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Zinc(II) as a Versatile Template for Efficient Dipolar and Octupolar Second-Order Nonlinear Optical Molecular Materials §
Open AccessArticle

Tuning the Linear and Nonlinear Optical Properties of Pyrene-Pyridine Chromophores by Protonation and Complexation to d10 Metal Centers §

1
Institute of Molecular Science and Technologies of CNR and INSTM RU, via Golgi 19, 20133 Milano, Italy
2
Department of Chemistry, Università degli Studi di Milano and INSTM RU, via Golgi 19, 20133 Milano, Italy
*
Authors to whom correspondence should be addressed.
§
This manuscript is dedicated to Prof. Renato Ugo, on the occasion of his 80th birthday, for his fundamental research in the field of organic and hybrid inorganic/organic materials with second-order NLO properties.
Inorganics 2019, 7(3), 38; https://doi.org/10.3390/inorganics7030038
Received: 17 January 2019 / Revised: 4 March 2019 / Accepted: 5 March 2019 / Published: 9 March 2019
(This article belongs to the Special Issue Metal Complexes as Nonlinear Optical Molecular Materials)
The linear and second-order nonlinear optical (NLO) properties of two pyrene-pyridine chromophores, namely, 4-(pyren-1-yl)pyridine (L1) and 4-(2-(pyren-1-yl)ethyl)pyridine (L2), were investigated and modulated by performing protonation/deprotonation cycles or by complexation to d10 metal centers such as Zn(II) and Cu(I) to form the monomeric [Zn(CH3CO2)2(L1)2] complex and the [CuI(L2)]n coordination polymer, respectively. The structures of L1, L2, [Zn(CH3CO2)2(L1)2] and [CuI(L2)]n were determined by means of single-crystal X-ray diffraction studies. The NLO response, measured by the electric-field-induced second harmonic generation (EFISH) technique, was positive for both chromophores and showed an inversion of the sign after exposure to HCl vapors. This process was completely reversible and the original values were restored by simple exposure to NH3 vapors. Coordination of L1 to Zn(II) also resulted in a negative NLO response, although smaller in magnitude compared to the protonated form, due to the weak Lewis acidity of the “Zn(CH3CO2)2” fragment. The results were also interpreted on the basis of DFT/TDDFT calculations. View Full-Text
Keywords: second-order nonlinear optics; EFISH technique; pyrene-pyridine chromophores; acidochromism second-order nonlinear optics; EFISH technique; pyrene-pyridine chromophores; acidochromism
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MDPI and ACS Style

Lucenti, E.; Forni, A.; Marinotto, D.; Previtali, A.; Righetto, S.; Cariati, E. Tuning the Linear and Nonlinear Optical Properties of Pyrene-Pyridine Chromophores by Protonation and Complexation to d10 Metal Centers §. Inorganics 2019, 7, 38.

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