The surface termination of a Fe (III) spin crossover molecular salt

Zaz, M. Zaid; Tamang, Binny; McElveen, Kayleigh; Mishra, Esha; Viswan, Gauthami; Chin, Wai Kiat; Subedi, Arjun; N’Daiye, Alpha T.; Lai, Rebecca Y.; Dowben, Peter A.

doi:10.1088/1361-648x/adaff9

Title: The surface termination of a Fe (III) spin crossover molecular salt

Journal Article · 12 February 2025 · Journal of Physics. Condensed Matter

DOI: https://doi.org/10.1088/1361-648x/adaff9 · OSTI ID:2530325

^[1]; Tamang, Binny ^[1]; McElveen, Kayleigh ^[1]; Mishra, Esha ^[2];

^[1];

^[3];

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Univ. of Nebraska, Lincoln, NE (United States)
Univ. of Nebraska, Lincoln, NE (United States); Berry College, Mount Berry, GA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

From a comparison of the known molecular stoichiometry and x-ray photoemission spectroscopy, it is evident that the Fe(III) spin crossover salt [Fe(qsal)₂Ni(dmit)₂] has a preferential surface termination with the Ni(dmit)₂ moiety, where qsal = N(8quinolyl)salicylaldimine, and dmit^2- = 1,3-dithiol-2-thione-4,5-dithiolato. This preferential surface termination leads to a significant surface to bulk core level shift for the Ni 2p x-ray photoemission core level, not seen in the corresponding Fe 2p core level spectra. A similar surface to bulk core level shift is seen in Pd 3d in the related [Fe(qsal)₂]₂Pd(dmit)₂. Inverse photoemission spectroscopy, compared with the x-ray absorption spectra at the Ni-L3,2 edge provides some indication of the density of states resulting from the dmit^2- = 1,3-dithiol-2-thione-4,5-dithiolato ligand unoccupied molecular orbitals and thus supports the evidence regarding surface termination in the Ni(dmit)₂ moiety.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2530325

Journal Information:: Journal of Physics. Condensed Matter, Journal Name: Journal of Physics. Condensed Matter Journal Issue: 13 Vol. 37; ISSN 0953-8984

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

References (33)

