Stimulus-responsive metallocenes: a photo/thermal switch enabled by the perfluorinated Cp* ligand
Sievers, Robin; Hartmann, Nick; Riemann, Paulin S.; Streit, Tim-Niclas; Malischewski, Moritz; Chemical Science 16 (2025) 11949–11953; doi:10.1039/D5SC02784E

data_1574729
_publ_section_title
;
 Stimulus-responsive metallocenes: a photo/thermal switch enabled by the
 perfluorinated Cp* ligand
;
_journal_issue                   26
_journal_name_full               'Chemical Science'
_journal_page_first              11949
_journal_page_last               11953
_journal_paper_doi               10.1039/D5SC02784E
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C33 H32 Fe N P2, 2(C H2 Cl2), C10 F15'
_chemical_formula_sum            'C45 H36 Cl4 F15 Fe N P2'
_chemical_formula_weight         1135.34
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yc'
_space_group_name_H-M_alt        'P 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-04-02
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-04-03 deposited with the CCDC.	2025-05-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 89.979(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.9310(9)
_cell_length_b                   15.9306(11)
_cell_length_c                   18.5289(13)
_cell_measurement_reflns_used    9966
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      26.334
_cell_measurement_theta_min      2.199
_cell_volume                     4702.5(5)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0551
_diffrn_reflns_av_unetI/netI     0.0503
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            77532
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.391
_diffrn_reflns_theta_min         1.808
_diffrn_source_current           0.0
_diffrn_source_power             0.0
_diffrn_source_voltage           0.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.711
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6262
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1110 before and 0.0574 after correction.
The Ratio of minimum to maximum transmission is 0.8401.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.604
_exptl_crystal_description       block
_exptl_crystal_F_000             2288
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.014
_refine_diff_density_min         -0.890
_refine_diff_density_rms         0.094
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.03(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.842
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1327
_refine_ls_number_reflns         19069
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      0.842
_refine_ls_R_factor_all          0.0681
_refine_ls_R_factor_gt           0.0563
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1714
_refine_ls_wR_factor_ref         0.1967
_reflns_Friedel_coverage         0.981
_reflns_Friedel_fraction_full    0.986
_reflns_Friedel_fraction_max     0.979
_reflns_number_gt                16515
_reflns_number_total             19069
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02784e2.cif
_cod_data_source_block           mo_mm_rs_rsfcdppe_0m
_cod_depositor_comments
'Adding full bibliography for 1574729--1574731.cif.'
_cod_database_code               1574729
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.932
_shelx_estimated_absorpt_t_min   0.932
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.97(2)
 0.03(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Others
 Fixed Sof: Cl00(0.5) Cl(0.5) F01B(0.6) F03G(0.6) F03H(0.6) F03R(0.6)
 F03T(0.6) Cl3(0.5) Cl4(0.5) F3(0.5) F4(0.5) F5(0.5) F2(0.5) F9(0.5) F7(0.5)
 F8(0.5) F10(0.5) F12(0.4) F11(0.4) F13(0.4) F14(0.4) F15(0.4) H1AA(0.5)
 H1AB(0.5) H1BC(0.5) H1BD(0.5) H2AA(0.5) H2AB(0.5) H2BC(0.5) H2BD(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C021(H02A,H02B), C02H(H02O,H02P), C02S(H02F,H02G), C03A(H03A,H03B), C03N(H03C,
 H03D), C03U(H03F,H03G), C1(H1AA,H1AB), C1(H1BC,H1BD), C2(H2AA,H2AB), C2(H2BC,
 H2BD)
4.b Aromatic/amide H refined with riding coordinates:
 C00V(H00V), C00W(H00W), C00Z(H00Z), C010(H010), C011(H011), C014(H014),
 C015(H015), C017(H017), C019(H019), C01C(H01C), C01E(H01E), C01F(H01F),
 C01G(H01G), C01M(H01M), C01N(H01N), C01P(H01P), C01Q(H01Q), C01R(H01R),
 C01S(H01S), C01T(H01T), C01U(H01U), C01W(H01W), C020(H020), C022(H022),
 C024(H024), C026(H026), C028(H028), C029(H029), C02A(H02H), C02D(H02L),
 C02F(H02M), C02G(H02N), C02I(H02Q), C02K(H02R), C02L(H02S), C02O(H02X),
 C02T(H02T), C02U(H02U), C02V(H02V), C02W(H02W), C02Y(H02Y), C030(H030),
 C031(H031), C032(H032), C033(H033), C034(H034), C036(H036), C037(H037),
 C038(H038), C03E(H03E)
4.c Idealised Me refined as rotating group:
 C02B(H02I,H02J,H02K), C02P(H02C,H02D,H02E)
;
_shelx_res_checksum              23505
_olex2_submission_special_instructions 'No special instructions were received'