In this report, we developed a novel strategy for constructing complex supramolecular self-assembly system. With this purpose, we selected a discotic benzene-1,3,5-tricarboxamide (BTA) molecule as the core, followed by grafting three dipicolinic acid (DPA) groups onto the DPA core, then yielding a new tri-ligand L3. The L3 itself is too small to form supramolecular polymers, but in the presence of appropriate metal ions, the DPA groups of L3 can form three coordination bonds to constrcut a large metal-ligand cluster. These cluster, namely the ‘supramolecular monomers’, contain 10 ligands and 9 metal ions, which can then stack into long filaments (with a cross-sectional diameter of 12 nm) driven by multiple hydrogen bonds between the BTA core. The formation and structure of the fiber are identical for various transition metal ions (i.e., Zn2+, Ni2+, Mn2+, Fe3+) or lanthanide ions (i.e., La3+, Eu3+, Tb3+, Gd3+), the latter enables introducing and regulating different metal-derived functionalities. For example, europium (Eu3+) and terbium (Tb3+) ions can bring luminescence property to the samples; gadolinium (Gd3+) ions can enhance the magnetic relativity of sample. By properly regulating the combination and mixing ratio of lanthanide ions, we can successfully prepare a binary or ternary system with tunable functions. Overall, with this strategy, we can obtain a doubly supramolecular polymer, connected axially by hydrogen bonds, and radially by coordination bonds. Not only does this realize a higher level of complexity, but it also allows to easily introduce and vary metal-derived functionalities.

In this report, we developed a novel strategy for constructing complex supramolecular self-assembly system. With this purpose, we selected a discotic benzene-1,3,5-tricarboxamide (BTA) molecule as the core, followed by grafting three dipicolinic acid (DPA) groups onto the DPA core, then yielding a new tri-ligand L~3~. The L~3~ itself is too small to form supramolecular polymers, but in the presence of appropriate metal ions, the DPA groups of L~3~ can form three coordination bonds to constrcut a large metal-ligand cluster. These cluster, namely the ‘supramolecular monomers’, contain 10 ligands and 9 metal ions, which can then stack into long filaments (with a cross-sectional diameter of 12 nm) driven by multiple hydrogen bonds between the BTA core. The formation and structure of the fiber are identical for various transition metal ions (_i.e._, Zn^2+^, Ni^2+^, Mn^2+^, Fe^3+^) or lanthanide ions (_i.e._, La^3+^, Eu^3+^, Tb^3+^, Gd^3+^), the latter enables introducing and regulating different metal-derived functionalities. For example, europium (Eu^3+^) and terbium (Tb^3+^) ions can bring luminescence property to the samples; gadolinium (Gd^3+^) ions can enhance the magnetic relativity of sample. By properly regulating the combination and mixing ratio of lanthanide ions, we can successfully prepare a binary or ternary system with tunable functions. Overall, with this strategy, we can obtain a doubly supramolecular polymer, connected axially by hydrogen bonds, and radially by coordination bonds. Not only does this realize a higher level of complexity, but it also allows to easily introduce and vary metal-derived functionalities.

Complex supramolecular fiber formed by coordination-induced self-assembly of benzene-1,3,5-tricarboxamide

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