Practical surface analysis by Auger and X-ray photoelectron spectroscopy. D. Briggs and M. P. Seah (Editors). John Wiley and Sons Ltd, Chichester, 1983, 533 pp., £44.50 Castle, J. E. Surface and Interface Analysis, Vol. 6, Issue 6 https://doi.org/10.1002/sia.740060611	journal	December 1984
Quantitative analysis of the inelastic background in surface electron spectroscopy Tougaard, Sven Surface and Interface Analysis, Vol. 11, Issue 9 https://doi.org/10.1002/sia.740110902	journal	June 1988
ESCA studies of nitrogen-containing stainless steels Lim, A. S.; Atrens, A. Applied Physics A Solids and Surfaces, Vol. 51, Issue 5, p. 411-418 https://doi.org/10.1007/BF00348382	journal	November 1990
A Round Robin on combined electrochemical and AES/ESCA characterization of the passive films on Fe Cr and Fe Cr Mo alloys Marcus, P.; Olefjord, I. Corrosion Science, Vol. 28, Issue 6, p. 589-602 https://doi.org/10.1016/0010-938X(88)90026-1	journal	January 1988
Surface core level spectroscopy of transition metals: A new tool for the determination of their surface structure Spanjaard, Daniel; Guillot, Claude; Desjonquères, Marie-Catherine Surface Science Reports, Vol. 5, Issue 1-2 https://doi.org/10.1016/0167-5729(85)90003-2	journal	July 1985
Core-level binding-energy shifts at surfaces and in solids Egelhoff, W. F. Surface Science Reports, Vol. 6, Issue 6-8 https://doi.org/10.1016/0167-5729(87)90007-0	journal	May 1987
The metallicity of thin films and overlayers Dowben, P. A. Surface Science Reports, Vol. 40, Issue 6-8 https://doi.org/10.1016/S0167-5729(00)00010-8	journal	November 2000
Comparing inverse photoemission and X-ray absorption spectroscopies Borca, C. N.; Komesu, Takashi; Dowben, P. A. Journal of Electron Spectroscopy and Related Phenomena, Vol. 122, Issue 3 https://doi.org/10.1016/S0368-2048(01)00364-4	journal	March 2002
XPS/GIXS study of thin oxide films formed on the Fe-40 %Cr alloy with trace of manganese Suzuki, S. Scripta Materialia, Vol. 36, Issue 8 https://doi.org/10.1016/S1359-6462(96)00466-6	journal	April 1997
Crystal structure, magnetic properties and Mössbauer studies of [Fe(qsal)₂][Ni(dmit)₂] Faulmann, Christophe; Dorbes, Stéphane; Lampert, Stéphane Inorganica Chimica Acta, Vol. 360, Issue 13, p. 3870-3878 https://doi.org/10.1016/j.ica.2007.03.022	journal	October 2007
X-ray photoelectron spectroscopic studies of palladium oxides and the palladium-oxygen electrode Kim, K. S.; Gossmann, A. F.; Winograd, Nicholas. Analytical Chemistry, Vol. 46, Issue 2 https://doi.org/10.1021/ac60338a037	journal	February 1974
Investigation of the High-Temperature Spin-Transition of a Mononuclear Iron(II) Complex Using X-ray Photoelectron Spectroscopy Craze, Alexander R.; Howard-Smith, Kyle J.; Bhadbhade, Mohan M. Inorganic Chemistry, Vol. 57, Issue 11 https://doi.org/10.1021/acs.inorgchem.8b00576	journal	May 2018
Complexities in the Molecular Spin Crossover Transition Zhang, Xin; Mu, Sai; Chastanet, Guillaume The Journal of Physical Chemistry C, Vol. 119, Issue 28 https://doi.org/10.1021/acs.jpcc.5b02220	journal	June 2015
Light-Induced Spin Crossover in an Fe(II) Low-Spin Complex Enabled by Surface Adsorption Rohlf, Sebastian; Gruber, Manuel; Flöser, Benedikt M. The Journal of Physical Chemistry Letters, Vol. 9, Issue 7, p. 1491-1496 https://doi.org/10.1021/acs.jpclett.8b00338	journal	March 2018
Spin-State Patterning in an Iron(II) Tripodal Spin-Crossover Complex Li, Li; Neville, Suzanne M.; Craze, Alexander R. ACS Omega, Vol. 2, Issue 7 https://doi.org/10.1021/acsomega.7b00630	journal	July 2017
Electrical Conductivity Modulation Coupled to a High-Spin−Low-Spin Conversion in the Molecular System [Fe ^III (qsal) ₂ ][Ni(dmit) ₂ ] ₃ ·CH ₃ CN·H ₂ O Takahashi, Kazuyuki; Cui, Heng-Bo; Okano, Yoshinori Inorganic Chemistry, Vol. 45, Issue 15 https://doi.org/10.1021/ic060852l	journal	July 2006
An ESCA study of the termination of the passivation of elemental metals Barr, Tery L. The Journal of Physical Chemistry, Vol. 82, Issue 16 https://doi.org/10.1021/j100505a006	journal	August 1978
