文摘
To understand the structure鈥損roperty relationship in functional macromolecules through side chain modulation, both the accurate determination of the position of modifiable groups along the polymer chain and their subsequent modifications using high fidelity methods are crucial. In this report, the polymer microstructure of a helical alkyne polycarbodiimide has directly been probed through 15N NMR spectroscopy on isotopic labeled poly(N-(3-ethynylphenyl)-15N鈥?hexyl)carbodiimide and found to be a highly regioregular polymer structure. This polymer undergoes facile and quantitative CuAAC 鈥渃lick鈥?chemistry, yielding perfectly alternating functional polymers. Advances have been made through the synthesis of new optically active alkyne polycarbodiimides with two independently modifiable pendant groups per repeat unit of polymers. Orthogonal postmodifications of the pendant groups were then performed to incorporate two different sets of small molecules in the repeat unit of polymers in a controlled manner and under mild reaction conditions using either sequential CuAAC 鈥渃lick鈥?reactions when two dissimilar alkyne groups are present or a combination of CuAAC and thiol鈥揺ne click chemistries when pendant groups bear alkyne and vinyl moieties.