CNMS Staff Science Highlight

1. CNMS Staff Science Highlight In Situ Formation of Pyridyl-Functionalized Poly(3-hexylthiophene)s via Quenching of the Grignard Metathesis Polymerization: Toward Ligands for Semiconductor Quantum Dots Scientific Achievement Demonstrated a facile one-pot method for preparing functional materials based on pyridyl-terminated poly(3-hexylthiophenese) (P3HTs). The pyridyl-functionalized P3HTs efficiently decorate CdSesemiconductor quantum dots (SQDs) and stabilize the morphology of CdSe/P3HT blends after thermal annealing. Significance This work establishes a “materials by design” approach, wherein theory, synthesis, and characterization are used to rationally design new materials for optoelectronic applications. The ability to manipulate end group compositions coupled with the propensity of pyridyl-functionalized P3HTs to ligate SQDs enables tuning the morphology of conjugated polymer/SQD blends to achieve improved hybrid photovoltaic materials. TEM micrographs of thin films consisting of 20 wt % surface-modified CdSe SQDs in a P3HT matrix (Mn = 25 kDa) showing arrest of CdSe aggregation for the pryidyl-funtionalized P3HT sample (right panel) vs native dodecyl-phosphonic acid ligand (left panel). Research Details • CNMS capability: Novel polymer synthesis and characterizations for the development of new soft materials. • Density functional theory calculations for guiding the selection of optimal end groups. • Pyridyl-functionalized P3HTs for ligands to decorate CdSe SQDs for stabilizing blend morphology. Binding energies calculated using density functional theory (DFT) were used to guide selection of pyridyl end groups for synthetic development. W. Michael Kochemba, Deanna L. Pickel, Bobby G. Sumpter, Jihua Chen, S. Michael Kilbey, Chem. Mater. DOI: 10.1021/cm302915hr.