We report a stable, water-soluble, mononuclear manganese(IV)
complex
[MnIV(H2
L)]·5H2O (Mn-HDCL) that acts as an efficient photothermal material. This
system is based on a hexahydrazide clathrochelate ligand (L/HDCL) and is obtained via an efficient one-pot templated synthesis
that avoids the need for harsh reaction conditions. Scanning tunneling
microscopy images reveal that Mn-HDCL exists as a 2D sheet-like structure.
In Mn-HDCL, the manganese(IV) ion is trapped within the cavity of
the cage-like ligand. This effectively shields the Mn(IV) ion from
the external environment while providing adequate water solubility.
As a result of orbital transitions involving the coordinated manganese(IV)
ion, as well as metal-to-ligand charge transfer effects, Mn-HDCL possesses
a large extinction coefficient and displays a photothermal performance
comparable to single-wall carbon nanotubes in the solid state. A high
photothermal conversion efficiency (ca. 71%) was achieved in aqueous
solution when subjected to near-infrared 730 nm laser photo-irradiation.
Mn-HDCL is paramagnetic and provides a modest increase in the T
1-weighted contrast of magnetic resonance images
both in vitro and in vivo. Mn-HDCL
was found to target tumors passively and allow tumor margins to be
distinguished in vivo in a mouse model. In addition,
it also exhibited an efficient laser-triggered photothermal therapy
effect in vitro and in vivo. We
thus propose that Mn-HDCL could have a role to play as a tumor-targeting
photothermal sensitizer.