Activating [4 + 4] photoreactivity in the solid-state via complexation: from 9-(methylaminomethyl)anthracene to its silver(i) complexes

Abstract

The [4 + 4] photoreactivity of the anthracene derivative 9-(methylaminomethyl)anthracene (MAMA) has been investigated in solution, gel medium and in the solid state. While quantitative formation of the cyloaddition photoproduct was achieved upon irradiation at λ = 365 nm of ethanol solutions of MAMA, only partial and slow conversion was detected in gels of low molecular weight gelators, and solid-state reactivity was not observed due to the unfavourable relative orientation of the anthracene moieties in the crystal. In hexafluorophosphate, tetrafluoroborate and nitrate silver(i) complexes, however, 9-(methylaminomethyl)anthracene exhibits a more favourable mutual orientation for the aromatic fragments, and [4 + 4] photoreactivity resulted. All compounds were structurally characterized via single crystal and/or X-ray powder diffraction and by Raman spectroscopy; this last technique proved effective in detection of the photoproduct in all solid state complexes.

Thermo- and light-triggered reversible interconversion of dysprosium–anthracene complexes and their responsive optical, magnetic and dielectric properties

“…It is worth mentioning that only a handful metal–anthracene complexes (Ru, 56 Re, 57 Cu, 36 Ag, 58 Pt, 35 and Ln 40,41 ) are known to undergo a [4 + 4] photocycloaddition reaction upon UV irradiation either in solution or in the solid state. Metal–organic systems showing both reversible thermochromism and photodimerization of anthracene have never been documented thus far.…”

Assembling photoactive materials from polycyclic aromatic hydrocarbons (PAHs): room temperature phosphorescence and excimer-emission in co-crystals with 1,4-diiodotetrafluorobenzene

“…84–86 Since then, the photoreactivity of anthracene and its derivatives within molecular crystals has fascinated scientists and has been the subject of intense research over the last decades, both for theoretical purposes and potential applications. 87–95…”

“…[84][85][86] Since then, the photoreactivity of anthracene and its derivatives within molecular crystals has fascinated scientists and has been the subject of intense research over the last decades, both for theoretical purposes and potential applications. [87][88][89][90][91][92][93][94][95] The arrangement of MA pairs in crystalline (MA) 4 •I2F4 is promising from a purely geometrical point of view; therefore the possible [4 + 4] photoreactivity of the co-crystal was investigated. UV irradiation experiments on the co-crystal were first conducted on the same specimen used for single crystal XRD data collection and structural determination.…”

Deeper Insight into Photopolymerization: The Synergy of Time-Resolved Nonuniform Sampling and Diffusion NMR

“…The scheme of the reaction is shown in Figure . Photodimerization of amine-based anthracene derivatives is well known in the literature, and head/tail isomers of dimers are the preferred products. − …”