A1 Journal article (refereed)
Metal–ligand bond in group-11 complexes and nanoclusters (2024)

Sabooni Asre Hazer, M., Malola, S., & Häkkinen, H. (2024). Metal–ligand bond in group-11 complexes and nanoclusters. Physical Chemistry Chemical Physics, Advance Article. https://doi.org/10.1039/D4CP00848K

JYU authors or editors

Publication details

All authors or editors: Sabooni Asre Hazer, Maryam; Malola, Sami; Häkkinen, Hannu

Journal or series: Physical Chemistry Chemical Physics

ISSN: 1463-9076

eISSN: 1463-9084

Publication year: 2024

Publication date: 09/07/2024

Volume: Advance Article

Publisher: Royal Society of Chemistry (RSC)

Publication country: United Kingdom

Publication language: English

DOI: https://doi.org/10.1039/D4CP00848K

Publication open access: Openly available

Publication channel open access: Partially open access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/96494

Abstract

Density functional theory is used to study geometric, energetic, and electronic properties of metal–ligand bonds in a series of group-11 metal complexes and ligand-protected metal clusters. We study complexes as the forms of M–L (L = SCH3, SC8H9, PPh3, NHCMe, NHCEt, NHCiPr, NHCBn, CCMe, CCPh) and L1–M–L2 (L1 = NHCBn, PPh3, and L2 = CCPh). Furthermore, we study clusters denoted as [M13L6Br6]− (L = PPh3, NHCMe, NHCEt, NHCiPr, NHCBn). The systems were studied at the standard GGA level using the PBE functional and including vdW corrections via BEEF-vdW. Generally, Au has the highest binding energies, followed by Cu and Ag. PBE and BEEF-vdW functionals show the order Ag–L > Au–L > Cu–L for bond lengths in both M–L complexes and metal clusters. In clusters, the smallest side group (CH3) in NHCs leads to the largest binding energy whereas no significant variations are seen concerning different side groups of NHC in M–L complexes. By analyzing the projected density of states and molecular orbitals in complexes and clusters, the M–thiolate bonds were shown to have σ and π bond characteristics whereas phosphines and carbenes were creating σ bonds to the transition metals. Interestingly, this analysis revealed divergent behavior for M–alkynyl complexes: while the CCMe group displayed both σ and π bonding features, the CCPh ligand was found to possess only σ bond properties in direct head-to-head binding configuration. Moreover, synergetic effects increase the average binding strength to the metal atom significantly in complexes of two different ligands and underline the potential of adding Cu to synthesize structurally richer cluster systems. This study helps in understanding the effects of different ligands on the stability of M–L complexes and clusters and suggests that PPh3 and NHCs-protected Cu clusters are most stable after Au clusters.

Keywords: nanoparticles; coordination complexes; ligands; chemical bonds

Contributing organizations

Ministry reporting: Yes

Preliminary JUFO rating: 3