1. ABOUT THE DATASET ------------ Title: Dataset supporting the article 'Determining structure and Zn-specific Lewis acid-base descriptors for diorganozincs in non-coordinating solvents using X-ray spectroscopy' Creator(s): Lewis G. Parker [1] orcid.org/0000-0001-8727-4116 and Kevin R. J. Lovelock[1] orcid.org/0000-0003-1431-269X. Organisation(s): [1] Department of Chemistry, University of Reading, Reading RG6 6DX, U.K. Rights-holder(s): Lewis G. Parker and University of Reading. Publication Year: 2025 Description: This compressed file is supplementary to the article cited in the 'Related publication' section below. Its contents are two-fold: (1) Experimental X-ray spectroscopy data (HERFD-XANES and R-/NR-VtC-XES) of multiple organozinc samples studied in the article, in .dat format which can be accessed using any text editor of choice (2) The output files of all the organozinc complexes studied computationally. These computational files will allow you to replicate the Density Functional Theory (DFT) ORCA calculations shown in the article. Cite as: L. G. Parker and K. R. J. Lovelock, 2025: Dataset supporting the article 'Determining structure and Zn-specific Lewis acid-base descriptors for diorganozincs in non-coordinating solvents using X-ray spectroscopy'. University of Reading. Dataset. https://doi.org/10.17864/1947.001460 Related publication: L. G. Parker, F. K. Towers Tompkins, J. M. Seymour, N. Oblewi, E. Gousseva, M. R. Daw, S. Hayama, R. P. Matthews, A. E. A. Fouda, J. D. Elliot, C. D. Smith and K. R. J. Lovelock, Comm. Chem., 2025, Submitted. Contact: Kevin R. J. Lovelock (k.r.j.lovelock@reading.ac.uk) 2. TERMS OF USE ------------ Copyright 2025 Lewis G. Parker and University of Reading. This dataset is licensed under a Creative Commons Attribution 4.0 International Licence: https://creativecommons.org/licenses/by/4.0/. 3. PROJECT AND FUNDING INFORMATION ------------ Title: Speciation of Organozinc Reagents: A Key Step Towards Understanding Reactivity Dates: Mar. 2020 - May. 2026 Funding organisation: The Royal Society Grant no.: RGF\EA\201064 Title: Quantifying Ion-Solvent Interactions Using X-Ray Photoelectron Spectroscopy Dates: Apr. 2022 - Mar. 2025 Funding organisation: The Royal Society Grant no.: URF\R\211005 Title: Electronic Structure of Liquid Phase Metal Complexes Dates: Jan. 2018 - Mar. 2025 Funding organisation: The Royal Society Grant no.: RGF\EA\180089 Title: Understanding Ionic Liquid Electrochemical Stability: Towards Superior Electrochemical Devices Dates: Oct. 2016 - Mar. 2022 Funding organisation: The Royal Society Grant no.: RGF\R1\180053 Title: X-ray Spectroscopy of Liquids: Quantifying Lewis Reactivity Dates: Feb. 2019 - Jan. 2023 Funding organisation: The Royal Society Grant no.: URF\R\150353 Title: University of Reading EPSRC ECR Equipment Bid Dates: Sep. 2018 - Jun. 2020 Funding organisation: EPSRC Grant no.: EP/S017828/1 Title: Various Diamond Light Source Beamtime Proposals Dates: Jan. 2020 - Jun. 2024 Funding organisation: Diamond