pH-switchability and second-order nonlinear optical properties of monocyclopentadienylruthenium(II)/iron(II) tetrazoles/tetrazolates: synthesis, characterization, and time-dependent density functional theory calculations

Florindo, Pedro R.Costa, Paulo J.Piedade, M. F. M.Robalo, Maria Paula2018-01-312018-01-312017-06-19FLORINDO, Pedro R.; [et al] – pH-switchability and second-order nonlinear optical properties of monocyclopentadienylruthenium(II)/iron(II) tetrazoles/tetrazolates: synthesis, characterization, and time-dependent density functional theory calculations. Inorganic Chemistry. ISSN 0020-1669. Vol. 56, N.º 12 (2017), pp. 6849-68630020-16691520-510Xhttp://hdl.handle.net/10400.21/7996Tetrazole/tetrazolate monocydopentadienyliron(II) and ruthenium(II) compounds of general formulas [(eta(5)-C5H5)M(dppe)(N-4(H)CC6H4NO2)][PF6]/[(eta(5)-C5H5)M(dppe)(N4CC6H4NO2] were investigated for their pH-switching second-order nonlinear optical (SONLO) properties. Compounds [(eta(5)-C5H5)M(dppe)(N4CC6H4NO2) (M = Fe, Ru) and compound [(eta(5)-C5H5)Ru(dppe)(N-4(H)CC6H4NO2)][PF6] were fully characterized by (H-1-, C-13-, P-31-) NMR, cyclic voltammetty, and elemental analysis, and compounds [(eta(5)-C5H5)Fe(dppe)(N4CC6H4NO2)] and [(eta(5)-C5H5)Ru(dppe)(N-4(H)CC6H4NO2)][PF6] were further characterized by single-crystal X-ray diffraction; the synthesis of [(eta(5)-C5H5)Fe(dppe)(N-4(H)CC6H4NO2)][PF6] was unsuccessful. Time-dependent density functional theory calculations were performed using PBE0 and CAM-B3LYP functionals to evaluate the first hyperpolarizability (beta(tot)) of the tetrazole/tetrazolate complexes and for a detailed analysis of the experimental data. Both functionals piedict (i) high first hyperpolarizabilities for the tetrazolate complexes [(eta(5)-C5H5)M(dppe)(N4CC6H4NO2)], with beta(tot)[Ru] approximate to 1.2 beta(tot)[Fe], and (ii) a 3-fold reduction in beta(tot)[Ru] protonation, in complex [(eta(5)-C5H5)Ru(dppe)(N-4(H)CC6H4NO2)](+), forecasting [(eta(5)-C5H5)Ru(dppe)(N4CC6H4NO2)]/[(eta(5)-C5H5)Ru(dppe)(N-4(H)CC6H4NO2)](+) complexes as on/off, pH-switchable SONLO forms.engCyclopentadienyl derivative complexesRay crystal structure1st hyperpolarizabilitiesOrganometallic complexesRuthenium(II) complexesCubic hyperpolarizabilitiesPhysical-propertiesElectron-acceptorLigandsChemistrypH-switchability and second-order nonlinear optical properties of monocyclopentadienylruthenium(II)/iron(II) tetrazoles/tetrazolates: synthesis, characterization, and time-dependent density functional theory calculationsjournal article10.1021/acs.inorgchem.7b00138