Composition Determination of Heterometallic Trinuclear Clusters via Anomalous X-ray and Neutron Diffraction

Cristin E. Juda; Claire E. Casaday; Justin J. Teesdale; Amymarie K. Bartholomew; Benjamin Lin; Kurtis M. Carsch; Rebecca A. Musgrave; Shao Liang Zheng; Xiaoping Wang; Christina M. Hoffmann; Su Yin Wang; Yu Sheng Chen; Theodore A. Betley

doi:10.1021/jacs.4c10226

Composition Determination of Heterometallic Trinuclear Clusters via Anomalous X-ray and Neutron Diffraction

Cristin E. Juda, Claire E. Casaday, Justin J. Teesdale, Amymarie K. Bartholomew, Benjamin Lin, Kurtis M. Carsch, Rebecca A. Musgrave, Shao Liang Zheng, Xiaoping Wang, Christina M. Hoffmann, Su Yin Wang, Yu Sheng Chen, Theodore A. Betley

Single Crystal Diffraction

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

Abstract

Anomalous X-ray diffraction (AXD) and neutron diffraction can be used to crystallographically distinguish between metals of similar electron density. Despite the use of AXD for structural characterization in mixed metal clusters, there are no benchmark studies evaluating the accuracy of AXD toward assessing elemental occupancy in molecules with comparisons with what is determined via neutron diffraction. We collected resonant diffraction data on several homo and heterometallic clusters and refined their anomalous scattering components to determine metal site occupancies. Theoretical resonant scattering terms for Fe⁰, Co⁰, and Zn⁰ were compared against experimental values, revealing theoretical values are ill-suited to serve as references for occupancy determination. The cluster featuring distinct cation and anion metal compositions [CoCp₂*][(^tbsL)Fe₃(μ³-NAr)] was used to assess the accuracy of different f′ references for occupancy determination (f′_theoretical ± 15-17%; f′_experimental ± 10%). This methodology was applied toward calculating the occupancy of three different clusters: (^tbsL)Fe₂Zn(py) (6), (^tbsL)Fe₂Zn(μ³-NAr)(py) (7), and [CoCp*₂][(^tbsL)Fe₂Zn(μ³-NAr)] (8). The first two clusters maintain 100% Fe/Zn site isolation, whereas 8 showed metal mixing within the sites. The large crystal size of 8 enabled collection of neutron diffraction data which was compared against the results found with AXD. The ability of AXD to replicate the metal occupancies as determined by neutron diffraction supports the AXD occupancy methodology developed herein. Furthermore, the advantages innate to AXD (e.g., smaller crystal sizes, shorter collection times, and greater availability of synchrotron resources) versus neutron diffraction further support the need for its development as a standard technique.

Original language	English
Pages (from-to)	30320-30331
Number of pages	12
Journal	Journal of the American Chemical Society
Volume	146
Issue number	44
DOIs	https://doi.org/10.1021/jacs.4c10226
State	Published - Nov 6 2024

Funding

C.E.J., C.E.C., and K.M.C. thank the NSF for Predoctoral Fellowships. K.M.C. acknowledges the Fannie & John Hertz Foundation for a predoctoral fellowship. A.K.B. is grateful for support from a Smith Family Graduate Science and Engineering Fellowship. R.A.M. gratefully acknowledges postdoctoral support from the European Union\u2019s Horizon 2020 Research and Innovation Programme under grant agreement no. 752684. T.A.B. acknowledges support through grants from the NIH (GM-098395), DOE (DE-SC0008313), NSF (CHE-2247817), and Harvard University. We thank the support from the X-ray core facility at Harvard University of the Major Research Instrumentation (MRI) Program of the National Science Foundation (NSF) under Award Numbers 2216066. Crystallographic data for 1 and 3 were obtained at ChemMatCARS Sector 15 at the Advanced Photon Source (APS). APS is a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract no. DE-AC02-06CH11357. ChemMatCARS Sector 15 is supported by the National Science Foundation under grant number NSF/CHE-1834750. This research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The beam time was allocated to BL012, the TOPAZ single crystal TOF Laue diffractometer on proposal number IPTS-19168.1. This work was adapted in part from the thesis work submitted by C.E.J., Harvard University.

