TY - JOUR
T1 - 4-Coinage Metal Tetrahedral Superatoms as Useful Building Blocks Related to Pyramidal Au20 Clusters (M = Cu, Ag, Au). Electronic and Bonding Properties from Relativistic DFT Calculations
T2 - Coinage Metal Tetrahedral Superatoms as Useful Building Blocks Related to Pyramidal Au20 Clusters (M = Cu, Ag, Au). Electronic and Bonding Properties from Relativistic DFT Calculations
AU - Gam, Franck
AU - Arratia-Pérez, Ramiro
AU - Kahlal, Samia
AU - Saillard, Jean Yves
AU - Muñoz-Castro, Alvaro
N1 - Funding Information:
The authors are thankful for financial support from FONDECYT 1180683, 1140359, and 1150629 and MILLENNIUM Project RC12001 grants. The authors acknowledge the GENCI French national computer resource (a0010807367). This research has been performed as part of the Chilean−French International Associated Laboratory for “Multifunctional Molecules and Materials” (LIA-CNRS N°1027). F.G. thanks the Reǵ ion Bretagne (ARED NANOCLU) and the Universidad Andreś Bello for a joint Ph.D. studentship.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/3/1
Y1 - 2018/3/1
N2 - Characterization of the tetrahedral Au20 structure in the gas phase remains a major landmark in gold cluster chemistry, where further efforts to stabilize this bare 20-electron superatom in solution to extend and understand its chemistry have failed so far. Here, we account for the structural, electronic, and bonding properties of [M16Ni24(CO)40]4- (M = Cu, Ag, Au) observed in solution for gold and silver. Our results show a direct electronic relationship with Au20, owing that such species share a common tetrahedral [M16]4- central core with a 1S21P61D102S2 jellium configuration. In the case of Au20, the [Au16]4- core is capped by four Au+ ions, whereas in [M16Ni24(CO)40]4- it is capped by four Ni6(CO)10 units. In both cases, the capping entities are a full part of the superatom entity, where it appears that the free (uncapped) [M16]4- species must be capped for further stabilization. It follows that the Ni6(CO)10 units in [M16Ni24(CO)40]4- should not be considered as external ligands as their bonding with the [M16]4- core is mainly associated with a delocalization of the 20 jellium electrons onto the Ni atoms. Thus, the [M16Ni24(CO)40]4- species can be seen as the solution version of tetrahedral M20 clusters, encouraging experimental efforts to further develop the chemistry of such complexes as M(111) finite surface section structures, with M = Ag and Au and, particularly promising, with M = Cu. Furthermore, optical properties were simulated to assist future experimental characterization.
AB - Characterization of the tetrahedral Au20 structure in the gas phase remains a major landmark in gold cluster chemistry, where further efforts to stabilize this bare 20-electron superatom in solution to extend and understand its chemistry have failed so far. Here, we account for the structural, electronic, and bonding properties of [M16Ni24(CO)40]4- (M = Cu, Ag, Au) observed in solution for gold and silver. Our results show a direct electronic relationship with Au20, owing that such species share a common tetrahedral [M16]4- central core with a 1S21P61D102S2 jellium configuration. In the case of Au20, the [Au16]4- core is capped by four Au+ ions, whereas in [M16Ni24(CO)40]4- it is capped by four Ni6(CO)10 units. In both cases, the capping entities are a full part of the superatom entity, where it appears that the free (uncapped) [M16]4- species must be capped for further stabilization. It follows that the Ni6(CO)10 units in [M16Ni24(CO)40]4- should not be considered as external ligands as their bonding with the [M16]4- core is mainly associated with a delocalization of the 20 jellium electrons onto the Ni atoms. Thus, the [M16Ni24(CO)40]4- species can be seen as the solution version of tetrahedral M20 clusters, encouraging experimental efforts to further develop the chemistry of such complexes as M(111) finite surface section structures, with M = Ag and Au and, particularly promising, with M = Cu. Furthermore, optical properties were simulated to assist future experimental characterization.
UR - http://www.scopus.com/inward/record.url?scp=85042764535&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcc.8b00227
DO - 10.1021/acs.jpcc.8b00227
M3 - Article
AN - SCOPUS:85042764535
SN - 1932-7447
VL - 122
SP - 4723
EP - 4730
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 8
ER -