Abstract
The possibility of prescribing local interactions between nano- and microscopic components that direct them to assemble in a predictable fashion is a central goal of nanotechnology research. In this article, we advance a new paradigm in which the self-assembly of DNA-functionalized colloidal particles is programmed using linker oligonucleotides dispersed in solution. We find a phase diagram that is surprisingly rich compared to phase diagrams typical of other DNA-functionalized colloidal particles that interact by direct hybridization, including a reentrant melting transition upon increasing linker concentration, and show that multiple linker species can be combined to prescribe many interactions simultaneously. A new theory predicts the observed phase behavior quantitatively without any fitting parameters. Taken together, these experiments and model lay the groundwork for future research in programmable self-assembly, enabling the possibility of programming the hundreds of specific interactions needed to assemble fully addressable, mesoscopic structures, while also expanding our fundamental understanding of the unique phase behavior possible in colloidal suspensions.