TY - JOUR
T1 - Cobalt Clusters with Cubane-Type Topologies Based on Trivacant Polyoxometalate Ligands
AU - Duan, Yan
AU - Clemente-Juan, Juan M.
AU - Giménez-Saiz, Carlos
AU - Coronado, Eugenio
N1 - Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/1/19
Y1 - 2016/1/19
N2 - Four novel cobalt-substituted polyoxometalates having cobalt cores exhibiting cubane or dicubane topologies have been synthesized and characterized by IR, elemental analysis, electrochemistry, UV-vis spectroscopy, X-ray single-crystal analysis, and magnetic studies. The tetracobalt(II)-substituted polyoxometalate [Co4(OH)3(H2O)6(PW9O34)]4- (1) consists of a trilacunary [B-α-PW9O34]9- unit which accommodates a cubane-like {CoII4O4} core. In the heptacobalt(II,III)-containing polyoxometalates [Co7(OH)6(H2O)6(PW9O34)2]9- (2), [Co7(OH)6(H2O)4(PW9O34)2]n9n- (3), and [Co7(OH)6(H2O)6(P2W15O56)2]15- (4), dicubane-like {CoII6CoIIIO8} cores are encapsulated between two heptadentate [B-α-PW9O34]9- (in 2 and 3) or [α-P2W15O56]15- (in 4) ligands. While 1, 2, and 4 are discrete polyoxometalates, 3 exhibits a polymeric, chain-like structure that results from the condensation of polyoxoanions of type 2. The magnetic properties of these complexes have been fitted according to an anisotropic exchange model in the low-temperature regime and discussed on the basis of ferromagnetic interactions between Co2+ ions with angles Co-L-Co (L = O, OH) close to orthogonality and weakly antiferromagnetic interactions between Co2+ ions connected through central diamagnetic Co3+ ion. Moreover, we will show the interest of the unique spin structures provided by these cubane and dicubane cobalt topologies in molecular spintronics (molecular spins addressed though an electric field) and quantum computing (spin qu-gates).
AB - Four novel cobalt-substituted polyoxometalates having cobalt cores exhibiting cubane or dicubane topologies have been synthesized and characterized by IR, elemental analysis, electrochemistry, UV-vis spectroscopy, X-ray single-crystal analysis, and magnetic studies. The tetracobalt(II)-substituted polyoxometalate [Co4(OH)3(H2O)6(PW9O34)]4- (1) consists of a trilacunary [B-α-PW9O34]9- unit which accommodates a cubane-like {CoII4O4} core. In the heptacobalt(II,III)-containing polyoxometalates [Co7(OH)6(H2O)6(PW9O34)2]9- (2), [Co7(OH)6(H2O)4(PW9O34)2]n9n- (3), and [Co7(OH)6(H2O)6(P2W15O56)2]15- (4), dicubane-like {CoII6CoIIIO8} cores are encapsulated between two heptadentate [B-α-PW9O34]9- (in 2 and 3) or [α-P2W15O56]15- (in 4) ligands. While 1, 2, and 4 are discrete polyoxometalates, 3 exhibits a polymeric, chain-like structure that results from the condensation of polyoxoanions of type 2. The magnetic properties of these complexes have been fitted according to an anisotropic exchange model in the low-temperature regime and discussed on the basis of ferromagnetic interactions between Co2+ ions with angles Co-L-Co (L = O, OH) close to orthogonality and weakly antiferromagnetic interactions between Co2+ ions connected through central diamagnetic Co3+ ion. Moreover, we will show the interest of the unique spin structures provided by these cubane and dicubane cobalt topologies in molecular spintronics (molecular spins addressed though an electric field) and quantum computing (spin qu-gates).
UR - http://www.scopus.com/inward/record.url?scp=84955516388&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.5b02532
DO - 10.1021/acs.inorgchem.5b02532
M3 - Article
AN - SCOPUS:84955516388
SN - 0020-1669
VL - 55
SP - 925
EP - 938
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 2
ER -