TY - JOUR
T1 - Complete Ag4M2(DMSA)4 (M = Ni, Pd, Pt, DMSA = Dimercaptosuccinic Acid) Cluster Series
T2 - Optical Properties, Stability, and Structural Characterization
AU - Biltek, Scott R.
AU - Reber, Arthur C.
AU - Khanna, Shiv N.
AU - Sen, Ayusman
N1 - Funding Information:
The experimental work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences. The theoretical work (A.C.R., S.N.K.) was supported by the U.S. Department of Energy (DE-SC0006420). The authors gratefully acknowledge Dr. Hemant Yennawar for helpful discussions regarding Xray crystallography.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/7/20
Y1 - 2017/7/20
N2 - The cluster series Ag4M2(DMSA)4 (M = Ni, Pd, Pt) has been synthesized and the optical spectra and stability have been examined as a function of the metal, M. We have also obtained the structure of Ag4Ni2(DMSA)4 using X-ray crystallography, confirming the previously calculated structure. In the optical spectrum, there is a significant blue shift as the substituted metal M progresses down the periodic table. Theoretical calculations suggest that the blue shift is due to the lowering in energy of the d orbitals of the transition metal, M; however the expected metal-metal excitations are optically weak, and the spectra are dominated by metal-ligand excitations. The Ag4Pd2(DMSA)4 species has exceptionally high stability relative to the previously reported Ni and Pt analogues.
AB - The cluster series Ag4M2(DMSA)4 (M = Ni, Pd, Pt) has been synthesized and the optical spectra and stability have been examined as a function of the metal, M. We have also obtained the structure of Ag4Ni2(DMSA)4 using X-ray crystallography, confirming the previously calculated structure. In the optical spectrum, there is a significant blue shift as the substituted metal M progresses down the periodic table. Theoretical calculations suggest that the blue shift is due to the lowering in energy of the d orbitals of the transition metal, M; however the expected metal-metal excitations are optically weak, and the spectra are dominated by metal-ligand excitations. The Ag4Pd2(DMSA)4 species has exceptionally high stability relative to the previously reported Ni and Pt analogues.
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U2 - 10.1021/acs.jpca.7b04669
DO - 10.1021/acs.jpca.7b04669
M3 - Article
C2 - 28657753
AN - SCOPUS:85025593513
SN - 1089-5639
VL - 121
SP - 5324
EP - 5331
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 28
ER -