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Updated: Jun 12, 2025

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes
Published on: April 1, 2013
What does it take to stabilize a naphthalene anion?
Jozef Ďurana1, Barbora Kocábková1, Jozef Rakovský1
1J. Heyrovský Institute of Physical Chemistry, v.v.i., Czech Academy of Sciences, Dolejškova 2155/3, 182 23 Prague, Czech Republic.
Abstract:
We investigate attachment of slow electrons (0-10 eV) to naphthalene (Np) clusters in a crossed beam experiment. Supersonic expansions under different conditions using different buffer gases generate the clusters: in He, Ne, and low pressure Ar, neat (Np)N clusters are formed, while we also observe mixed clusters of naphthalene with rare-gas atoms in co-expansion with Ar above 0.5 bar and with Kr. Negatively charged (Np)n- and Rgm(Np)n- (Rg = Ar, Kr) clusters are analyzed by mass spectrometry, and electron energy dependent ion yields are measured. We show that the smallest stable naphthalene complex with an excess electron, the dimer (Np)2- anion, cannot be formed in a binary collision of a free electron with (Np)2 dimer, nor with (Np)3 trimer. Evaporation of a weakly bound Ar atom(s) from a mixed ArM(Np)2 cluster following electron attachment leads to the dimer (Np)2- anion. Larger (Np)n-, n > 3, transient cluster anions decay via evaporation of an Np unit on a timescale of tens of microseconds. The self-scavenging process opens around 6 eV, where a naphthalene unit is electronically excited by the incoming electron, which is slowed down and trapped. However, the transient negative ion is efficiently stabilized only in the mixed clusters, from which Ar atom(s) can be evaporated.
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