Photophysical Properties and Kinetic Studies of 2-Vinylpyridine-Based Cycloplatinated(II) Complexes Containing Various Phosphine Ligands

Vahideh Dolatyari; Hamid R Shahsavari; Sepideh Habibzadeh; Reza Babadi Aghakhanpour; Sareh Paziresh; Mohsen Golbon Haghighi; Mohammad Reza Halvagar

doi:10.3390/molecules26072034

Photophysical Properties and Kinetic Studies of 2-Vinylpyridine-Based Cycloplatinated(II) Complexes Containing Various Phosphine Ligands

Molecules. 2021 Apr 2;26(7):2034. doi: 10.3390/molecules26072034.

Authors

Vahideh Dolatyari¹, Hamid R Shahsavari¹, Sepideh Habibzadeh², Reza Babadi Aghakhanpour¹, Sareh Paziresh¹, Mohsen Golbon Haghighi³, Mohammad Reza Halvagar⁴

Affiliations

¹ Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan 45137-66731, Iran.
² Department of Chemistry, Payame Noor University, Tehran P.O. BOX 19395-4697, Iran.
³ Department of Chemistry, Shahid Beheshti University, Evin, Tehran 19839-69411, Iran.
⁴ Department of Inorganic Chemistry, Chemistry and Chemical Engineering Research Center of Iran, Tehran 14968-13151, Iran.

Abstract

A series of cycloplatinated(II) complexes with general formula of [PtMe(Vpy)(PR₃)], Vpy = 2-vinylpyridine and PR₃ = PPh₃ (1a); PPh₂Me (1b); PPhMe₂ (1c), were synthesized and characterized by means of spectroscopic methods. These cycloplatinated(II) complexes were luminescent at room temperature in the yellow-orange region's structured bands. The PPhMe₂ derivative was the strongest emissive among the complexes, and the complex with PPh₃ was the weakest one. Similar to many luminescent cycloplatinated(II) complexes, the emission was mainly localized on the Vpy cyclometalated ligand as the main chromophoric moiety. The present cycloplatinated(II) complexes were oxidatively reacted with MeI to yield the corresponding cycloplatinated(IV) complexes. The kinetic studies of the reaction point out to an S_N2 mechanism. The complex with PPhMe₂ ligand exhibited the fastest oxidative addition reaction due to the most electron-rich Pt(II) center in its structure, whereas the PPh₃ derivative showed the slowest one. Interestingly, for the PPhMe₂ analog, the trans isomer was stable and could be isolated as both kinetic and thermodynamic product, while the other two underwent trans to cis isomerization.

Keywords: 2-vinylpyridine; cycloplatinated(II); kinetic; phosphine; photophysics.