LEAPS-MPS: Covalent Hybridization of Atomically Precise Metal Nanoclusters

In this project, funded by the MPS-LEAPS (Launching Early-Career Academic Pathways) program and managed by the Division of Chemistry (CHE), Professor Hesari and his students at the State University of New York at Oswego will study the development of atomically precise metal nanoclusters (APMNCs), approximately 1-2 nm in size. These nanoclusters will be decorated with task-specific thiol ligands to form hybridized APMNCs. APMNCs have been used as catalysts, photocatalysts, and photoelectrocatalysts for important reactions such as carbon dioxide reduction, hydrogen production, and light emission via electrogenerated chemiluminescence (ECL). Their performance can be improved by creating networks that enhance electronic communication. However, the challenge so far has been to control the rational connection of APMNCs rather than allowing random assembly. Professor Hesari and his students will design and synthesize functionalized organothiol ligands that promote hybridization reactions. To achieve these objectives, they will use various synthesis methods to produce the targeted thiols and incorporate them into the APMNCs. Their research could reveal new insights into the fundamental properties of APMNCs’ self-assembled nanostructures.

Professor Hesari and his students will synthesize the designed thiol ligands and characterize them using various analytical techniques, such as proton and carbon nuclear magnetic resonance (NMR), infrared (IR) spectroscopy, UV-Visible spectroscopy, mass spectrometry, and electrochemistry. They will conduct the hybridization reactions under controlled conditions. The physicochemical and structural properties of the hybridized nanoclusters will be examined using techniques including single-crystal X-ray crystallography, NMR, UV-visible and fluorescence spectroscopy, mass spectrometry, and electrochemistry. Density functional theory (DFT) will be used to learn more about the electronic properties of the hybridized APMNCs. This approach paves the way for creating a new class of nanomaterials under controlled conditions, opening broad opportunities for applying these methods to other classes of nanomaterials. Additionally, the students involved in this project are gaining multidisciplinary experience, ranging from molecular synthesis to DFT calculations. This research is integrated with undergraduate and graduate courses at SUNY Oswego, designed to introduce students to nanomaterials design, synthesis, and their electronic and electrochemical properties for photoelectrochemical applications.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

Award Number: 2532484
Principal Investigator: Mahdi Hesari
Funds Obligated: $249,971
State: NY