In this study we combined QM calculations and NMR measurements to understand at a detailed level the complex interplay of structural/electronic properties with the effects of the solvent in the NLO activity of push pull systems, quantiﬁed in terms of variations of the static hyperpolarizability. Different parameters (bond lengths and bond length alternation, vibrational frequencies, electronic charge distribution) are introduced and tested to rationalize both the solvent sensitivity of three molecular systems (namely, p-nitroaniline, ethyl 4-ammino benzoate, and 5-nitro-1H-indole) and the differences among them. This analysis has ﬁnally allowed us to establish a clear correlation between the charge transfer behavior of the systems, their NLO properties, and NMR parameters also validating simpli ﬁed but e ﬀective chemical analyses based on resonance limit forms.
|Autori interni:||JURINOVICH, SANDRO|
CATALANO, DONATA INES MARIA
|Autori:||A. MARINI; S. MACCHI; S. JURINOVICH; D. CATALANO; MENNUCCI B|
|Titolo:||Integrated NMR and Computational Study of Push–Pull NLO Probes: Interplay of Solvent and Structural Effects|
|Anno del prodotto:||2011|
|Digital Object Identifier (DOI):||10.1021/jp203864a|
|Appare nelle tipologie:||1.1 Articolo in rivista|