Bulky adamantanethiolate and cyclohexanethiolate ligands favor smaller gold nanoparticles with altered discrete sizes.
Use of bulky ligands (BLs) in the synthesis of metal nanoparticles (NPs) gives smaller core sizes, sharpens the size distribution, and alters the discrete sizes. For BLs, the highly curved surface of small NPs may facilitate growth, but as the size increases and the surface flattens, NP growth may terminate when the ligand monolayer blocks BLs from transporting metal atoms to the NP core. Batches of thiolate-stabilized Au NPs were synthesized using equimolar amounts of 1-adamantanethiol (AdSH), cyclohexanethiol (CySH), or n-hexanethiol (C6SH). The bulky CyS- and AdS-stabilized NPs have smaller, more monodisperse sizes than the C6S-stabilized NPs. As the bulkiness increases, the near-infrared luminescence intensity increases, which is characteristic of small Au NPs. Four new discrete sizes were measured by MALDI-TOF mass spectrometry, Au(30)(SAd)(18), Au(39)(SAd)(23), Au(65)(SCy)(30), and Au(67)(SCy)(30). No Au(25)(SAd)(18) was observed, which suggests that this structure would be too sterically crowded. Use of BLs may also lead to the discovery of new discrete sizes in other systems.
Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695, USA.
Peter J
PJ
Krommenhoek
Junwei
J
Wang
Nathaniel
N
Hentz
Aaron C
AC
Johnston-Peck
Krystian A
KA
Kozek
Gregory
G
Kalyuzhny
Joseph B
JB
Tracy
D000218:Adamantane; D003460:Crystallization / Q000379:methods; D003510:Cyclohexanes / Q000737:chemistry*; D006046:Gold / Q000737:chemistry*; D008024:Ligands; D046911:Macromolecular Substances / Q000737:chemistry; D008422:Materials Testing; D008968:Molecular Conformation; D053758:Nanoparticles / Q000737:chemistry* / Q000648:ultrastructure*; D010316:Particle Size; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013499:Surface Properties
D003510:Cyclohexanes; D008024:Ligands; D046911:Macromolecular Substances; D013438:Sulfhydryl Compounds; D006046:Gold; D000218:Adamantane