A solvothermal synthetic procedure has been exploited to prepare the new [Cu3L(NO3)6]n coordination polymer (1) by reaction of the polydentate N,N′-{2,4-di-[(di-pyridin-2-yl)amine]- 1,3,5-triazine}ethylenediamine ligand (opytrizediam L) with copper(II) nitrate. 1 has been structurally characterized by means of the conventional X-ray single-crystal diffraction technique. It crystallizes in the monoclinic C2/c space group with a = 16.830(3), b = 20.701(4), c = 18.170(4) Å, β = 113.26(3)°, V = 5816(2) Å^3, Z = 4. 1 consists of trinuclear Cu3L(NO3)5 units connected by means of a nitrato-O,O′ bridge. The resulting chains are involved in weak interchain head-to-tail π-π stacking interactions. In the presence of moisture, 1 is readily converted into the hydrated [Cu3L(NO3) 5](NO3)·H2O form (2). This second phase, monoclinic P21/c, consists of isolated [Cu3L(NO3)5]+ and (NO3)- ions which accommodate water molecules in the crystal lattice. These subtle chemical and structural modifications accompanying the moisture-triggered 1-to-2 transformation have been demonstrated through an X-ray powder diffraction study. A thermodiffractometric analysis has evidenced that this solid-to-solid transformation is fully reversible, i.e., thermally induced dehydration of 2 restores 1. The analysis of the temperature dependence of the magnetic susceptibility for 2 has revealed very weak ferromagnetic interactions, consistent with the large Cu⋯Cu separation (ca. 7.5 Å) in the trinuclear units.

Moisture-triggered 1,3,5-triazine-based Cu(II) molecular switch: a combined X-ray single-crystal and powder diffraction study

MASCIOCCHI, NORBERTO;GALLI, SIMONA;
2005

Abstract

A solvothermal synthetic procedure has been exploited to prepare the new [Cu3L(NO3)6]n coordination polymer (1) by reaction of the polydentate N,N′-{2,4-di-[(di-pyridin-2-yl)amine]- 1,3,5-triazine}ethylenediamine ligand (opytrizediam L) with copper(II) nitrate. 1 has been structurally characterized by means of the conventional X-ray single-crystal diffraction technique. It crystallizes in the monoclinic C2/c space group with a = 16.830(3), b = 20.701(4), c = 18.170(4) Å, β = 113.26(3)°, V = 5816(2) Å^3, Z = 4. 1 consists of trinuclear Cu3L(NO3)5 units connected by means of a nitrato-O,O′ bridge. The resulting chains are involved in weak interchain head-to-tail π-π stacking interactions. In the presence of moisture, 1 is readily converted into the hydrated [Cu3L(NO3) 5](NO3)·H2O form (2). This second phase, monoclinic P21/c, consists of isolated [Cu3L(NO3)5]+ and (NO3)- ions which accommodate water molecules in the crystal lattice. These subtle chemical and structural modifications accompanying the moisture-triggered 1-to-2 transformation have been demonstrated through an X-ray powder diffraction study. A thermodiffractometric analysis has evidenced that this solid-to-solid transformation is fully reversible, i.e., thermally induced dehydration of 2 restores 1. The analysis of the temperature dependence of the magnetic susceptibility for 2 has revealed very weak ferromagnetic interactions, consistent with the large Cu⋯Cu separation (ca. 7.5 Å) in the trinuclear units.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11383/1495149
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