Light Source Proposal no.: SP24305, SP28565, SP30597, SP33520, and SP36798 4. CONTENTS ------------ File listing This compressed file is organised into two main directories: '~/1.experiments' and '~/2.calculations'. -------- '~/1.experiments' This directory is further organised into three directories: '~/1.experiments/1.1.HERFD_XAS', '~/1.experiments/1.2.NR_VtC_XES' and '~/1.experiments/1.3.R_VtC_XES'. ------ '~/1.experiments/1.1.HERFD_XAS' This directory contains eleven directories which each contain the raw experimental data, in the form of .dat files, used to make the figures in the main article and supplementary information. Naming conventions of .dat files have not been changed from the initial experiment. 1. '0p1M_Et2Zn_hexane' --> 0.1 M ZnEt2 in hexane. Directory contains three .dat files 2. '0p1M_Et2Zn_toluene' --> 0.1 M ZnEt2 in toluene. Directory contains two .dat files 3. '0p1M_iPr2Zn_toluene --> 0.1 M Zn(i-Pr)2 in toluene. Directory contains two .dat files 4. '0p1M_Me2Zn_toluene' --> 0.1 M ZnMe2 in toluene. Directory contains four .dat files 5. '0p1M_Ph2Zn_toluene' --> 0.1 M ZnPh2 in toluene. Directory contains two .dat files 6. '0p1M_ZnCl2_H2O' --> 0.1 M ZnCl2 in water ([Zn(OH2)6]2+). Directory contains two .dat files 7. '0p1M_ZnCl2_THF' --> 0.1 M ZnCl2 in THF. Directory contains three .dat files 8. '0p1M_ZnTfO2_MeCN' --> 0.1 M ZnTfO2 in acetonitrile (Zn(NCMe)6]2+). Directory contains five .dat files 9. '0p033M_C6F5_2Zn_toluene --> 0.1 M Zn(C6F5)2 in toluene. Directory contains three .dat files 10. 'omimCl_ZnCl2_0pt33' --> x = 0.33 ZnCl2 in 1–octyl–3–methylimidazolium chloride ([ZnCl4]2-). Directory contains two .dat files 11. 'Zn_foil_reference' --> Solid Zn foil. Each .dat file contains the raw data required to make all of the graphs within the article and supplementary information. The HERFD-XA spectra were processed (average and normalised) using Athena from the Demeter software package and the .dat files can be opened using this software. --- '~/1.experiments/1.1.HERFD_XAS/Zn_foil_reference' This directory contains four directories which each contain the raw experimental data, in the form of .dat files, used as reference for HERFD-XAS experiments. Each of the directory name denotes a different beamtime experiment from which data was collected. 1. 'SP28565' Directory contains one .dat file 2. 'SP30597' Directory contains one .dat file 3. 'SP33520' Directory contains one .dat file 4. 'SP36798' Directory contains three .dat file ------ '~/1.experiments/1.2.NR_VtC_XES' This directory contains nine directories which each contain the raw experimental data, in the form of .dat files, used to make the figures in the main article and supplementary information. Naming conventions of .dat files have not been changed from the initial experiment. 