More Like this

1. Ru(II) Complexes with a Chemical and Redox-Active S ₂ N ₂ Ligand: Structures, Electrochemistry, and Metal–Ligand Cooperativity

   https://doi.org/10.1021/acs.organomet.7b00623  

   Durgaprasad, Gummadi; Luna, Javier A.; Spielvogel, Kyle D.; Haas, Christian; Shaw, Scott K.; Daly, Scott R. (October 2017, Organometallics)
2. Crystal structure of bulky-ligand-protected Au ₂₄ (S-C ₄ H ₉ ) ₁₆

   https://doi.org/10.1107/s2053229622006738  

   Wijesinghe, Kalpani Hirunika; Oliver, Allen G.; Dass, Amala (August 2022, Acta Crystallographica Section C Structural Chemistry)

   Atomically precise thiolate-protected gold nanomolecules have attracted interest due to their distinct electronic and chemical properties. The structure of these nanomolecules is important for understanding their peculiar properties. Here, we report the X-ray crystal structure of a 24-atom gold nanomolecule protected by 16 tert -butylthiolate ligands. The composition of Au 24 (S-C 4 H 9 ) 16 {poly[hexadecakis(μ- tert -butylthiolato)tetracosagold]} was confirmed by X-ray crystallography and electrospray ionization mass spectrometry (ESI–MS). The nanomolecule was synthesized in a one-phase synthesis and crystallized from a hexane–ethanol layered solution. The X-ray structure confirms the 16-atom core protected by two monomeric and two trimeric staples with four bridging ligands. The Au 24 (S-C 4 H 9 ) 16 cluster follows the shell-closing magic number of 8. 

   more » « less
3. Ligand exchange on Au ₃₈ (SR) ₂₄ : substituent site effects of aromatic thiols

   https://doi.org/10.1039/d0nr01430c  

   Li, Yingwei; Juarez-Mosqueda, Rosalba; Song, Yongbo; Zhang, Yuzhuo; Chai, Jinsong; Mpourmpakis, Giannis; Jin, Rongchao (May 2020, Nanoscale)

   Understanding the critical roles of ligands ( e.g. thiolates, SR) in the formation of metal nanoclusters of specific sizes has long been an intriguing task since the report of ligand exchange-induced transformation of Au 38 (SR) 24 into Au 36 (SR′) 24 . Herein, we conduct a systematic study of ligand exchange on Au 38 (SC 2 H 4 Ph) 24 with 21 incoming thiols and reveal that the size/structure preference is dependent on the substituent site. Specifically, ortho -substituted benzenethiols preserve the structure of Au 38 (SR) 24 , while para - or non-substituted benzenethiols cause its transformation into Au 36 (SR) 24 . Strong electron-donating or -withdrawing groups do not make a difference, but they will inhibit full ligand exchange. Moreover, the crystal structure of Au 38 (SR) 24 (SR = 2,4-dimethylbenzenethiolate) exhibits distinctive π⋯π stacking and “anagostic” interactions (indicated by substantially short Au⋯H distances). Theoretical calculations reveal the increased energies of frontier orbitals for aromatic ligand-protected Au 38 , indicating decreased electronic stability. However, this adverse effect could be compensated for by the Au⋯H–C interactions, which improve the geometric stability when ortho -substituted benzenethiols are used. Overall, this work reveals the substituent site effects based on the Au 38 model, and highlights the long-neglected “anagostic” interactions on the surface of Au-SR NCs which improve the structural stability. 

   more » « less
4. Surface ligand networking promotes intersystem crossing in the Au ₁₈ (SR) ₁₄ nanocluster

   https://doi.org/10.1039/D5NH00358J  

   He, Guiying; Liu, Zhongyu; Wang, Yitong; Sfeir, Matthew Y; Jin, Rongchao (January 2025, Nanoscale Horizons)

   The excited state behavior of Au₁₈(SR)₁₄nanoclusters can be controlled by tailoring the surface ligands; specifically, the aromatic ligands’ networking can promote the intersystem crossing in Au₁₈(SR)₁₄compared to the case of non-aromatic ligands. 

   more » « less
5. Post-Synthetic Doping and Ligand Engineering of Cs ₂ AgInCl ₆ Double Perovskite Nanocrystals

   https://doi.org/10.1021/acs.jpcc.3c05901  

   Dube, Lacie; Saghy, Peter; Chen, Ou (November 2023, The Journal of Physical Chemistry C)