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Abstract
A simple route to the preparation of benzodipyrrolidone (BDP) based monomeric building blocks containing 2,2′:6′,2″-terpyridines is reported from a common precursor 4′-(4-pinacolatoboronphenyl)-2,2′:6′,2″-terpyridine via Suzuki coupling reaction. Self-assembly polymerization with ruthenium (II) ions under mild conditions yielded a series of novel metallo-supramolecular polymers with weak donor-acceptor (D-A) structures based on benzodipyrrolidone. The structure of the bridge connected BDP with terpyridine have a significant impact on the wavelength and intensity of the intramolecular charge transfer (ICT) absorption peak. The resulting metallo-polymers exhibited strong double absorption bands around 315 nm and 510 nm involved in π-π* transitions and ICT or metal to ligand charge transfer (MLCT) absorption bands. The forming of D-A structure and coordination with ruthenium (II) ions is favorable to narrow the energy gap and the energy gaps of the resulting metallo-supramolecular polymers are 2.01 and 1.62 eV, respectively.
Highlights
Based on intermolecular non-covalent interactions, supramolecular chemistry has become one of the most interesting fields in modern chemistry (Lehn, 2002)
These complexes possess a distorted octahedral geometry and thereby a linear bilateral conformation of ligands can be obtained, which is critical in construction of metallo-supramolecular polymers and well-defined architectures based on the coordination interactions between terpyridine and metal center (Pandey et al, 2016; Winter and Schubert, 2016; Yin et al, 2018)
The lower wavelength absorption can be attributed to the π-π∗ electronic transitions of the conjugated structures, while the longer wavelength absorption can be attributed to the intramolecular charge transfer transition (ICT) inside the monomers containing electron-withdrawing unit BDP (A) and electron-donating unit (D) phenyl or thiophene rings
Summary
Based on intermolecular non-covalent interactions, supramolecular chemistry has become one of the most interesting fields in modern chemistry (Lehn, 2002). 2,2′:6′,2′′-Terpyridine is a tridentate ligand which could form stable complexes by coordinating with a wide range of transition metal ions in their low oxidation states based on strong metal-lignd (d-π∗) back donation (Wild et al, 2011). These complexes possess a distorted octahedral geometry and thereby a linear bilateral conformation of ligands can be obtained, which is critical in construction of metallo-supramolecular polymers and well-defined architectures based on the coordination interactions between terpyridine and metal center (Pandey et al, 2016; Winter and Schubert, 2016; Yin et al, 2018). The polymers showed very attractive properties, and full characteristics have been carried out
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