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Functional Heterometallic Layered Hybrid Magnets by Double Ion‐Exchange
Author(s) -
Delahaye Emilie,
EyeleMezui Séraphin,
Diop Mayoro,
Leuvrey Cédric,
Foix Dominique,
Gonbeau Danielle,
Rabu Pierre,
Rogez Guillaume
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201101220
Subject(s) - chemistry , cobalt , hydroxide , copper , cobalt hydroxide , ion exchange , inorganic chemistry , layered double hydroxides , ion , nuclear chemistry , organic chemistry , electrochemistry , electrode
New hybrid compounds have been synthesized by functionalization of cobalt and copper layered hydroxides by salen complexes. Two kinds of compounds have been obtained from [M(SalenSO 3 Na 2 )] (M = Cu 2+ , Ni 2+ , Co 2+ and Zn 2+ ) and the preintercalated copper and cobalt hydroxides Cu 2 (OH) 3 (DS) and Co 2 (OH) 3 (DS 0 ) [SalenSO 3 Na 2 = N , N′ ‐bis(5‐sulfonatosalicylidene)‐1,2‐diaminoethane disodium salt, DS – = dodecylsulfate, DS 0 – = dodecylsulfonate]. The reaction of [M(SalenSO 3 Na 2 )] with layered copper hydroxide led to the anion‐exchanged compounds Cu 2 (OH) 3.00 (CuSalenSO 3 ) 0.50 · 0.20H 2 O [Cu(SalenSO 3 )⊂Cu ( 1 )] and Cu 2 (OH) 3.24 (NiSalenSO 3 ) 0.38 · 2.6H 2 O [Ni(SalenSO 3 )⊂Cu ( 2 )] where M = Cu 2+ or Ni 2+ . Similarly, the reaction with layered cobalt hydroxide leads to the exchanged compounds Co 2 (OH) 3.18 (NiSalenSO 3 ) 0.41 · 4.0H 2 O [Ni(SalenSO 3 )⊂Co ( 6 )] and Co 2 (OH) 3.44 (CoSalenSO 3 ) 0.28 · 3.7H 2 O [Co(SalenSO 3 )⊂Co ( 8 )] where M = Ni 2+ or Co 2+ . The reaction of [M(SalenSO 3 )Na 2 ] with layered copper hydroxide where M = Co 2+ or Zn 2+ and that of layered cobalt hydroxide where M = Cu 2+ or Zn 2+ resulted in the modification of the host structure because of concomitant partial cation exchange between the salen complex and the inorganic layers. Mixed‐ion‐exchanged compounds were obtained, Cu 1.16 Co 0.84 (OH) 3.28 (CoSalenSO 3 ) 0.36 · 6.4H 2 O [Co(SalenSO 3 )⊂Cu/Co ( 4 )], Cu 0.7 Zn 1.30 (OH) 3.20 (ZnSalenSO 3 ) 0.40 · 2.11H 2 O [Zn(SalenSO 3 )⊂Cu/Zn ( 3 )], Co 1.72 Cu 0.28 (OH) 3.28 (CuSalenSO 3 ) 0.36 · 3.20H 2 O [Cu(SalenSO 3 )⊂Co/Cu ( 5 )] and Co 0.80 Zn 1.20 (OH) 3.20 (ZnSalenSO) 0.40 · 2.25H 2 O [Zn(SalenSO 3 )⊂Co/Zn ( 7 )]. The magnetic behaviour of the compounds is drastically modified depending on the structure of the inorganic layers induced by the functionalization and partial cation exchange. The hybrid copper layered hydroxides show antiferromagnetic (for 3 ) or weak ferromagnetic (for 1 , 2 and 4 ) behaviour. The cobalt analogues 5 , 6 and 8 are ferrimagnets with ordering temperatures at ca. 6 K, whereas the Co/Zn heterometallic layered simple hydroxide 7 presents dominant antiferromagnetic interactions.