Lanthanide trivalent ions (Ln3+) are of intense interests as they show narrow band emissions with high quantum yields when binding with suitable chromophoric ligands. However, compared to transition metals, lanthanide ions often exhibit a diverse range of coordination geometries upon coordinated with tridentate ligands, such as 2,2':6',2''-terpyridine (tpy). To solve this issue, we designed a model system with adjacent tpys, which provide specific coordination sites for lanthanide ions to fit in. As such, a well-controlled binding mode with Ln:tpy at 1:2 ratio was achieved, which was and evidenced characterized by electrospray ionization mass spectroscopy (ESI- MS) and nuclear magnetic resonance (NMR). Based on this strategy, we further constructed metallo-supramolecular polymer (MSP) possessing similar binding behavior as the model system. The MSP was successfully prepared through covalent polymerization followed by coordination-driven self-assembly. Both monomer and polymer are fully characterized by 1H, 13C, 2D correlation spectroscopy (2D-COSY, NOESY) NMR, and Matrix-assisted Laser Desorption/ionization mass spectrometry (MALDI TOF MS). In order to gain more insights into the coordination configuration of lanthanide ions in the MSP, atomic force microscopy (AFM), and scanning tunneling microscopy (STM) will be performed in the future.

Self-assembly of metalo-supramolecular belt and characterization by sSanning tunneling microscopy

ACS Spring 2022

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