1. '0p1M_Et2Zn_toluene' --> 0.1 M ZnEt2 in toluene. Directory contains three .dat files 2. '0p1M_iPr2Zn_toluene --> 0.1 M Zn(i-Pr)2 in toluene. Directory contains seven .dat files 3. '0p1M_Me2Zn_toluene' --> 0.1 M ZnMe2 in toluene. Directory contains seven .dat files 4. '0p1M_Ph2Zn_toluene' --> 0.1 M ZnPh2 in toluene. Directory contains one .dat files 5. '0p1M_ZnCl2_H2O' --> 0.1 M ZnCl2 in water ([Zn(OH2)6]2+). Directory contains three .dat files 6. '0p1M_ZnCl2_THF' --> 0.1 M ZnCl2 in THF. Directory contains three .dat files 7. '0p1M_ZnTfO2_MeCN' --> 0.1 M ZnTfO2 in acetonitrile (Zn(NCMe)6]2+). Directory contains seven .dat files 8. '0p033M_C6F5_2Zn_toluene --> 0.1 M Zn(C6F5)2 in toluene. Directory contains one .dat files 9. 'Zn_foil_reference' --> Solid Zn foil. Each .dat file contains the raw data required to make all of the graphs within the article and supplementary information. The NR-VtC-XE spectra were processed using Igor 8.0 and the .dat files can be opened using this software. The NR-VtC-XE spectra requires a single correction shift in emission energy to correct for errors in the spectrometer setup which can be found in the supplementary information. --- '~/1.experiments/1.2.NR_VtC_XES/Zn_foil_reference' This directory contains two directories which each contain the raw experimental data, in the form of .dat files, used as reference for NR-VtC-XES experiments. Each of the directory name denotes a different beamtime experiment from which data was collected. 1. 'SP28565' Directory contains four .dat file 2. 'SP30597' Directory contains one .dat file ------ '~/1.experiments/1.3.R_VtC_XES' This directory contains nine directories which each contain the raw experimental data, in the form of .dat files, used to make the figures in the main article and supplementary information. Naming conventions of .dat files has not been changed from the initial experiment. 1. '0p1M_Et2Zn_toluene' --> 0.1 M ZnEt2 in toluene. Directory contains one .dat file 2. '0p1M_iPr2Zn_toluene --> 0.1 M Zn(i-Pr)2 in toluene. Directory contains one .dat file 3. '0p1M_Me2Zn_toluene' --> 0.1 M ZnMe2 in toluene. Directory contains one .dat file 4. '0p1M_Ph2Zn_toluene' --> 0.1 M ZnPh2 in toluene. Directory contains one .dat file 5. '0p1M_ZnCl2_H2O' --> 0.1 M ZnCl2 in water ([Zn(OH2)6]2+). Directory contains one .dat file 6. '0p1M_ZnCl2_THF' --> 0.1 M ZnCl2 in THF. Directory contains one .dat file 7. '0p1M_ZnTfO2_MeCN' --> 0.1 M ZnTfO2 in acetonitrile (Zn(NCMe)6]2+). Directory contains one .dat file 8. '0p033M_C6F5_2Zn_toluene --> 0.1 M Zn(C6F5)2 in toluene. Directory contains one .dat file 9. 'omimCl_ZnCl2_0pt33' --> x = 0.33 ZnCl2 in 1–octyl–3–methylimidazolium chloride ([ZnCl4]2-). Directory contains one .dat file Each .dat file contains the raw data required to make all of the graphs within the article and supplementary information. The R-VtC-XES were processed using Igor 8.0 and the .dat files can be opened using this software. The R-VtC-XE spectra requires a single correction shift in emission energy to correct for errors in the spectrometer setup which can be found in the supplementary information. -------- '~/2.calculations' This directory is further organised into four directories: '~/2.calculations/2.1.gbw_files', '~/2.calculations/2.2.KS_DFT_XES', '~/2.calculations/2.3.MS_RASPT2' and '~/2.calculations/2.4.TDDFT_XAS'. ------ '~/2.calculations/2.1.gbw_files' This directory contains 19 .gbw files and 1 .txt file. The .gbw files can be converted to .molden.input files using ORCAs built in "ORCA_2MKL (.gbwfile) -molden" function for further processing in MultiWFN. 