Tuning the electronic properties of hexanuclear cobalt sulfide superatoms via ligand substitution

Liu, Gaoxiang; Pinkard, Andrew; Ciborowski, Sandra M.; Chauhan, Vikas; Zhu, Zhaoguo; Aydt, Alexander P.; Khanna, Shiv N.; Roy, Xavier; Bowen, Kit H.

doi:10.1039/c8sc03862g

Title: Tuning the electronic properties of hexanuclear cobalt sulfide superatoms via ligand substitution

Journal Article · Tue Jan 01 00:00:00 EST 2019 · Chemical Science

DOI:https://doi.org/10.1039/c8sc03862g· OSTI ID:1624968

^[1]; Pinkard, Andrew ^[2];

^[1]; Chauhan, Vikas ^[3]; Zhu, Zhaoguo ^[1]; Aydt, Alexander P. ^[2];

^[3];

^[2]; Bowen, Kit H. ^[1]

Department of Chemistry; Johns Hopkins University; Baltimore; USA
Department of Chemistry; Columbia University; New York; USA
Department of Physics; Virginia Commonwealth University; Richmond; USA

Molecular clusters are attractive superatomic building blocks for creating materials with tailored properties due to their unique combination of atomic precision, tunability and functionality. The ligands passivating these superatomic clusters offer an exciting opportunity to control their electronic properties while preserving their closed shells and electron counts, which is not achievable in conventional atoms. Here we demonstrate this concept by measuring the anion photoelectron spectra of a series of hexanuclear cobalt sulfide superatomic clusters with different ratios of electron-donating and electron-withdrawing ligands, Co₆S₈(PEt₃)_6-x(CO)_x (x = 0–3). We find that Co₆S₈(PEt₃)₆ has a low electron affinity (EA) of 1.1 eV, and that the successive replacement of PEt3 ligands with CO gradually shifts its electronic spectrum to lower energy and increases its EA to 1.8 eV. Density functional theory calculations reveal that the increase of EA results from a monotonic lowering of the cluster highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO). Our work provides unique insights into the electronic structure and tunability of superatomic building blocks.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Energy Research Scientific Computing Center; Office of Naval Research (ONR), Multidisciplinary University Research Initiative (MURI); US Air Force Office of Scientific Research (AFOSR); National Science Foundation (NSF)

Grant/Contract Number:: AC02-05CH11231; N00014-15-1-2681; FA9550-15-1-0259; DMR-1420634; FA9550-18-1-0020; FA9550-18-1-0511

OSTI ID:: 1624968

Journal Information:: Chemical Science, Vol. 10, Issue 6; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 20 works

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