Intimate organic–inorganic nanocomposites via rationally designed conjugated polymer-grafted precursors

Semiconducting organic-inorganic nanocomposites comprising the conjugated polymer poly(3-hexylthiophene) (P3HT) in intimate contact with CdSe nanocrystals were crafted by exploiting rationally designed P3HT-grafted cadmium precursors (i.e., Cd-P3HT complexes). The bifunctional ligand 4-bromobenzyl phosphonic acid (BPA-Br) that possesses two terminal functional groups at each end was employed, enabling the coordination of BPA-Br with Cd first to yield Cd-phosphonic acid complexes (Cd-BPA-Br) followed by the subsequent substitution of the bromide moiety into the azide (N3) group to form N3-functionalized Cd-phosphonic acid complexes (Cd-BPA-N3). Cd-P3HT complexes were then synthesized via a click reaction between Cd-BPA-N3 and ethynyl-terminated P3HT (P3HT-[triple bond, length as m-dash]). The success of the click reaction was confirmed by spectroscopic measurements. The morphology of CdSe nanocrystals (i.e., quantum dot and multi-branched) in P3HT-CdSe nanocrystal nanocomposites can be altered by tuning the concentration of Cd-P3HT complexes and the addition of excess Cd-BPA-Br (i.e., Cd-P3HT solely for the synthesis of CdSe quantum dots, and Cd-P3HT and Cd-BPA-Br at the ratio Cd-P3HT : Cd-BPA-Br = 1 : 1 for the synthesis of multi-branched CdSe nanocrystals). The photophysical properties of the resulting P3HT-CdSe nanocomposites were examined via absorption and photoluminescence studies. In comparison with P3HT-[triple bond, length as m-dash], the significant emission quenching of nanocomposites suggested the efficient charge transfer at the P3HT/CdSe interface. It is noteworthy that the implementation of judiciously synthesized Cd-P3HT complexes as precursors rendered the in situ synthesis of P3HT-CdSe nanocrystal nanocomposites, dispensing with the need for the use of insulating aliphatic ligands and tedious ligand exchange procedures for the preparation of functional polymer-tethered nanocrystals.