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Issue 6, 2006
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A time-dependent density functional theory investigation on the nature of the electronic transitions involved in the nonlinear optical response of [Ru(CF3CO2)3T] (T = 4′-(C6H4-p-NBu2)-2,2′:6′,2″-terpyridine)

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Abstract

We report a theoretical study based on density functional theory (DFT) and time-dependent DFT (TDDFT) calculations on the nature and role of the absorption bands involved in the nonlinear optical response of the complexes [Ru(CF3CO2)3T] (T = T1, T2; T1 = 4′-(C6H4-p-NBu2)-2,2′:6′,2″-terpyridine, T2 = 4′-(C6H4-p-NMe2)-2,2′:6′,2″-terpyridine). Geometry optimizations, performed without any symmetry constraints, confirm a twisting of the –C6H4-p-NBu2 moiety with respect to the plane of the chelated terpyridine. Despite this lack of strong π interaction, TDDFT excited states calculations of the electronic spectrum in solution provide evidence of a relevant role of the NBu2 donor group in the low-energy LMCT band at 911 nm. Calculations also show that the two bands at higher energy (508 and 455 nm) are not attributable only to LMCT and ILCT transitions but to a mixing of ILCT/MLCT and ILCT/π−π* transitions, respectively. The 911 nm LMCT band, appearing at lower wavelength of the second harmonic (670 nm) of the EFISH experiment, controls the negative value of the second-order NLO response. This is confirmed by our calculations of the static component β0zzz of the quadratic hyperpolarizability tensor, showing a large positive value. In addition we have found that the increase of the dipole moment upon excitation occurs, in all the characterized transitions, along the dipole moment axis, thus explaining why the EFISH and solvatochromic experimental values of the quadratic hyperpolarizability agree as sign and value.

Graphical abstract: A time-dependent density functional theory investigation on the nature of the electronic transitions involved in the nonlinear optical response of [Ru(CF3CO2)3T] (T = 4′-(C6H4-p-NBu2)-2,2′:6′,2″-terpyridine)

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Publication details

The article was received on 28 Jun 2005, accepted on 11 Oct 2005 and first published on 07 Nov 2005


Article type: Paper
DOI: 10.1039/B509123C
Citation: Dalton Trans., 2006,0, 852-859
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    A time-dependent density functional theory investigation on the nature of the electronic transitions involved in the nonlinear optical response of [Ru(CF3CO2)3T] (T = 4′-(C6H4-p-NBu2)-2,2′:6′,2″-terpyridine)

    F. De Angelis, S. Fantacci, A. Sgamelotti, F. Cariati, D. Roberto, F. Tessore and R. Ugo, Dalton Trans., 2006, 0, 852
    DOI: 10.1039/B509123C

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