recorded at 223 K), two out of three Fe(II) ions are found in a high-spin (HS) state, whereas one Fe(II) ion shows a low-spin (LS) state. The assignment of different energetic ground states of Fe(II) ions is corroborated by spectroscopic studies: Both solid-state and solution UV-Vis spectra of 2 (at ambient temperature) display absorption bands owing to the presence of both HS and LS Fe(II) ions. Removal of occluded DMF molecules from the crystal lattices of 1 and 2 in high vacuum leads to fully desolvated powders, termed hereafter 1a and 2a, respectively. Mössbauer studies on 2a show that all three Fe(II) ions are in HS state at 160 K, and upon cooling to 7 K, the central Fe(II) ion undergoes a HS→LS transition while the HS states of the other Fe(II) ions remains unchanged. The cyclic voltammogram of 2 (chloroform solution) exhibits a single reversible oxidation regardless of different Fe(II) spin states in the nonanuclear core of 2.
Biswas
Shyam
S
Ulm University, Institute of Inorganic Chemistry II, Materials and Catalysis, Albert-Einstein-Allee 11, D-89081, Ulm, Germany.
Tonigold
Markus
M
Kelm
Harald
H
Krüger
Hans-Jörg
HJ
Volkmer
Dirk
D