The
development of heterogeneous catalysts capable of selectively
converting lignin model compounds into products of added value offers
an exciting avenue to explore in the production of renewable chemical
feedstocks. The use of metal–organic frameworks (MOFs) in such
chemical transformations relies largely on the presence of accessible
open metal sites found within highly porous networks that simultaneously
allow for fast transport and strong interactions with desired substrates.
Here, we present the first systematic study on the modulation of catalytic
performance of a cationic framework, [Cu2(L)(H2O)2](NO3)2·5.5H2O (L = 1,1′-bis(3,5-dicarboxylatophenyl)-4,4′-bipyridinium),
achieved through the exchange of anionic guests. Remarkably, the catalytic
activity proves to be highly anion-dependent, with a nearly 10-fold
increase toward the aerobic C–C bond cleavage of a lignin model
compound when different anionic species are incorporated within the
MOF. Moreover, we demonstrate that the cationic nature of the MOF,
imparted by the incorporation of viologen moieties within the linker,
tunes the electrophilicity of the active copper(II) sites, resulting
in stronger interactions with the substrate. As such, the copper-based
framework exhibits enhanced catalytic performance when compared to
its neutral counterpart, emphasizing the appeal of charged frameworks
for use as green heterogeneous catalysts.