In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2010, No. 26 ( 2010-09), p. 4166-4174
Abstract:
We present the magneto–structural correlations for two novel discrete cyano‐bridged assemblies based on cationic complexes of manganese(II) with diimine ligands and octacyanotungstate(V) ions. The crystal structure of [Mn II (terpy)(dmf)(H 2 O) 2 ][Mn II (terpy)(H 2 O)(dmf)(μ‐NC)W V (CN) 7 ] 2 · 6H 2 O ( 1 ) (terpy = 2,2′;6′,2″‐terpyridine, dmf = dimethylformamide) contains dinuclear {Mn II W V } – cyano‐bridged anions, while the crystal structure of [Mn II (phen) 3 ] 2 [Mn II (phen) 2 (μ‐NC) 2 W V (CN) 6 ] 2 (ClO 4 ) 2 · 9H 2 O ( 2 ) (phen = 1,10‐phenanthroline) is built of tetranuclear {Mn II 2 W V 2 } 2– square anions. Intramolecular Mn–W magnetic interactions through the cyano bridges are represented by magnetic coupling constants J = –39 cm –1 for the {Mn II W V } – unit in 1 and J 1 = –25.7 and J 2 = –16.7 cm –1 for the {Mn II 2 W V 2 } 2– unit in 2 . J and J 1 represent relatively strong W–CN–Mn interactions and are ascribed to the bridges in b positions of TPRS‐8 (trigonal prism square‐face bicapped) of [W(CN) 8 ] 3– polyhedra, favoring the strongest electronic interactions between the d –d orbital of W and the π* orbitals of CN – , whereas J 2 is related to the m vertex of [W(CN) 8 ] 3– . The magnetic properties of 1 and 2 are compared with reference compounds and discussed in the context of the type of coordination polyhedra of [W(CN) 8 ] 3– as well as the metric parameters of cyano‐bridged W–CN–Mn linkages. We found the type of coordination polyhedra and bridging mode of [W(CN) 8 ] 3– to be the most important factors influencing the magnitude of the Mn–W magnetic interaction.
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2010:26
DOI:
10.1002/ejic.201000280
Language:
English
Publisher:
Wiley
Publication Date:
2010
detail.hit.zdb_id:
1475009-0
