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On the Jahn-Teller Effect in Silver Complexes of Dimethyl Amino Phenyl Substituted Phthalocyanine
1Department of Physical Chemistry, Slovak Technical University, Radlinskeho 9, SK-81237 Bratislava, Slovakia.
Abstract:
The structures of Ag complexes with dimethyl amino phenyl substituted phthalocyanine m[dmaphPcAg]q of various charges q and in the 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. The 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 a 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.
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