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Hydrogen-Bonding Interactions Trigger Induction of Chirality via Formation of a Cyclic Dimer.

A rationalization for the chirality transfer mechanism in the supramolecular host-guest assemblies of an achiral Zn(II) porphyrin dimer (host) and a series of chiral diamines and diamino esters (substrates) via cyclic dimer formation has been reported for the first time. Stepwise formations of 2:2 host-guest cyclic dimers and 1:2 host-guest monomeric complexes have been observed via intermolecular assembling and disassembling processes. A large bisignate CD couplet was observed for the cyclic dimer, whereas the monomeric complexes exhibited negligible CD intensity. Crystallographic characterizations demonstrate that the strong intermolecular H bonding in cyclic dimers is responsible for their stability over the linear chain, which thereby display high-intensity bisignate CD couplets. In order to minimize the steric crowding within the host-guest assembly, the cyclic dimer switches its helicity toward the conformer having less steric hindrance. The cyclic scaffold is oriented according to the pre-existing chirality of the substrate in both the solid and solution phases: the substrates having R chirality display a negative CD couplet, whereas the substrates with S chirality display a positive couplet. Opposite signs for the CD couplets between R and S substrates suggest that the stereographic projection at the chiral centers solely dictates the overall helicity of the cyclic dimer. DFT studies further support the experimental observations.