NDLI: Comparative study of spectroscopic properties of the low-lying electronic states of 2,4-pentadien-1-iminium cation and its N-substituted analogues

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Comparative study of spectroscopic properties of the low-lying electronic states of 2,4-pentadien-1-iminium cation and its N-substituted analogues

Content Provider	Springer Nature Link
Author	CHATTOPADHYAY, ANJAN
Copyright Year	2012
Abstract	Semiempirical and ab initio-based CI methods have been employed to study the low-lying electronic states of 2,4-pentadien-1-iminium cation and its N-substituted analogues with electron-donating (methyl, isopropyl) and electron-withdrawing (fluoromethyl) groups on nitrogen. Variations of the dihedral angles (Γ$_{3}$, Γ$_{4}$) of the ground state have given the global minima and global maxima at (180°, 180°) and (90°, 0°) conformations, respectively, with some exceptions in the case of fluoromethyl compound. Increase in the +I effect on nitrogen shifts the TICT conical intersection point away from the 90° (Γ$_{3}$ dihedral angle) value, when the Γ$_{4}$ value is kept fixed at 180°. Transition moment values of the allowed S$_{0}$(1A$_{g}$ –like) →S$_{1}$ (2B$_{u}$–like) transitions are expectedly higher than the forbidden S$_{0}$(1A$_{g}$ –like) →S$_{2}$(2A$_{g}$ –like) transitions by almost 5.6 D. Radiative lifetime values of the first excited states are calculated to be around 215 ps for all the four compounds. At (180°, 180°) conformation the vertical excitation energy (VEE) between the S$_{0}$ and S$_{1}$ states of the 2,4-pentadieniminium cation is found to be 3.3 eV, which corresponds to the absorption wavelength value of roughly 375 nm. The VEE value increases with substituents having +I effect on nitrogen, while for the fluoromethyl compound it is calculated to be around 2.85 eV. The energy gap between the first two excited singlet states is found to have the least value in the isopropyl-substituted compound, where the S$_{2}$ state contains a huge contribution from the HOMO$^{2}$→LUMO$^{2}$ configuration. Graphical Abstract Substitution of electron-donating groups (methyl, isopropyl) on the nitrogen of 2,4-pentadien-1-iminium cation shifts the TICT conical intersection position (with respect to the Γ3 dihedral angle) away from the 90° value, when Γ4 is kept fixed at 180°. This is due to the stabilization of the covalent-ground state (S0) and destabilization of the first excited singlet state (S1).
Starting Page	985
Ending Page	994
Page Count	10
File Format	PDF
ISSN	09743626
Journal	Journal of Chemical Sciences
Volume Number	124
Issue Number	5
e-ISSN	09737103
Language	English
Publisher	Springer-Verlag
Publisher Date	2012-10-12
Publisher Institution	Indian Academy of Sciences
Publisher Place	India
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Protonated Schiff base configuration interaction TICT conical intersection Chemistry/Food Science
Content Type	Text
Resource Type	Article
Subject	Chemistry

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