Engineering solid-state photoreactivity within silver(I) organosulfonate complexes containing an ester-functionalized reactant molecule

Abstract

The formation, structure, and photoreactivity of a pair of silver(I) complexes based upon either trifluoromethanesulfonate [Ag(CF₃SO₃)] or p-toluenesulfonate [Ag(C₇H₇SO₃)] anions along with the ester-based reactant molecule trans-1-(4-methylbenzoate)-2-(4-pyridyl)ethylene (1) are reported. In both complexes, silver(I) ions form coordinated covalent bonds to the 4-pyridyl group on the olefin containing reactant molecule and due to either argentophilic interactions or close packing of a pair of silver(I) ions ultimately places a pair of carbon-carbon bonds (C = C) on neighboring molecules of 1 in a suitable position to undergo a solid-state [2 + 2] cycloaddition reaction. In particular, the complexes [Ag(CF₃SO₃)(1)₂]·CH₃CN and [Ag₂(C₇H₇SO₃)₂(1)₄] both undergo a quantitative photoreaction to yield the head-to-head photoproduct rctt-1,2-bis(4-methylbenzoate)-3,4-bis(4-pyridyl)cyclobutane (2) upon exposure to ultraviolet light.

Graphical Abstract

Keywords:

• Argentophilic interactions
• [2 + 2] cycloaddition reactions
• crystal engineering
• solid state
• silver(I) organosulfonate

Acknowledgements

R. H. G. gratefully acknowledges financial support from Webster University in the form of various Faculty Research Grants. G. M. F. gratefully acknowledges financial support from Illinois State University in the form of instrumentation upkeep including cryogens. These materials are required based upon work supported by the National Science Foundation through the Major Research Instrumentation Program (CHE 1039689).

Disclosure statement

No potential conflict of interest was reported by the authors.