Article
Version 1
Preserved in Portico This version is not peer-reviewed
On the Jahn-Teller Effect in Silver Complexes of Dimethyl Amino Phenyl Substituted Phthalocyanine
Version 1
: Received: 11 September 2023 / Approved: 12 September 2023 / Online: 13 September 2023 (10:19:19 CEST)
A peer-reviewed article of this Preprint also exists.
Breza, M. On the Jahn–Teller Effect in Silver Complexes of Dimethyl Amino Phenyl Substituted Phthalocyanine. Molecules 2023, 28, 7019. Breza, M. On the Jahn–Teller Effect in Silver Complexes of Dimethyl Amino Phenyl Substituted Phthalocyanine. Molecules 2023, 28, 7019.
Abstract
The structures of Ag complexes with dimethyl amino phenyl substituted phtalocyanine m[dmaphPcAg]q of various charges q and in two lowest spin states m were optimized using the B3LYP method within the D4h symmetry group and its subgroups. The most stable reaction intermediate in the supposed photoinitiation reaction is 3[dmaphPcAg]-. Group-theoretical analysis of the optimized structures and of their electron states reveals two symmetry-descent mechanisms. Stable structures of maximal symmetry of complexes 1[dmaphPcAg]+, 3[dmaphPcAg]+, 2[dmaphPcAg]0 and 4[dmaphPcAg]2- correspond to the D4 group as a consequence of the pseudo-Jahn-Teller effect within unstable D4h structure. Complexes 4[dmaphPcAg]0, 1[dmaphPcAg]-, 3[dmaphPcAg]- and 2[dmaphPcAg]2- with double degenerate electron ground states in D4h symmetry structures undergo a symmetry descent to stable structures corresponding to maximal D2 symmetry not because of a simple Jahn-Teller effect but due to hidden pseudo-Jahn-Teller effect (strong vibronic interaction between excited electron states). The reduction of the neutral photoinitiator causes symmetry descent to its anionic intermediate because of vibronic interactions that must significantly affect the polymerization reactions.
Keywords
DFT; TD-DFT; symmetry descent; electron states; vibronic interactions
Subject
Chemistry and Materials Science, Theoretical Chemistry
Copyright: This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Comments (0)
We encourage comments and feedback from a broad range of readers. See criteria for comments and our Diversity statement.
Leave a public commentSend a private comment to the author(s)
* All users must log in before leaving a comment
