Abstract
Organic/inorganic hybrid nanoscale materials possess fascinating optical, electronic, magnetic, and catalytic properties that are promising for a variety of practical applications. Such properties can be dramatically affected by the hierarchical structure and molecular organization in the nanomaterials. Herein, we employed surface-initiated Kumada catalyst-transfer polymerization to prepare hybrid materials consisting of shells of conjugated polymers (CPs) - polythiophene or poly(p-phenylene) - and their block copolymers covalently attached to the surface of silica nanoparticles. Because of the controlled chain-growth mechanism of surface-initiated polymerization, we obtained structurally well-defined CP blocks in the diblock copolymer shells, which produced distinct spectroscopic properties related to the intraparticle excitation energy transfer between the nanoscale polymer shell components, as well as the formation of interfacial exciplex states. The spectroscopic phenomena were further understood via time-resolved transient absorption spectroscopy studies. Overall, the surface-initiated polymerization provided an efficient tool to prepare structurally defined and highly stable organic polymer shell-inorganic core nanoparticles with tunable spectroscopic characteristics not achievable from corresponding single-component systems.
| Original language | English |
|---|---|
| Pages (from-to) | 6963-6975 |
| Number of pages | 13 |
| Journal | Journal of Physical Chemistry C |
| Volume | 122 |
| Issue number | 12 |
| DOIs | |
| State | Published - Mar 29 2018 |
| Externally published | Yes |
Funding
This research was supported by the U.S. Department of Energy under EPSCoR grant no. DE-SC0012432 with additional support from the Louisiana Board of Regents. The initial synthetic studies were supported by the National Science Foundation (grant DMR-1006336). C.R. acknowledges the Hightower Family Fund (School of Materials Science and Engineering, Georgia Tech). Kind appreciation is due to Ying Xiao (LSU Shared Instrumentation Facility) and Dr. Jibao He (Tulane University Coordinated Instrumentation Facility) for help with electron microscopy imaging and Dr. Rafael Cueto (LSU Chemistry Department) for helping with TGA experiments. We also acknowledge Carrie Gao for general help with EQ-SANS beamline at the Oak Ridge National Laboratory (ORNL). The research at ORNL Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences U.S. Department of Energy. This research was supported by the U.S. Department of Energy under EPSCoR grant no. DE-SC0012432 with additional support from the Louisiana Board of Regents. The initial synthetic studies were supported by the National Science Foundation (grant DMR-1006336). C.R. acknowledges the Hightower Family Fund (School of Materials Science and Engineering, Georgia Tech). Kind appreciation is due to Ying Xiao (LSU Shared Instrumentation Facility) and Dr. Jibao He (Tulane University Coordinated Instrumentation Facility) for help with electron microscopy imaging and Dr. Rafael Cueto (LSU Chemistry Department) for helping with TGA experiments. We also acknowledge Carrie Gao for general help with EQ-SANS beamline at the Oak Ridge National Laboratory (ORNL). The research at ORNL Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy.
| Funders | Funder number |
|---|---|
| Hightower Family Fund | |
| Office of Basic Energy Sciences | |
| Scientific User Facilities Division | |
| National Science Foundation | DMR-1006336 |
| U.S. Department of Energy | |
| Office of Experimental Program to Stimulate Competitive Research | |
| Oak Ridge National Laboratory | |
| National Science Foundation |