1. '2_3_5_6-C6F4H1_2_Zn_PCM_Toluene.gbw' --> Zn(2,3,5,6-C6F4H1)2 2. '2_4_6-C6F3H2_2_Zn_PCM_Toluene.gbw' --> Zn(2,4,6-C6F3H2)2 3. '2_6-C6F2H3_2_Zn_PCM_Toluene.gbw' --> Zn(2,6-C6F2H3)2 4. '3_4_5-C6F3H2_2_Zn_PCM_Toluene.gbw' --> Zn(3,4,5-C6F3H2)2 5. '3_5-C6F2H4_2_Zn_PCM_Toluene.gbw' --> Zn(3,5-C6F2H3)2 6. '4-C6F3H2_2_Zn_PCM_Toluene.gbw' --> Zn(4-C6F1H4)2 7. 'C6F5_2Zn_PCM_Toluene.gbw' 8. 'iPr2Zn_PCM_Toluene.gbw' 9. 'Me2Zn_PCM_Toluene.gbw' 10. 'n-Bu2Zn_PCM_Toluene.gbw' 11. 'n-Pr2Zn_PCM_Toluene.gbw' 12. 'Ph2Zn_PCM_Toluene.gbw' 13. 'tBu2Zn_PCM_Toluene.gbw' 14. 'ZnCl2_2THF_PCM_THF.gbw' 15. 'ZnCl4_2-_PCM_ep11p40.gbw' 16. 'ZnEt2_PCM_Hexane.gbw' 17. 'ZnEt2_PCM_Toluene.gbw' 18. 'ZnNCMe_6_2+_PCM_MeCN.gbw' 19. 'ZnOH2_6_2+_PCM_Water.gbw' 20. 'README.txt' .txt file documenting how to convert .gbw to .molden.input using ORCA ------ '~/2.calculations/2.2.KS_DFT_XES' This directory contains twenty .out files. The .out files contain the following: calculated Zn 1s X-ray emission spectra, molecular orbitals (which can be viewed in a software such as Avogadro) and XYZ coordinates (XYZ coordinates can also found in listed in the supplementary information). Calculated spectra feature in both the article and the supplementary information. 1. 'Zn1s_XES_2_3_5_6-C6F4H1_2_Zn_PCM_Toluene.out' --> Zn(2,3,5,6-C6F4H1)2 2. 'Zn1s_XES_2_4_6-C6F3H2_2_Zn_PCM_Toluene.out' --> Zn(2,4,6-C6F3H2)2 3. 'Zn1s_XES_2_6-C6F2H3_2_Zn_PCM_Toluene.out' --> Zn(2,6-C6F2H3)2 4. 'Zn1s_XES_3_4_5-C6F3H2_2_Zn_PCM_Toluene.out' --> Zn(3,4,5-C6F3H2)2 5. 'Zn1s_XES_3_5-C6F2H3_2_Zn_PCM_Toluene.out' --> Zn(3,5-C6F2H3)2 6. 'Zn1s_XES_4-C6F1H4_2_Zn_PCM_Toluene.out' --> Zn(4-C6F1H4)2 7. 'Zn1s_XES_C6F5_2_Zn_PCM_Toluene.out' 8. 'Zn1s_XES_iPr2Zn_PCM_Toluene.out' 9. 'Zn1s_XES_Me2Zn_PCM_Toluene.out' 8. 'Zn1s_XES_n-Bu2Zn_PCM_Toluene.out' 9. 'Zn1s_XES_n-Pr2Zn_PCM_Toluene.out' 10. 'Zn1s_XES_Ph2Zn_PCM_Toluene.out' 11. 'Zn1s_XES_tBu2Zn_PCM_Toluene.out' 12. 'Zn1s_XES_ZnCl2_2THF_PCM_THF.out' 13. 'Zn1s_XES_ZnCl4_2-_PCM_ep11p40.out' 14. 'Zn1s_XES_ZnEt2_PCM_Hexane.out' 15. 'Zn1s_XES_ZnEt2_PCM_Toluene.out' 16. 'Zn1s_XES_ZnNCMe_6_2+_PCM_MeCN.out' 17. 'Zn1s_XES_ZnOH2_6_2+_PCM_Water.out' 18. 'Zn1s_Zn1_XES_ZnPh2_2_PCM_Toluene.out' --> [ZnPh2]2, Zn 1s XES focused on Zn atom 1, XYZ coordinates taken from [ZnPh2]2 crystal structure (Markies et. al., https://doi.org/10.1016/0022-328X(90)85161-Q) 19. 'Zn1s_Zn2_XES_ZnPh2_2_PCM_Toluene.out' --> [ZnPh2]2, Zn 1s XES focused on Zn atom 2, XYZ coordinates taken from [ZnPh2]2 crystal structure (Markies et. al., https://doi.org/10.1016/0022-328X(90)85161-Q) 20. 