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A cyanide‐bridged Fe III –Mn II heterobimetallic one‐dimensional coordination polymer: synthesis, crystal structure, experimental and theoretical magnetism investigation
Author(s) -
Lan Wenlong,
Zhou Zhen,
Li Jie,
Dou Yong,
Hao Xiaoyun,
Yang Lu,
Liu Hui,
Li Dacheng,
Liu Qingyun,
Zhang Daopeng
Publication year - 2019
Publication title -
acta crystallographica section c
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.304
H-Index - 17
ISSN - 2053-2296
DOI - 10.1107/s2053229619013172
Subject(s) - crystallography , crystal structure , chemistry , antiferromagnetism , supramolecular chemistry , pyridine , cyanide , perchlorate , magnetic susceptibility , magnetism , coordination polymer , single crystal , bipyridine , cationic polymerization , ion , inorganic chemistry , polymer chemistry , medicinal chemistry , physics , organic chemistry , quantum mechanics , condensed matter physics
A new cyanide‐bridged Fe III –Mn II heterobimetallic coordination polymer (CP), namely catena ‐poly[[[ N , N ′‐(1,2‐phenylene)bis(pyridine‐2‐carboxamidato)‐κ 4 N , N ′, N ′′, N ′′′]iron(III)]‐μ‐cyanido‐κ 2 C : N ‐[bis(4,4′‐bipyridine‐κ N )bis(methanol‐κ O )manganese(II)]‐μ‐cyanido‐κ 2 N : C ], {[FeMn(C 18 H 12 N 4 O 2 )(CN) 2 (C 10 H 8 N 2 ) 2 (CH 3 OH) 2 ]ClO 4 } n , ( 1 ), was prepared by the self‐assembly of the trans ‐dicyanidoiron(III)‐containing building block [Fe(bpb)(CN) 2 ] − [bpb 2− = N , N ′‐(1,2‐phenylene)bis(pyridine‐2‐carboxamidate)], [Mn(ClO 4 ) 2 ]·6H 2 O and 4,4′‐bipyridine, and was structurally characterized by elemental analysis, IR spectroscopy, single‐crystal X‐ray crystallography and powder X‐ray diffraction (PXRD). Single‐crystal X‐ray diffraction analysis shows that CP 1 possesses a cationic linear chain structure consisting of alternating cyanide‐bridged Fe–Mn units, with free perchlorate as the charge‐balancing anion, which can be further extended into a two‐dimensional supramolecular sheet structure via inter‐chain π–π interactions between the 4,4′‐bipyridine ligands. Within the chain, each Mn II ion is six‐coordinated by an N 6 unit and is involved in a slightly distorted octahedral coordination geometry. Investigation of the magnetic properties of 1 reveals an antiferromagnetic coupling between the cyanide‐bridged Fe III and Mn II ions. A best fit of the magnetic susceptibility based on the one‐dimensional alternating chain model leads to the magnetic coupling constants J 1 = −1.35 and J 2 = −1.05 cm −1 , and the antiferromagnetic coupling was further confirmed by spin Hamiltonian‐based density functional theoretical (DFT) calculations.