In order to investigate photophysical properties and crystallization medium effects, three Cu complexes, [CuI(PCy3)]2(1), [Cu(I)(PPh2Me)]4(2), and [Cu4(I)4(PPh2py)2] (3) were prepared and characterized using single crystal X-ray crystallography, solid state NMR, UV–Vis, and IR spectroscopy. In 1, as previously reported, Cu2I2core is a square dimer with alternating copper and iodides positioned in the corners. Each copper atom is surrounded by two bridging iodides and a terminal tricyclohexylphosphine ligand. The cluster 2 adopts a cubane-like Cu4I4core, while in cluster 3 (as thf solvate) a Cu4I2distorted octahedral core is decorated with two bridging iodides and two chelating P^N ligands. The solid state31P NMR analysis showed the presence in the powder of several polymorphs, the most abundant of which being, in the case of 2, the cubane-like structure resolved by XRD methods, and in the case of 3, a butterfly structure, different from that found for 3·thf. The solid state blue photoluminescence intensity in 1 is dependent upon its poly- or single-crystallinity. While dimer 1 in polycrystalline form is a stronger blue light emitter under 254 nm light irradiation than in 365 nm, in single crystalline phase it shows a similar higher intensity blue luminescence under lower energy light (365 nm) irradiation. On the other hand, clusters 2 and 3 do not show phase-dependent luminescence intensity variation. Time-dependent Density Functional Theory (TD-DFT) showed that the emission in 1 and 3 is assigned to a mixed metal to ligand and halide to ligand charge transfer, (X + M)LCT. In 2, a dual emission band at low temperature was observed which was attributed to3CC (LE band) and3XLCT (HE band). Thermochromism and mechanochromism of complexes 1–3 were also investigated.

Dinuclear and tetranuclear copper(I) iodide complexes with P and P^N donor ligands: Structural and photoluminescence studies / Neshat, Abdollah; Aghakhanpour, Reza Babadi; Mastrorilli, Piero; Todisco, Stefano; Molani, Farzad; Wojtczak, Andrzej. - In: POLYHEDRON. - ISSN 0277-5387. - STAMPA. - 154:(2018), pp. 217-228. [10.1016/j.poly.2018.07.045]

Dinuclear and tetranuclear copper(I) iodide complexes with P and P^N donor ligands: Structural and photoluminescence studies

Mastrorilli, Piero;Todisco, Stefano;
2018-01-01

Abstract

In order to investigate photophysical properties and crystallization medium effects, three Cu complexes, [CuI(PCy3)]2(1), [Cu(I)(PPh2Me)]4(2), and [Cu4(I)4(PPh2py)2] (3) were prepared and characterized using single crystal X-ray crystallography, solid state NMR, UV–Vis, and IR spectroscopy. In 1, as previously reported, Cu2I2core is a square dimer with alternating copper and iodides positioned in the corners. Each copper atom is surrounded by two bridging iodides and a terminal tricyclohexylphosphine ligand. The cluster 2 adopts a cubane-like Cu4I4core, while in cluster 3 (as thf solvate) a Cu4I2distorted octahedral core is decorated with two bridging iodides and two chelating P^N ligands. The solid state31P NMR analysis showed the presence in the powder of several polymorphs, the most abundant of which being, in the case of 2, the cubane-like structure resolved by XRD methods, and in the case of 3, a butterfly structure, different from that found for 3·thf. The solid state blue photoluminescence intensity in 1 is dependent upon its poly- or single-crystallinity. While dimer 1 in polycrystalline form is a stronger blue light emitter under 254 nm light irradiation than in 365 nm, in single crystalline phase it shows a similar higher intensity blue luminescence under lower energy light (365 nm) irradiation. On the other hand, clusters 2 and 3 do not show phase-dependent luminescence intensity variation. Time-dependent Density Functional Theory (TD-DFT) showed that the emission in 1 and 3 is assigned to a mixed metal to ligand and halide to ligand charge transfer, (X + M)LCT. In 2, a dual emission band at low temperature was observed which was attributed to3CC (LE band) and3XLCT (HE band). Thermochromism and mechanochromism of complexes 1–3 were also investigated.
2018
Dinuclear and tetranuclear copper(I) iodide complexes with P and P^N donor ligands: Structural and photoluminescence studies / Neshat, Abdollah; Aghakhanpour, Reza Babadi; Mastrorilli, Piero; Todisco, Stefano; Molani, Farzad; Wojtczak, Andrzej. - In: POLYHEDRON. - ISSN 0277-5387. - STAMPA. - 154:(2018), pp. 217-228. [10.1016/j.poly.2018.07.045]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11589/139419
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