Modulating the spin-flip rates and emission energies through ligand design in chromium(iii) molecular rubies.
Ye, Yating; Poncet, Maxime; Yaltseva, Polina; Salcedo-Abraira, Pablo; Rodríguez-Diéguez, Antonio; Martín, Javier Heredia; Cuevas-Contreras, Laura; Cruz, Carlos M.; Doistau, Benjamin; Piguet, Claude; Wenger, Oliver S.; Herrera, Juan Manuel; Jiménez, Juan-Ramón; Chemical science 16 (2025) 5205–5213; doi:10.1039/d4sc08021a

data_1573950
_publ_section_title
;
 Modulating the spin-flip rates and emission energies through ligand
 design in chromium(iii) molecular rubies.
;
_journal_issue                   12
_journal_name_full               'Chemical science'
_journal_page_first              5205
_journal_page_last               5213
_journal_paper_doi               10.1039/d4sc08021a
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C42 H34 Cr N10, 3(C F3 O3 S), 10[H2O]'
_chemical_formula_sum            'C45 H54 Cr F9 N10 O19 S3'
_chemical_formula_weight         1358.16
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-09
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-10-09 deposited with the CCDC.	2025-02-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.8078(9)
_cell_length_b                   21.0257(10)
_cell_length_c                   11.4987(5)
_cell_measurement_reflns_used    9922
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      26.366
_cell_measurement_theta_min      2.179
_cell_volume                     5997.7(4)
_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  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0473
_diffrn_reflns_av_unetI/netI     0.0293
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            49184
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         1.906
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.400
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6698
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0782 before and 0.0472 after correction.
The Ratio of minimum to maximum transmission is 0.8986.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.504
_exptl_crystal_description       block
_exptl_crystal_F_000             2796
_exptl_crystal_size_max          0.246
_exptl_crystal_size_mid          0.221
_exptl_crystal_size_min          0.216
_refine_diff_density_max         2.188
_refine_diff_density_min         -1.229
_refine_diff_density_rms         0.153
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.51(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.687
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     654
_refine_ls_number_reflns         10588
_refine_ls_number_restraints     1284
_refine_ls_restrained_S_all      1.661
_refine_ls_R_factor_all          0.1117
_refine_ls_R_factor_gt           0.1037
_refine_ls_shift/su_max          0.000
_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          0.3308
_refine_ls_wR_factor_ref         0.3517
_reflns_Friedel_coverage         0.896
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                9583
_reflns_number_total             10588
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08021a2.cif
_cod_data_source_block           mo_yt187_bis_0m
_cod_depositor_comments
'Adding full bibliography for 1573949--1573951.cif.'
_cod_database_code               1573950
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.918
_shelx_estimated_absorpt_t_min   0.908
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.49(6)
 0.51(6)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Restrained distances
 O7T-N9
 -3 with sigma of 0.02
 C36-C37A \\sim C36-C37B
 with sigma of 0.02
 C41A-C40A \\sim C41B-C40B
 with sigma of 0.02
 C41A-C42A \\sim C41B-C42B
 with sigma of 0.02
 C40A-C39A \\sim C40B-C39B
 with sigma of 0.02
 C39A-C38A \\sim C39B-C38B
 with sigma of 0.02