Funders	Funder number
Harvard University of the Major Research Instrumentation
Harvard University
Hertz Foundation
Office of Science
Materials Research Institute, Pennsylvania State University
Oak Ridge National Laboratory	IPTS-19168.1
Oak Ridge National Laboratory
National Science Foundation	2216066
National Science Foundation
National Institutes of Health	GM-098395
National Institutes of Health
Horizon 2020 Framework Programme	752684
Horizon 2020 Framework Programme
U.S. Department of Energy	CHE-2247817, DE-SC0008313
U.S. Department of Energy
Argonne National Laboratory	DE-AC02-06CH11357, NSF/CHE-1834750
Argonne National Laboratory

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Juda, C. E., Casaday, C. E., Teesdale, J. J., Bartholomew, A. K., Lin, B., Carsch, K. M., Musgrave, R. A., Zheng, S. L., Wang, X., Hoffmann, C. M., Wang, S. Y., Chen, Y. S., & Betley, T. A. (2024). Composition Determination of Heterometallic Trinuclear Clusters via Anomalous X-ray and Neutron Diffraction. Journal of the American Chemical Society, 146(44), 30320-30331. https://doi.org/10.1021/jacs.4c10226

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title = "Composition Determination of Heterometallic Trinuclear Clusters via Anomalous X-ray and Neutron Diffraction",

abstract = "Anomalous X-ray diffraction (AXD) and neutron diffraction can be used to crystallographically distinguish between metals of similar electron density. Despite the use of AXD for structural characterization in mixed metal clusters, there are no benchmark studies evaluating the accuracy of AXD toward assessing elemental occupancy in molecules with comparisons with what is determined via neutron diffraction. We collected resonant diffraction data on several homo and heterometallic clusters and refined their anomalous scattering components to determine metal site occupancies. Theoretical resonant scattering terms for Fe0, Co0, and Zn0 were compared against experimental values, revealing theoretical values are ill-suited to serve as references for occupancy determination. The cluster featuring distinct cation and anion metal compositions [CoCp2*][(tbsL)Fe3(μ3-NAr)] was used to assess the accuracy of different f′ references for occupancy determination (f′theoretical ± 15-17%; f′experimental ± 10%). This methodology was applied toward calculating the occupancy of three different clusters: (tbsL)Fe2Zn(py) (6), (tbsL)Fe2Zn(μ3-NAr)(py) (7), and [CoCp*2][(tbsL)Fe2Zn(μ3-NAr)] (8). The first two clusters maintain 100% Fe/Zn site isolation, whereas 8 showed metal mixing within the sites. The large crystal size of 8 enabled collection of neutron diffraction data which was compared against the results found with AXD. The ability of AXD to replicate the metal occupancies as determined by neutron diffraction supports the AXD occupancy methodology developed herein. Furthermore, the advantages innate to AXD (e.g., smaller crystal sizes, shorter collection times, and greater availability of synchrotron resources) versus neutron diffraction further support the need for its development as a standard technique.",

author = "Juda, {Cristin E.} and Casaday, {Claire E.} and Teesdale, {Justin J.} and Bartholomew, {Amymarie K.} and Benjamin Lin and Carsch, {Kurtis M.} and Musgrave, {Rebecca A.} and Zheng, {Shao Liang} and Xiaoping Wang and Hoffmann, {Christina M.} and Wang, {Su Yin} and Chen, {Yu Sheng} and Betley, {Theodore A.}",

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Juda, CE, Casaday, CE, Teesdale, JJ, Bartholomew, AK, Lin, B, Carsch, KM, Musgrave, RA, Zheng, SL, Wang, X , Hoffmann, CM, Wang, SY, Chen, YS & Betley, TA 2024, 'Composition Determination of Heterometallic Trinuclear Clusters via Anomalous X-ray and Neutron Diffraction', Journal of the American Chemical Society, vol. 146, no. 44, pp. 30320-30331. https://doi.org/10.1021/jacs.4c10226

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T1 - Composition Determination of Heterometallic Trinuclear Clusters via Anomalous X-ray and Neutron Diffraction

AU - Juda, Cristin E.

