Abstract
The self-assembly of ligand-metal-ligand sandwich complexes involving a novel quinoxaline-containing crown ether, 1, was studied by electrospray ionization mass spectrometry (ESI-MS). Donor-acceptor π-stacking interactions between the electron-poor quinoxaline group of 1 and electron-rich benzene groups from benzo- or dibenzo-18-crown-6 were found to significantly enhance the formation of mixed-ligand sandwich complexes with a free energy gain of up to 17 kJ/mol relative to sandwich formation involving macrocycles without such aromatic functionalities. The relative intensities of the sandwich complexes were greatest with the alkali metals Na+, K+, and Rb+ as well as with the ammonium ion in equimolar concentrations with the macrocycles. The preferential formation of the mixed-ligand sandwich complexes demonstrated that donor-acceptor π-stacking interactions contribute to the assembly of molecular structures and can be monitored by ESI-MS.
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Published online May 25, 2005
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Sherman, C.L., Brodbelt, J.S., Marchand, A.P. et al. Electrospray ionization mass spectrometric detection of self-assembly of a crown ether complex directed by π-stacking interactions. J Am Soc Mass Spectrom 16, 1162–1171 (2005). https://doi.org/10.1016/j.jasms.2005.03.014
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DOI: https://doi.org/10.1016/j.jasms.2005.03.014