Direct monitoring of spin transitions in a dinuclear triple-stranded helicate iron(ii) complex through X-ray photoelectron spectroscopy Li, Li; Craze, Alexander R.; Akiyoshi, Ryohei Dalton Transactions, Vol. 47, Issue 8 https://doi.org/10.1039/C7DT04190J	journal	January 2018
Room temperature control of spin states in a thin film of a photochromic iron( ii ) complex Poggini, Lorenzo; Milek, Magdalena; Londi, Giacomo Materials Horizons, Vol. 5, Issue 3 https://doi.org/10.1039/C7MH01042G	journal	January 2018
Probing the unpaired Fe spins across the spin crossover of a coordination polymer Ekanayaka, Thilini K.; Kurz, Hannah; Dale, Ashley S. Materials Advances, Vol. 2, Issue 2 https://doi.org/10.1039/D0MA00612B	journal	January 2021
Evidence for surface effects on the intermolecular interactions in Fe(ii) spin crossover coordination polymers Ekanayaka, Thilini K.; Kurz, Hannah; McElveen, Kayleigh A. Physical Chemistry Chemical Physics, Vol. 24, Issue 2 https://doi.org/10.1039/D1CP04243B	journal	January 2022
A complementary characterisation technique for spin crossover materials; the application of X-ray photoelectron spectroscopy for future device applications Craze, Alexander R.; Marjo, Christopher E.; Li, Feng Dalton Transactions, Vol. 51, Issue 2, p. 428-441 https://doi.org/10.1039/D1DT03446D	journal	November 2021
Electronic structure of cobalt valence tautomeric molecules in different environments Mishra, Esha; Ekanayaka, Thilini K.; Panagiotakopoulos, Theodoros Nanoscale, Vol. 15, Issue 5 https://doi.org/10.1039/D2NR06834F	journal	January 2023
Surface stabilisation of the high-spin state of Fe(ii) spin-crossover complexes Serra, Alejandro Martínez; Dhingra, Archit; Asensio, María Carmen Physical Chemistry Chemical Physics, Vol. 25, Issue 21, p. 14736-14741 https://doi.org/10.1039/D3CP00863K	journal	January 2023
Is the surface of Hofmann-like spin-crossover {Fe(pz)[Pt(CN)₄]} the same as its bulk? Martínez Serra, Alejandro; Dhingra, Archit; Asensio, María Carmen Dalton Transactions, Vol. 52, Issue 30, p. 10305-10309 https://doi.org/10.1039/D3DT01955A	journal	July 2023
Iron(ii) spin crossover films on Au(111): scanning probe microscopy and photoelectron spectroscopy Pronschinske, Alex; Bruce, Robert C.; Lewis, Geoff Chemical Communications, Vol. 49, Issue 89 https://doi.org/10.1039/c3cc44904a	journal	January 2013
Inverse photoemission Smith, N. V. Reports on Progress in Physics, Vol. 51, Issue 9 https://doi.org/10.1088/0034-4885/51/9/003	journal	September 1988
High-Resolution X-Ray Photoemission Spectrum of the Valence Bands of Gold Shirley, D. A. Physical Review B, Vol. 5, Issue 12 https://doi.org/10.1103/PhysRevB.5.4709	journal	June 1972
Core-Level Binding Energy and Density of States from the Surface Atoms of Gold Citrin, P. H.; Wertheim, G. K.; Baer, Y. Physical Review Letters, Vol. 41, Issue 20 https://doi.org/10.1103/PhysRevLett.41.1425	journal	November 1978
Direct Observation of 4ƒ Splitting between (110) Surface and Bulk Atoms of W Duc, Tran Minh; Guillot, C.; Lassailly, Y. Physical Review Letters, Vol. 43, Issue 11, p. 789-792 https://doi.org/10.1103/PhysRevLett.43.789	journal	September 1979
Recent advances in x‐ray photoelectron spectroscopy studies of oxides Barr, Tery L. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 9, Issue 3 https://doi.org/10.1116/1.577464	journal	May 1991
Photoemission Study of Temperature-Induced and Photoinduced Spin-State Transitions in Spin-Crossover Complex [Fe(ptz) ₆ ](BF ₄ ) ₂ Son, Jin-Young; Takubo, Kou; Asakura, Daisuke Journal of the Physical Society of Japan, Vol. 76, Issue 8 https://doi.org/10.1143/JPSJ.76.084703	journal	August 2007
Resistance to Pitting and Chemical Composition of Passive Films of a Fe‐17%Cr Alloy in Chloride‐Containing Acid Solution Yang, W. P.; Costa, D.; Marcus, P. Journal of The Electrochemical Society, Vol. 141, Issue 10, p. 2669-2676 https://doi.org/10.1149/1.2059166	journal	October 1994

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