AU - Casaday, Claire E.

AU - Teesdale, Justin J.

AU - Bartholomew, Amymarie K.

AU - Lin, Benjamin

AU - Carsch, Kurtis M.

AU - Musgrave, Rebecca A.

AU - Zheng, Shao Liang

AU - Wang, Xiaoping

AU - Hoffmann, Christina M.

AU - Wang, Su Yin

AU - Chen, Yu Sheng

AU - Betley, Theodore A.

PY - 2024/11/6

Y1 - 2024/11/6

N2 - Anomalous X-ray diffraction (AXD) and neutron diffraction can be used to crystallographically distinguish between metals of similar electron density. Despite the use of AXD for structural characterization in mixed metal clusters, there are no benchmark studies evaluating the accuracy of AXD toward assessing elemental occupancy in molecules with comparisons with what is determined via neutron diffraction. We collected resonant diffraction data on several homo and heterometallic clusters and refined their anomalous scattering components to determine metal site occupancies. Theoretical resonant scattering terms for Fe0, Co0, and Zn0 were compared against experimental values, revealing theoretical values are ill-suited to serve as references for occupancy determination. The cluster featuring distinct cation and anion metal compositions [CoCp2*][(tbsL)Fe3(μ3-NAr)] was used to assess the accuracy of different f′ references for occupancy determination (f′theoretical ± 15-17%; f′experimental ± 10%). This methodology was applied toward calculating the occupancy of three different clusters: (tbsL)Fe2Zn(py) (6), (tbsL)Fe2Zn(μ3-NAr)(py) (7), and [CoCp*2][(tbsL)Fe2Zn(μ3-NAr)] (8). The first two clusters maintain 100% Fe/Zn site isolation, whereas 8 showed metal mixing within the sites. The large crystal size of 8 enabled collection of neutron diffraction data which was compared against the results found with AXD. The ability of AXD to replicate the metal occupancies as determined by neutron diffraction supports the AXD occupancy methodology developed herein. Furthermore, the advantages innate to AXD (e.g., smaller crystal sizes, shorter collection times, and greater availability of synchrotron resources) versus neutron diffraction further support the need for its development as a standard technique.

AB - Anomalous X-ray diffraction (AXD) and neutron diffraction can be used to crystallographically distinguish between metals of similar electron density. Despite the use of AXD for structural characterization in mixed metal clusters, there are no benchmark studies evaluating the accuracy of AXD toward assessing elemental occupancy in molecules with comparisons with what is determined via neutron diffraction. We collected resonant diffraction data on several homo and heterometallic clusters and refined their anomalous scattering components to determine metal site occupancies. Theoretical resonant scattering terms for Fe0, Co0, and Zn0 were compared against experimental values, revealing theoretical values are ill-suited to serve as references for occupancy determination. The cluster featuring distinct cation and anion metal compositions [CoCp2*][(tbsL)Fe3(μ3-NAr)] was used to assess the accuracy of different f′ references for occupancy determination (f′theoretical ± 15-17%; f′experimental ± 10%). This methodology was applied toward calculating the occupancy of three different clusters: (tbsL)Fe2Zn(py) (6), (tbsL)Fe2Zn(μ3-NAr)(py) (7), and [CoCp*2][(tbsL)Fe2Zn(μ3-NAr)] (8). The first two clusters maintain 100% Fe/Zn site isolation, whereas 8 showed metal mixing within the sites. The large crystal size of 8 enabled collection of neutron diffraction data which was compared against the results found with AXD. The ability of AXD to replicate the metal occupancies as determined by neutron diffraction supports the AXD occupancy methodology developed herein. Furthermore, the advantages innate to AXD (e.g., smaller crystal sizes, shorter collection times, and greater availability of synchrotron resources) versus neutron diffraction further support the need for its development as a standard technique.

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Composition Determination of Heterometallic Trinuclear Clusters via Anomalous X-ray and Neutron Diffraction

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