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Polyfunctional inorganic-organic hybrid materials: An unusual kind of NLO active layered mixed metal oxalates with tunable magnetic properties and very large second harmonic generation

GALLI, SIMONA;
2007-01-01
2007
17616190
WOS:000248281100042
2-s2.0-34547659842
Mixed M(II)/M(III) metal oxalates, as "stripes" connected through strong hydrogen bonding by para-dimethylaminobenzaldeide (DAMBA) and water, form an organic-inorganic 2D network that enables segregation in layers of the cationic organic NLO-phore trans-4-(4-dimethylaminostyryl)-1-methylpyridinium, [DAMS+]. The crystalline hybrid materials obtained have the general formula [DAMS]4[M2M'(C2O4)6]*2DAMBA*2H2O (M = Rh, Fe, Cr; M' = Mn, Zn), and their overall three-dimensional packing is non-centrosymmetric and polar, therefore suitable for second harmonic generation (SHG). All the compounds investigated are characterized by an exceptional SHG activity, due both to the large molecular quadratic hyperpolarizability of [DAMS+] and to the efficiency of the crystalline network which organizes [DAMS+] into head-to-tail arranged J-type aggregates. The tunability of the pairs of metal ions allows exploiting also the magnetic functionality of the materials. Examples containing antiferro-, ferro-, and ferri-magnetic interactions (mediated by oxalato bridges) are obtained by coupling proper M(III) ions (Fe, Cr, Rh) with M(II) (Mn, Zn). This shed light on the role of weak next-nearest-neighbor interactions and main nearest-neighbor couplings along "stripes" of mixed M(II)/M(III) metal oxalates of the organic-inorganic 2D network, thus suggesting that these hybrid materials may display isotropic 1D magnetic properties along the mixed M(II)/M(III) metal oxalates "stripes".
Cariati, Elena; Macchi, Roberto; Roberto, Dominique; Ugo, Renato; Galli, Simona; Casati, Nicola; Macchi, Piero; Sironi, Angelo; Bogani, Lapo; Caneschi, Andrea; Gatteschi, Dante
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11383/1671298
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