Abstract
New crystal structure of Eu(DMF)4(H2O) 3Co(CN)6•H2O (DMF = N,N′- dimethylformamide) (Eu-Co) has been determined to be monoclinic, P2(1)/n, a = 19.796(12) Å, b = 8.862(11) Å, c = 17.525(10) Å, β = 96.26(5)°, V = 3056(5) Å3, Z = 4. The Eu(III) ion adopts an antiprismatic eight-coordination and forms a cyano bridge with r(Eu-N) = 2.496(7) Å and Θ(Eu-N-C) = 165.7(7)° to the Co(III) ion. The complex exhibits some common features with the Eu-Fe complex. Diffuse reflectance electronic spectra and magnetic susceptibility of Eu-Cr, Eu-Mn, Eu-Fe, and Eu-Co complexes were compared. By substituting the metal ions, both electronic and structural features affected the charge transfer bands and superexchange interactions concerning cyanide ligands. In addition, only Eu-Co exhibited 5 D 0 → 7 F 2 and 5 D 0 → 7 F 1 luminescence bands at 16300 cm-1 and 16900 cm-1, respectively at 298 K (λex = 360 nm (27000 cm-1)), because quenching by cyano-bridged ions did not prevent Eu(III) ion from exhibiting emission. Thus, only Eu-Co may be suitable for verification of an assumption of mechanism concerning drastic photoinduced magnetic changes for Nd-Fe. Merely small decrease of magnetization was observed for Eu-Co after UV light irradiation at 2.0 K. This result was attributed to slight structural changes around cyano bridges without transitions of spin states.
| Original language | English |
|---|---|
| Pages (from-to) | 194-198 |
| Number of pages | 5 |
| Journal | Chemical Papers |
| Volume | 61 |
| Issue number | 3 |
| DOIs | |
| Publication status | Published - 2007 Jun |
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Keywords
- Cobalt(III)
- Crystal structure
- Europium(III)
- Magnetism
- Spectroscopy
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Structure of cyano-bridged Eu(III)-Co(III) bimetallic assembly and its application to photophysical verification of photomagnetic phenomenon. / Akitsu, T.; Einaga, Yasuaki.
In: Chemical Papers, Vol. 61, No. 3, 06.2007, p. 194-198.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Structure of cyano-bridged Eu(III)-Co(III) bimetallic assembly and its application to photophysical verification of photomagnetic phenomenon
AU - Akitsu, T.
AU - Einaga, Yasuaki
PY - 2007/6
Y1 - 2007/6
N2 - New crystal structure of Eu(DMF)4(H2O) 3Co(CN)6•H2O (DMF = N,N′- dimethylformamide) (Eu-Co) has been determined to be monoclinic, P2(1)/n, a = 19.796(12) Å, b = 8.862(11) Å, c = 17.525(10) Å, β = 96.26(5)°, V = 3056(5) Å3, Z = 4. The Eu(III) ion adopts an antiprismatic eight-coordination and forms a cyano bridge with r(Eu-N) = 2.496(7) Å and Θ(Eu-N-C) = 165.7(7)° to the Co(III) ion. The complex exhibits some common features with the Eu-Fe complex. Diffuse reflectance electronic spectra and magnetic susceptibility of Eu-Cr, Eu-Mn, Eu-Fe, and Eu-Co complexes were compared. By substituting the metal ions, both electronic and structural features affected the charge transfer bands and superexchange interactions concerning cyanide ligands. In addition, only Eu-Co exhibited 5 D 0 → 7 F 2 and 5 D 0 → 7 F 1 luminescence bands at 16300 cm-1 and 16900 cm-1, respectively at 298 K (λex = 360 nm (27000 cm-1)), because quenching by cyano-bridged ions did not prevent Eu(III) ion from exhibiting emission. Thus, only Eu-Co may be suitable for verification of an assumption of mechanism concerning drastic photoinduced magnetic changes for Nd-Fe. Merely small decrease of magnetization was observed for Eu-Co after UV light irradiation at 2.0 K. This result was attributed to slight structural changes around cyano bridges without transitions of spin states.
AB - New crystal structure of Eu(DMF)4(H2O) 3Co(CN)6•H2O (DMF = N,N′- dimethylformamide) (Eu-Co) has been determined to be monoclinic, P2(1)/n, a = 19.796(12) Å, b = 8.862(11) Å, c = 17.525(10) Å, β = 96.26(5)°, V = 3056(5) Å3, Z = 4. The Eu(III) ion adopts an antiprismatic eight-coordination and forms a cyano bridge with r(Eu-N) = 2.496(7) Å and Θ(Eu-N-C) = 165.7(7)° to the Co(III) ion. The complex exhibits some common features with the Eu-Fe complex. Diffuse reflectance electronic spectra and magnetic susceptibility of Eu-Cr, Eu-Mn, Eu-Fe, and Eu-Co complexes were compared. By substituting the metal ions, both electronic and structural features affected the charge transfer bands and superexchange interactions concerning cyanide ligands. In addition, only Eu-Co exhibited 5 D 0 → 7 F 2 and 5 D 0 → 7 F 1 luminescence bands at 16300 cm-1 and 16900 cm-1, respectively at 298 K (λex = 360 nm (27000 cm-1)), because quenching by cyano-bridged ions did not prevent Eu(III) ion from exhibiting emission. Thus, only Eu-Co may be suitable for verification of an assumption of mechanism concerning drastic photoinduced magnetic changes for Nd-Fe. Merely small decrease of magnetization was observed for Eu-Co after UV light irradiation at 2.0 K. This result was attributed to slight structural changes around cyano bridges without transitions of spin states.
KW - Cobalt(III)
KW - Crystal structure
KW - Europium(III)
KW - Magnetism
KW - Spectroscopy
UR - http://www.scopus.com/inward/record.url?scp=34248398535&partnerID=8YFLogxK
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U2 - 10.2478/s11696-007-0019-2
DO - 10.2478/s11696-007-0019-2
M3 - Article
VL - 61
SP - 194
EP - 198
JO - Chemical Papers
JF - Chemical Papers
SN - 0366-6352
IS - 3
ER -