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".

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 / E. Cariati, R. Macchi, D.M. Roberto, R. Ugo, S. Galli, N.P. Casati, P. Macchi, A.A.D. Sironi, L. Bogani, A. Caneschi, D. Gatteschi. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - 129:30(2007), pp. 9410-9420.

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

E. Cariati
Primo
;
R. Macchi
Secondo
;
D.M. Roberto;R. Ugo;N.P. Casati;P. Macchi;A.A.D. Sironi;
2007

Abstract

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".
Settore CHIM/03 - Chimica Generale e Inorganica
2007
http://pubs.acs.org/cgi-bin/article.cgi/jacsat/2007/129/i30/pdf/ja0710712.pdf
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/40515
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