'Zn1s_XES_Znboth_ZnPh2_2_PCM_Toluene.out' --> [ZnPh2]2, Zn 1s XES focused on both Zn atoms, XYZ coordinates taken from [ZnPh2]2 crystal structure (Markies et. al., https://doi.org/10.1016/0022-328X(90)85161-Q) ------ '~/2.calculations/2.3.MS_RASPT2' This directory contains eight .txt files. The .txt files contain the calculated spectra, both original and normalised. Further details on MS-RASPT2 calculations can be found in the article. For further inquiries please contact Adam E. A. Fouda: foudaae@anl.gov 1. 'C6F52Zn_Toluene_spec_norm.txt' 2. 'C6F52Zn_Toluene_spec.txt' 3. 'Et2Zn_Toluene_spec_norm.txt' 4. 'Et2Zn_Toluene_spec.txt' 5. 'iPr2Zn_Toluene_spec_norm.txt' 6. 'iPr2Zn_Toluene_spec.txt' 7. 'ZnCl42_epsilon11p40_spec_norm.txt' 8. 'ZnCl42_epsilon11p40_spec.txt' ------ '~/2.calculations/2.4.TDDFT_XAS' This directory contains twenty four .out files and one directory. The .out files contain the following: calculated Zn 1s X-ray absorption spectra, molecular orbitals (which can be viewed in a software such as Avogadro) and XYZ coordinates (XYZ coordinates can also found in listed in the supplementary information). Calculated spectra feature in both the article and the supplementary information. 1. 'Zn1s_XAS_2_3_5_6-C6F4H1_2_Zn_PCM_Toluene.out' --> Zn(2,3,5,6-C6F4H1)2 2. 'Zn1s_XAS_2_4_6-C6F3H2_2_Zn_PCM_Toluene.out' --> Zn(2,4,6-C6F3H2)2 3. 'Zn1s_XAS_2_6-C6F2H3_2_Zn_PCM_Toluene.out' --> Zn(2,6-C6F2H3)2 4. 'Zn1s_XAS_3_4_5-C6F3H2_2_Zn_PCM_Toluene.out' --> Zn(3,4,5-C6F3H2)2 5. 'Zn1s_XAS_3_5-C6F2H3_2_Zn_PCM_Toluene.out' --> Zn(3,5-C6F2H3)2 6. 'Zn1s_XAS_4-C6F1H4_2_Zn_PCM_Toluene.out' --> Zn(4-C6F1H4)2 7. 'Zn1s_XAS_iPr2Zn_PCM_Toluene.out' 8. 'Zn1s_XAS_Me2Zn_PCM_Toluene.out' 9. 'Zn1s_XAS_n-Bu2Zn_PCM_Toluene.out' 10. 'Zn1s_XAS_n-Pr2Zn_PCM_Toluene.out' 11. 'Zn1s_XAS_tBu2Zn_PCM_Toluene.out' 12. 'Zn1s_XAS_ZnCl2_2THF_PCM_THF.out' 13. 'Zn1s_XAS_ZnCl4_2-_PCM_ep11p40.out' 14. 'Zn1s_XAS_ZnEt2_PCM_Hexane.out' 15. 'Zn1s_XAS_ZnEt2_PCM_Toluene.out' 16. 'Zn1s_XAS_ZnNCMe_6_2+_PCM_MeCN.out' 17. 'Zn1s_XAS_ZnOH2_6_2+_PCM_Water.out' 18. 'eclipsed_Zn1s_XAS_C6F5_2_Zn_PCM_Toluene.out' 19. 'eclipsed_Zn1s_XAS_Ph2Zn_PCM_Toluene.out' 20. 'staggered_Zn1s_XAS_C6F5_2Zn_PCM_Toluene.out' 21. 'staggered_Zn1s_XAS_Ph2Zn_PCM_Toluene.out' 22. 'Zn1s_Zn1_XAS_ZnPh2_2_PCM_Toluene.out' --> [ZnPh2]2, Zn 1s XAS focused on Zn atom 1, XYZ coordinates taken from [ZnPh2]2 crystal structure (Markies et. al., https://doi.org/10.1016/0022-328X(90)85161-Q) 23. 'Zn1s_Zn2_XAS_ZnPh2_2_PCM_Toluene.out' --> [ZnPh2]2, Zn 1s XAS focused on Zn atom 2, XYZ coordinates taken from [ZnPh2]2 crystal structure (Markies et. al., https://doi.org/10.1016/0022-328X(90)85161-Q) 24. 'Zn1s_ZnBoth_ZnPh2_2_PCM_Toluene.out' --> [ZnPh2]2, Zn 1s XES focused on both Zn atoms, XYZ coordinates taken from [ZnPh2]2 crystal structure (Markies et. al., https://doi.org/10.1016/0022-328X(90)85161-Q) 25. 