Abstract
The 14-membered cyclic diamide 1,4,8,11-tetraazacyclotetradecane-5,12-dione (5,12-dioxocyclam) can be considered as a trans-autodiprotected tetraazamacrocycle and provides a convenient starting material for the preparation of macrobicyclic receptors. As an example, the secondary amine nitrogen atoms located at the 1 and 8 positions were cross-bridged with a 1,3-pyridyl strap, affording the constrained ansa-dioxocyclam ligand 1,9,12,18,22-pentaazatricyclo[7.6.6.13,7]docosa-3,5,7(22)-triene-13,19-dione (L1). The proton binding properties of this cage-type compound, which possesses a hemispherical cavity, were fully investigated by spectroscopic (IR, NMR, UV, MALDI-TOF MS), quantum chemical, and potentiometric methods. While both bridgehead tertiary amines have their free lone pairs oriented inside the cavity, intramolecular hydrogen bonding was found to play a key role in determining the structural features of the free base and its protonated forms. L1 behaves as a diprotic base in water with log K011 = 8.94(1) and log K012 = 2.32(9), but most interestingly shows slow proton-transfer rates on the NMR timescale.
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