 C38A-C37A \\sim C38B-C37B
 with sigma of 0.02
 C37A-C42A \\sim C37B-C42B
 with sigma of 0.02
 C42A-N6 \\sim C42B-N6
 with sigma of 0.02
 C36-C38A \\sim C36-C38B
 with sigma of 0.04
 C36-C42A \\sim C36-C42B
 with sigma of 0.04
 C41A-C39A \\sim C41B-C39B
 with sigma of 0.04
 C41A-C37A \\sim C41B-C37B
 with sigma of 0.04
 C41A-N6 \\sim C41B-N6
 with sigma of 0.04
 C40A-C38A \\sim C40B-C38B
 with sigma of 0.04
 C40A-C42A \\sim C40B-C42B
 with sigma of 0.04
 C39A-C37A \\sim C39B-C37B
 with sigma of 0.04
 C38A-C42A \\sim C38B-C42B
 with sigma of 0.04
 C37A-N6 \\sim C37B-N6
 with sigma of 0.04
 C2T-F6T \\sim C2T-F4T \\sim C2T-F5T
 with sigma of 0.02
 F6T-F4T \\sim F4T-F5T \\sim F5T-F6T
 with sigma of 0.04
 S2T-F6T \\sim S2T-F4T \\sim S2T-F5T
 with sigma of 0.04
 S2T-O5T \\sim S2T-O6T \\sim S2T-O4T
 with sigma of 0.02
 O5T-O6T \\sim O6T-O4T \\sim O5T-O4T
 with sigma of 0.04
 C2T-O5T \\sim C2T-O6T \\sim C2T-O4T
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
C1T \\sim S1T \\sim O2T \\sim O3T \\sim O1T \\sim F3T \\sim F2T \\sim F1T:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C5 \\sim Cr1 \\sim N3 \\sim N5 \\sim N10 \\sim N1 \\sim N8 \\sim N6 \\sim C9
\\sim C13 \\sim N4 \\sim C21 \\sim N9 \\sim C22 \\sim N2 \\sim C1 \\sim C34
\\sim C30 \\sim C42B \\sim C42A \\sim N7 \\sim C10 \\sim C8 \\sim C12 \\sim C14
\\sim C15 \\sim C16 \\sim C20 \\sim C29 \\sim C28 \\sim C27 \\sim C23 \\sim C7
\\sim C6 \\sim C2 \\sim C33 \\sim C35 \\sim C31 \\sim C41B \\sim C37B \\sim
C41A \\sim C37A \\sim C36 \\sim C11 \\sim C17 \\sim C19 \\sim C26 \\sim C24
\\sim C3 \\sim C4 \\sim C32 \\sim C40B \\sim C38B \\sim C40A \\sim C38A \\sim
C18 \\sim C25 \\sim C39B \\sim C39A \\sim C14: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C2T \\sim F6T \\sim F4T \\sim F5T \\sim S2T \\sim O5T \\sim O6T \\sim O4T:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(F6T) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N1) = Uanis(N6)
Uanis(N4) = Uanis(N2)
Uanis(C8) = Uanis(C14)
5. Rigid body (RIGU) restrains
 N4, C4, Cr1, N3, N5, N10, N1, N8, N6, C9, C13, C21, N9, C22, N2, C1, C30, C34,
  N7, C42B, C42A, C10, C8, C12, C14, C15, C16, C20, C29, C28, C27, C23, C7, C6,
 C2, C5, C31, C33, C35, C36, C41B, C37B, C41A, C37A, C11, C17, C19, C26, C24,
 C3, C32, C40B, C38B, C40A, C38A, C18, C25, C39B, C39A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C2T, F6T, F4T, F5T, S2T, O5T, O6T, O4T
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H36A)=Sof(C41B)=Sof(H41B)=Sof(C40B)=Sof(H40B)=Sof(C39B)=Sof(H39B)=
 Sof(C38B)=Sof(H38B)=Sof(C37B)=Sof(C42B)=1-FVAR(1)
 Sof(H36)=Sof(C41A)=Sof(H41A)=Sof(C40A)=Sof(H40A)=Sof(C39A)=Sof(H39A)=
 Sof(C38A)=Sof(H38A)=Sof(C37A)=Sof(C42A)=FVAR(1)
7.a Free rotating group:
 C2T(F6T,F4T,F5T,S2T,O5T,O6T,O4T)
7.b Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C35(H35A,H35B), C8(H8A,H8B), C14(H14A,H14B)
7.c Aromatic/amide H refined with riding coordinates:
 C28(H28), C36(H36), C36(H36A), C41A(H41A), C40A(H40A), C39A(H39A), C38A(H38A),
  C17(H17), C18(H18), C19(H19), C20(H20), C32(H32), C31(H31), C33(H33),
 C10(H10), C2(H2), C3(H3), C4(H4), C5(H5), C25(H25), C7(H7), C12(H12), C23(H23),
  C15(H15), C26(H26), C24(H24), C11(H11), C41B(H41B), C40B(H40B), C39B(H39B),
 C38B(H38B)
7.d Fitted hexagon refined as free rotating group:
 C41A(C40A,C39A,C38A,C37A,C42A), C16(C17,C18,C19,C20,C21), C32(C31,C30,N8,C34,
 C33), C6(C1,C2,C3,C4,C5), C41B(C40B,C39B,C38B,C37B,C42B)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 402 electrons were 
found in a volume of 1636\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
10[H2O] per formula unit 
which account for 400 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              98918
_shelx_fab_checksum              62521
_olex2_submission_special_instructions 'No special instructions were received'