Synthesis, molecular structure, vibrational studies, optical properties and electrical conduction mechanism of the new hybrid compound based on selenate

DFT computation, Hirshfeld surfaces analysis, non-linear optical and spectroscopic investigations of a novel non-centrosymmetric organic –inorganic hybrid material [(CH3CH2)4N]HSeO4(H2SeO4)2

“…The high value of dipole moment is observed for μx component at 12.6018D; for the y and z directions, these values are equal to -4.2282 D and 1.7615 D respectively. For the [(C3H7)4N]HSeO4(H2SeO4)2 compound [14], the highest dipole moment value was observed for the μz component (12.8146D), while μx and μy values were calculated at 0.1703D and -2.2407D, respectively. The transformation of the high value of dipole moment from the a direction to the c direction is in well agreement with the space groups notation Ia and Cc assigned to [(C2H5)4N]HSeO4(H2SeO4)2 and [(C3H7)4N]HSeO4(H2SeO4)2, respectively.…”

“…In contrast, for the [(C3H7)4N]HSeO4(H2SeO4)2 material, the selenate inorganic layers were built up by infinite chains of [(H2SeO4)2HSeO4] nn anions parallel to the bdirection [14]; while, the midplanes of the selenates groups, are located at z =1/4 and z =3/4. The d(D…A) hydrogen bonding vary in 2.480(16) -2.788 (19) Å for [(C2H5)4N]HSeO4(H2SeO4)2 [15], and in 2.29(2) -2.42(2) Å in [(C3H7)4N]HSeO4(H2SeO4)2 [14], indicating that that the hydrogen bonding are more strong in the compound containing the terapropylammonium cations. Even if the tetrapropylammonium are voluminous than the tetraethylammonium cations, one can state that the unit cell volume (A°3) [2010.37(8)] of [(C3H7)4N]HSeO4(H2SeO4)2 is small than that found for [(C2H5)4N]HSeO4(H2SeO4)2 [2181.…”

“…The prominent regions observed in the fingerprint plots (figure 6 To compare the tetraethylammonium crystal packing to that of terapropylammonium [14], the Hirshfeld surfaces and fingerprint plots mapped with dnorm are constructed for the [(C3H7)4N]HSeO4(H2SeO4)2 compound, as presented in the figures 7 and 8. Indeed, The prominent regions observed in the fingerprint plots (figure 7-a The table 3 illustrates the percentage contributions of the different contacts in the crystal packing of the two selenate compounds, with the characteristic de and di distances observed for the important contacts O….H/H…O, H….H/H…H, and O...O/O…O.…”

“…These materials have a noncentrosymmetric unit cell, which may reflect the possibility to obtain good materials for NLO, whereas their applications are limited due to their thermal, poor mechanical stabilities, and the lack of sufficiently large single crystals of optical quality. As a result, several reports of macroscopic and microscopic responses for organic-inorganic (NLO) systems have recently appeared in the literature [12][13][14]. The DFT/B3LYP-31G(d) calculated polarizability α, hyperpolarizability β, and electric dipole μ, showed good NLO properties for the [(C3H7)4N]HSeO4(H2SeO4)2 material, crystallized in the monoclinic space group Ia (Z = 4, a = 7.3160(2) Å, b = 31.7630(4) Å, c = 8.6890(2) Å, β = 95.340(2)°) [14].…”

“…As a result, several reports of macroscopic and microscopic responses for organic-inorganic (NLO) systems have recently appeared in the literature [12][13][14]. The DFT/B3LYP-31G(d) calculated polarizability α, hyperpolarizability β, and electric dipole μ, showed good NLO properties for the [(C3H7)4N]HSeO4(H2SeO4)2 material, crystallized in the monoclinic space group Ia (Z = 4, a = 7.3160(2) Å, b = 31.7630(4) Å, c = 8.6890(2) Å, β = 95.340(2)°) [14]. The vibrational properties of this compound were also studied by the Infrared, Raman and RMN spectroscopy [14].…”