'TDDFT_rotation_calculations' --> Directory of Zn 1s TDDFT calculations oof organozinc complexes at fixed bend and dihedral angles (below) --- '~/2.calculations/2.4.TDDFT_XAS/TDDFT_rotation_calculations' This directory is further organised into three directories: '~/2.calculations/2.4.TDDFT_XAS/TDDFT_rotation_calculations/Et2Zn_PCM_hexane_dihedral', '~/2.calculations/2.4.TDDFT_XAS/TDDFT_rotation_calculations/Et2Zn_PCM_toluene_bend' and '~/2.calculations/2.4.TDDFT_XAS/TDDFT_rotation_calculations/Ph2Zn_PCM_hexane_dihedral'. - '~/2.calculations/2.4.TDDFT_XAS/TDDFT_rotation_calculations/Et2Zn_PCM_hexane_dihedral' This directory contains eight .out files. The .out files contain the following: calculated Zn 1s X-ray absorption spectra, molecular orbitals (which can be viewed in a software such as Avogadro) and XYZ coordinates (XYZ coordinates can also found in listed in the supplementary information). Calculated spectra feature in the supplementary information of the linked article. 1. 'Dihedral_Rot_90_Zn1s_XAS_ZnEt2_PCM_Hexane.out' 2. 'Dihedral_Rot_105_Zn1s_XAS_ZnEt2_PCM_Hexane.out' 3. 'Dihedral_Rot_120_Zn1s_XAS_ZnEt2_PCM_Hexane.out' 4. 'Dihedral_Rot_135_Zn1s_XAS_ZnEt2_PCM_Hexane.out' 5. 'Dihedral_Rot_150_Zn1s_XAS_ZnEt2_PCM_Hexane.out' 6. 'Dihedral_Rot_153p9_Zn1s_XAS_ZnEt2_PCM_Hexane.out' 7. 'Dihedral_Rot_165_Zn1s_XAS_ZnEt2_PCM_Hexane.out' 8. 'Dihedral_Rot_180_Zn1s_XAS_ZnEt2_PCM_Hexane.out' - '~/2.calculations/2.4.TDDFT_XAS/TDDFT_rotation_calculations/Et2Zn_PCM_toluene_bend' This directory contains six .out files. The .out files contain the following: calculated Zn 1s X-ray absorption spectra, molecular orbitals (which can be viewed in a software such as Avogadro) and XYZ coordinates (XYZ coordinates can also found in listed in the supplementary information). Calculated spectra feature in the supplementary information of the linked article. 1. 'Zn1s_XAS_bend_140p0_deg_Et2Zn_PCM_toluene.out' 2. 'Zn1s_XAS_bend_151p4_deg_Et2Zn_PCM_toluene.out' 3. 'Zn1s_XAS_bend_162p9_deg_Et2Zn_PCM_toluene.out' 4. 'Zn1s_XAS_bend_168p6_deg_Et2Zn_PCM_toluene.out' 5. 'Zn1s_XAS_bend_174p0_deg_Et2Zn_PCM_toluene.out' 6. 'Zn1s_XAS_bend_180p0_deg_Et2Zn_PCM_toluene.out' - '~/2.calculations/2.4.TDDFT_XAS/TDDFT_rotation_calculations/Ph2Zn_PCM_hexane_dihedral' This directory contains five .out files. The .out files contain the following: calculated Zn 1s X-ray absorption spectra, molecular orbitals (which can be viewed in a software such as Avogadro) and XYZ coordinates (XYZ coordinates can also found in listed in the supplementary information). Calculated spectra feature in the supplementary information of the linked article 1. Dihedral_Rot_101_Zn1s_XAS_ZnPh2_PCM_Hexane.out 2. Dihedral_Rot_118_Zn1s_XAS_ZnPh2_PCM_Hexane.out 3. Dihedral_Rot_138_Zn1s_XAS_ZnPh2_PCM_Hexane.out 4. Dihedral_Rot_150_Zn1s_XAS_ZnPh2_PCM_Hexane.out 5. Dihedral_Rot_178_Zn1s_XAS_ZnPh2_PCM_Hexane.out 5. METHODS ----------- All methods on how the X-ray emission spectroscopy datasets were obtained as well as the methods and parameters used to run all calculations can be found in the article cited in section 1. We have included example ORCA submission scripts in the supplementary information. Any questions on the methods can be directed to Kevin R. J. Lovelock (k.r.j.lovelock@reading.ac.uk).