TY - JOUR
T1 - Encapsulation of [Mn(bpy)3]2+ cations in 2D [Mn(dca)3]- sheet
T2 - Synthesis, X-ray structure and EPR study
AU - Mal, Dasarath
AU - Koner, Subratanath
AU - Tuchagues, Jean Pierre
AU - Rosair, Georgina M.
PY - 2007/8/1
Y1 - 2007/8/1
N2 - The reaction of Mn(NO3)2 · 4H2O, 2,2'-bipyridine (bpy) and sodium dicyanamide (dca) in aqueous medium yielded the {[Mn(bpy)3][Mn(dca)3]2}n (1). The single-crystal X-ray analysis of 1 revealed that the anionic part of the complex, [Mn(dca)3]-, features infinite 2D sheets with a honeycomb-like porous structure having a void space of ca. 12 Å in which [Mn(bpy)3]2+ cations are encapsulated to yield a fascinating molecular assembly. MnII ions possess an octahedral geometry both in the anionic and cationic components of complex 1. In the anionic component, each MnII ion is bridged by three pairs of dicyanamide anions in an end-to-end fashion with two other MnII ions from adjacent [Mn(dca)3]- moieties. This type of linking propagates parallel to the bc crystallographic plane to form 2D sheets. [Mn(bpy)3]2+ is found to have somewhat "squeezed" upon encapsulation. No measurable magnetic interaction was evidenced through variable temperature magnetic susceptibility measurements. However, in addition to the broad g ˜ 2 resonance typical of magnetically diluted [Mn(bpy)3]2+ cations, EPR spectroscopy evidenced exchange narrowing of the [Mn(dca)3]- resonance at g ˜ 2 thus indicating operation of weak magnetic interactions extended over the whole 2D network through the dca- bridges. © 2007 Elsevier B.V. All rights reserved.
AB - The reaction of Mn(NO3)2 · 4H2O, 2,2'-bipyridine (bpy) and sodium dicyanamide (dca) in aqueous medium yielded the {[Mn(bpy)3][Mn(dca)3]2}n (1). The single-crystal X-ray analysis of 1 revealed that the anionic part of the complex, [Mn(dca)3]-, features infinite 2D sheets with a honeycomb-like porous structure having a void space of ca. 12 Å in which [Mn(bpy)3]2+ cations are encapsulated to yield a fascinating molecular assembly. MnII ions possess an octahedral geometry both in the anionic and cationic components of complex 1. In the anionic component, each MnII ion is bridged by three pairs of dicyanamide anions in an end-to-end fashion with two other MnII ions from adjacent [Mn(dca)3]- moieties. This type of linking propagates parallel to the bc crystallographic plane to form 2D sheets. [Mn(bpy)3]2+ is found to have somewhat "squeezed" upon encapsulation. No measurable magnetic interaction was evidenced through variable temperature magnetic susceptibility measurements. However, in addition to the broad g ˜ 2 resonance typical of magnetically diluted [Mn(bpy)3]2+ cations, EPR spectroscopy evidenced exchange narrowing of the [Mn(dca)3]- resonance at g ˜ 2 thus indicating operation of weak magnetic interactions extended over the whole 2D network through the dca- bridges. © 2007 Elsevier B.V. All rights reserved.
KW - Crystal structure
KW - EPR spectroscopy
KW - Manganese(II) dca complex
KW - Two-dimensional structure
UR - http://www.scopus.com/inward/record.url?scp=34447101010&partnerID=8YFLogxK
U2 - 10.1016/j.ica.2007.04.040
DO - 10.1016/j.ica.2007.04.040
M3 - Article
SN - 0020-1693
VL - 360
SP - 3575
EP - 3580
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
IS - 11
ER -