Accommodating Unwelcome
Guests in Inorganic Layered
Hosts: Inclusion of Chloranil in a Layered Double Hydroxide
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Abstract
The host–guest chemistry of most inorganic layered
solids
is limited to ion-exchange reactions. The guest species are either
cations or anions to compensate for the charge deficit, either positive
or negative, of the inorganic layers. Here, we outline a strategy
to include neutral molecules like <i>ortho</i>- and <i>para</i>-chloranil, that are known to be good acceptors in donor–acceptor
or charge-transfer complexes, within the galleries of a layered solid.
We have succeeded in including neutral <i>ortho-</i> and <i>para</i>-chloranil molecules within the galleries of an Mg-Al
layered double hydroxide (LDH) by using charge-transfer interactions
with preintercalated <i>p</i>-aminobenzoate ions as the
driving force. The <i>p</i>-aminobenzoate ions are introduced
in the Mg-Al LDH via ion exchange. The intercalated LDH can adsorb <i>ortho-</i> and <i>para</i>-chloranil from chloroform
solutions by forming charge-transfer complexes with the <i>p</i>-aminobenzoate anions present in the galleries. We use X-ray diffraction,
spectroscopy, and molecular dynamics simulations to establish the
nature of interactions and arrangement of the charge-transfer complex
within the galleries of the layered double hydroxide