Abstract
Two new fluoromanganates(III) of 1,2-bis(4-pyridyl)ethane (bpa) and trans-1,2-bis(4-pyridyl)ethylene (bpe), LH(2)[MnF(4)(H(2)O)(2)](2) (L = bpa or bpe), have been prepared and their structure have been solved by single-crystal X-ray diffraction. The [MnF(4)(H(2)O)(2)](-) anion displays an octahedral geometry with a strong Jahn-Teller tetragonal distortion along the H(2)O-Mn-OH(2) axis. The equatorial metal-ligand distances (Mn-F 1.827(1)-1.859(2) A) are shorter than the axial ones (Mn-O 2.203(2)-2.234(2) A). Three polarized absorption bands at 22,500, 18,300 and 14,500 cm(-1) are observed in the optical spectra of (bpaH(2))[MnF(4)(H(2)O)(2)](2). Finally, we present theoretical calculations on the equilibrium bond distances as well as the crystal-field electron structure using density functional methods. The calculated Mn-F bond distances (1.85 A) are in agreement with the experimental data but the obtained Mn-O distances (2.53-2.56 A) are higher than the experimental one as usually found in similar Jahn-Teller distorted systems. The calculated d-d transition energies are compared with experimental energies derived from the optical spectra. The variation of the HOMO energy and transition energies against the Mn-O distance is also shown.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.