Shun-Ze Zhan

Two polar and tropical coordinated decanuclear regioisomeric cuprofullerenes with Cu ^I atoms coordinating on CC bonds of the two polar zones around pentagons and the tropical zone of the equator have been successfully assembled, respectively.

The first coordination‐saturated buckyball with a C₆₀ molecule totally encased in an icosidodecahedral Cu₃₀ in a (μ₃₀‐(η²)₃₀)‐fashion, namely C₆₀@Cu₃₀@Cl₃₆N₁₂, has been successfully realized by a C₆₀‐templated assembly. The 48 outmost coordinating atoms (36Cl+12N) comprise a new simple polyhedron that is described by a ccf topology. Charge transfer from (Cu^I, Cl) to C₆₀ explains the expansion of the light absorption up to 700 nm, and accounts for an ultrafast photophysical process that underpins its high photothermal conversion efficiency. This work makes a giant step forward in exohedral metallofullerene (ExMF) chemistry.

The first coordination‐saturated buckyball with a C₆₀ molecule totally encased in an icosidodecahedral Cu₃₀ in a (μ₃₀‐(η²)₃₀)‐fashion, namely C₆₀@Cu₃₀@Cl₃₆N₁₂, has been successfully realized by a C₆₀‐templated assembly. The 48 outmost coordinating atoms (36Cl+12N) comprise a new simple polyhedron that is described by a ccf topology. Charge transfer from (Cu^I, Cl) to C₆₀ explains the expansion of the light absorption up to 700 nm, and accounts for an ultrafast photophysical process that underpins its high photothermal conversion efficiency. This work makes a giant step forward in exohedral metallofullerene (ExMF) chemistry.

Two metallofullerene frameworks (MFFs) constructed from a penta‐shell Keplerate cuprofullerene chloride, C₆₀@Cu₂₄@Cl₄₄@Cu₁₂@Cl₁₂, have been successfully prepared via a C₆₀‐templated symmetry‐driven strategy. The icosahedral cuprofullerene chloride is assembled on a C₆₀ molecule through [η²‐(C=C)]−Cu^I and Cu^I−Cl coordination bonds, resulting in the penta‐shell Keplerate with the C₆₀ core canopied by 24 Cu, 44 Cl, 12 Cu and 12 Cl atoms that fulfill the tic@rco@oae@ico@ico penta‐shell polyhedral configuration. By sharing the outmost‐shell Cl atoms, the cuprofullerene chlorides are connected into 2D or 3D (snf net) frameworks. TD‐DFT calculations reveal that the charge transfer from the outmost Cu^I and Cl to C₆₀ core is responsible for their light absorption expansion to near‐infrared region, implying anionic halogenation may be an effective strategy to tune the light absorption properties of metallofullerene materials.

Two metallofullerene frameworks (MFFs) constructed from a penta‐shell Keplerate cuprofullerene chloride, C₆₀@Cu₂₄@Cl₄₄@Cu₁₂@Cl₁₂, have been successfully prepared via a C₆₀‐templated symmetry‐driven strategy. The icosahedral cuprofullerene chloride is assembled on a C₆₀ molecule through [η²‐(C=C)]−Cu^I and Cu^I−Cl coordination bonds, resulting in the penta‐shell Keplerate with the C₆₀ core canopied by 24 Cu, 44 Cl, 12 Cu and 12 Cl atoms that fulfill the tic@rco@oae@ico@ico penta‐shell polyhedral configuration. By sharing the outmost‐shell Cl atoms, the cuprofullerene chlorides are connected into 2D or 3D (snf net) frameworks. TD‐DFT calculations reveal that the charge transfer from the outmost Cu^I and Cl to C₆₀ core is responsible for their light absorption expansion to near‐infrared region, implying anionic halogenation may be an effective strategy to tune the light absorption properties of metallofullerene materials.

A fluorescent polycatenated hydrogen-bonded organic framework (MEP-HOF) has been developed using a C₃-symmetric rigid macrocycle as the exclusive building block. Stabilised by intermolecular non-covalent interactions in the solid state, the tri-carboxylated macrocycles form supramolecular embraced pairs which further assemble the interwoven three-dimensional H-bond network with a degree of catenation of seven. The MEP-HOF features easy preparation and regeneration, and its fluorescent properties could be utilised as a sensitive sensor for nitrobenzene detection in water with a detection limit of 61.8 ± 2.2 ppb.

Two 2D coordination sheets with narrow bandgap based on tetranuclear cuprofullerene pentafluorobenzoate constructed with linear (μ₂–η²:η²)₂-C₆₀ connecting Cu^I/Cu^II pentafluorobenzoate polymeric chains, were realized under solvothermal conditions.