Novel intercalation host system based on transition metal (Fe{sup 2+}, Co{sup 2+}, Mn{sup 2+})-chloranilate coordination polymers. Single crystal structures and properties
- Shizuoka Univ. (Japan). Dept. of Chemistry
- Kyoto Univ., Yoshida, Sakyo (Japan)
- Tokyo Metropolitan Univ., Hachioji (Japan). Dept. of Chemistry
The new iron(II), cobalt(II), and manganese(II) intercalation compounds {l_brace}[M(CA)(H{sub 2}O){sub 2}](G){r_brace}{sub n} (M = Fe{sup 2+}, Co{sup 2+}, Mn{sup 2+}; H{sub 2}CA = chloranilic acid (C{sub 6}H{sub 2}O{sub 4}Cl{sub 2}); G = H{sub 2}O and phenazine (C{sub 12}H{sub 8}N{sub 2}; phz)) have been synthesized and characterized. {l_brace}[Fe(CA)(H{sub 2}O){sub 2}](H{sub 2}O){r_brace}{sub n} (1a) crystallizes in the monoclinic space group C2/c (No. 15) with a = 4.914(2) {angstrom}, b = 14.222(2) {angstrom}, c = 13.987(2) {angstrom}, {beta} = 94.98(2){degree}, V = 973.8(4) {angstrom}{sup 3}, and Z = 4. {l_brace}[Fe(CA)(H{sub 2}O){sub 2}](phz){r_brace}{sub n} (2a) crystallizes in the triclinic space group P{bar 1} (No. 2) with a = 8.079(2) {angstrom}, b = 11.366(3) {angstrom}, c = 5.055(2) {angstrom}, {alpha} = 96.57(3){degree}, {beta} = 98.70(3){degree}, {gamma} = 83.07(2){degree}, V = 453.3(3) {angstrom}{sup 3}, and Z = 1. {l_brace}[M(CA)(H{sub 2}O){sub 2}](H{sub 2}O){r_brace}{sub n} (M = Co{sup 2+} (1b), Mn{sup 2+} (1c)) are isomorphous to 1a. For 1a--c, crystal structures consist of uncoordinated guest water molecules and one-dimensional zigzag [M(CA)(H{sub 2}O){sub 2}]{sub k} chains. The crystal structures of 2a--c consist of uncoordinated phenazine molecules and straight [M(CA)(H{sub 2}O){sub 2}]{sub k} chains (type II). The {sup 57}Fe Moessbauer spectra of 1a and 2a consist of a single quadrupole doublet with IS = 1.16 mm/s (1a), 1.16 mm/s (2a) and QS = 2.53 mm/s (1a), 1.46 mm/s (2a) at 298 K, indicating that the oxidation state of the iron in both complexes is two. The magnetic susceptibilities were measured from 2 to 300 K and analyzed by a one-dimensional Heisenberg-exchange model to yield J = {minus}0.74 cm{sup {minus}1}, g = 2.01, {rho} = 1.4% (1c) and J = {minus}0.65 cm{sup {minus}1}, g = 2.02, {rho} = 9.0% (2c).
- OSTI ID:
- 328232
- Journal Information:
- Chemistry of Materials, Vol. 10, Issue 12; Other Information: PBD: Dec 1998
- Country of Publication:
- United States
- Language:
- English
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