Complete Ag4M2(DMSA)4 (M = Ni, Pd, Pt, DMSA = Dimercaptosuccinic Acid) Cluster Series: Optical Properties, Stability, and Structural Characterization

Scott R. Biltek; Arthur C. Reber; Shiv N. Khanna; Ayusman Sen

doi:10.1021/acs.jpca.7b04669

Complete Ag₄M₂(DMSA)₄ (M = Ni, Pd, Pt, DMSA = Dimercaptosuccinic Acid) Cluster Series: Optical Properties, Stability, and Structural Characterization

Scott R. Biltek
, Arthur C. Reber
, Shiv N. Khanna
, Ayusman Sen

Chemistry

Research output: Contribution to journal › Article › peer-review

10 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	5324-5331
Number of pages	8
Journal	Journal of Physical Chemistry A
Volume	121
Issue number	28
DOIs	https://doi.org/10.1021/acs.jpca.7b04669
State	Published - Jul 20 2017

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry

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10.1021/acs.jpca.7b04669

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@article{3d7827e17a194451a1ad5604ef71b75d,

title = "Complete Ag4M2(DMSA)4 (M = Ni, Pd, Pt, DMSA = Dimercaptosuccinic Acid) Cluster Series: Optical Properties, Stability, and Structural Characterization",

abstract = "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.",

author = "Biltek, \{Scott R.\} and Reber, \{Arthur C.\} and Khanna, \{Shiv N.\} and Ayusman Sen",

note = "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: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = jul,

day = "20",

doi = "10.1021/acs.jpca.7b04669",

language = "English (US)",

volume = "121",

pages = "5324--5331",

journal = "Journal of Physical Chemistry A",

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publisher = "American Chemical Society",

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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 -

Complete Ag₄M₂(DMSA)₄ (M = Ni, Pd, Pt, DMSA = Dimercaptosuccinic Acid) Cluster Series: Optical Properties, Stability, and Structural Characterization

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