Novel Intercalation Host System Based on Transition Metal (Fe2+, Co2+, Mn2+)-Chloranilate Coordination Polymers. Single Crystal Structures and Properties
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- 作者：Satoshi Kawata ; Susumu Kitagawa ; Hitoshi Kumagai ; Tetsuya Ishiyama ; Kenji Honda ; Hiroshi Tobita ; Keiichi Adachi ; and Motomi Katada
- 刊名：Chemistry of Materials
- 出版年：1998
- 出版时间：December 1998
- 年：1998
- 卷：10
- 期：12
- 页码：3902 - 3912
- 全文大小：168K
- 年卷期：v.10,no.12(December 1998)
- ISSN：1520-5002
文摘
The new iron(II), cobalt(II), and manganese(II) intercalation compounds {[M(CA)(H2O)2](G)}n (M = Fe2+, Co2+, Mn2+; H2CA = chloranilic acid (C6H2O4Cl2); G = H2O and phenazine(C12H8N2; phz)) have been synthesized and characterized. {[Fe(CA)(H2O)2](H2O)}n (1a)crystallizes in the monoclinic space group C2/c (No. 15) with a = 4.914(2) Å, b = 14.222(2)Å, c = 13.987(2) Å, 
= 94.98(2)
, V = 973.8(4) Å3, and Z = 4. {[Fe(CA)(H2O)2](phz)}n (2a)crystallizes in the triclinic space group P
(No. 2) with a = 8.079(2) Å, b = 11.366(3) Å, c =5.055(2) Å, 
= 96.57(3), = 98.70(3), 
= 83.07(2), V = 453.3(3) Å3, and Z = 1. {[M(CA)(H2O)2](H2O)}n (M = Co2+ (1b), Mn2+ (1c)) are isomorphous to 1a. For 1a-c, crystalstructures consist of uncoordinated guest water molecules and one-dimensional zigzag[M(CA)(H2O)2]k chains. Two water molecules occupying cis positions and two chloranilatefilling the remaining sites in a bis bidentate fashion create the octahedral environmentaround the metal ion to form a zigzag chain (type I), which extends along the diagonalbetween the a and c axes. The adjacent chains are interlinked by hydrogen bonds, thusforming layers, which spread out along the ac plane. Water molecules are intercalatedbetween the {[M(CA)(H2O)2]k}l layers. The intercalation mode of the water molecules isdifferent from those in {[M(CA)(H2O)2](phz)}n (M = Fe2+ (2a), Co2+ (2b), Mn2+ (2c)), whichare isomorphous each other. The crystal structures of 2a-c consist of uncoordinatedphenazine molecules and straight [M(CA)(H2O)2]k chains (type II). Infinite, nearly coplanarlinear chains are formed by metal ions and the bis-chelating CA2- anions, which extendalong the a direction, and are linked by hydrogen bonds between the coordinated water andthe oxygen atoms of the CA2- on the adjacent chains, forming a two-dimensional sheet, whichspreads out along the ac plane. The intercalated phenazines are stacked along the c axisperpendicular to the [M(CA)(H2O)2]k chain, and the planes of the phenazine molecules aretilted to the stacking direction, forming a segregated columnar structure between the{[M(CA)(H2O)2]k}l layers. The 57Fe Mössbauer spectra of 1a and 2a consist of a singlequadrupole 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 istwo. The magnetic susceptibilities were measured from 2 to 300 K and analyzed by a one-dimensional Heisenberg-exchange model to yield J = -0.74 cm-1, g = 2.01, 
= 1.4% (1c)and J = -0.65 cm-1, g = 2.02, = 9.0% (2c).
= 94.98(2), V = 973.8(4) Å3, and Z = 4. {[Fe(CA)(H2O)2](phz)}n (2a)crystallizes in the triclinic space group P (No. 2) with a = 8.079(2) Å, b = 11.366(3) Å, c =5.055(2) Å, = 96.57(3), = 98.70(3), = 83.07(2), V = 453.3(3) Å3, and Z = 1. {[M(CA)(H2O)2](H2O)}n (M = Co2+ (1b), Mn2+ (1c)) are isomorphous to 1a. For 1a-c, crystalstructures consist of uncoordinated guest water molecules and one-dimensional zigzag[M(CA)(H2O)2]k chains. Two water molecules occupying cis positions and two chloranilatefilling the remaining sites in a bis bidentate fashion create the octahedral environmentaround the metal ion to form a zigzag chain (type I), which extends along the diagonalbetween the a and c axes. The adjacent chains are interlinked by hydrogen bonds, thusforming layers, which spread out along the ac plane. Water molecules are intercalatedbetween the {[M(CA)(H2O)2]k}l layers. The intercalation mode of the water molecules isdifferent from those in {[M(CA)(H2O)2](phz)}n (M = Fe2+ (2a), Co2+ (2b), Mn2+ (2c)), whichare isomorphous each other. The crystal structures of 2a-c consist of uncoordinatedphenazine molecules and straight [M(CA)(H2O)2]k chains (type II). Infinite, nearly coplanarlinear chains are formed by metal ions and the bis-chelating CA2- anions, which extendalong the a direction, and are linked by hydrogen bonds between the coordinated water andthe oxygen atoms of the CA2- on the adjacent chains, forming a two-dimensional sheet, whichspreads out along the ac plane. The intercalated phenazines are stacked along the c axisperpendicular to the [M(CA)(H2O)2]k chain, and the planes of the phenazine molecules aretilted to the stacking direction, forming a segregated columnar structure between the{[M(CA)(H2O)2]k}l layers. The 57Fe Mössbauer spectra of 1a and 2a consist of a singlequadrupole 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 istwo. The magnetic susceptibilities were measured from 2 to 300 K and analyzed by a one-dimensional Heisenberg-exchange model to yield J = -0.74 cm-1, g = 2.01, = 1.4% (1c)and J = -0.65 cm-1, g = 2.02, = 9.0% (2c).