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_1573951
_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_formula_moiety
'C34 H38 Cr I4.001 N10, 3(C F3 O3 S), C4 H10 O, C2 H3 N'
_chemical_formula_sum            'C43 H51 Cr F9 I4 N11 O10 S3'
_chemical_formula_weight         1708.72
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     heavy
_audit_creation_date             2023-05-17
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-11-22 deposited with the CCDC.	2025-02-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.6638(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.8195(5)
_cell_length_b                   22.8812(10)
_cell_length_c                   22.7016(10)
_cell_measurement_reflns_used    9867
_cell_measurement_temperature    100
_cell_measurement_theta_max      23.268
_cell_measurement_theta_min      2.300
_cell_volume                     6033.5(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  'SHELXL 2013/4 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker VENTURE'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0548
_diffrn_reflns_av_unetI/netI     0.0369
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            92085
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.303
_diffrn_reflns_theta_min         1.966
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    2.428
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.6479
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0865 before and 0.0509 after correction. The Ratio of minimum to maximum transmission is 0.6479. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'metallic orangish red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.881
_exptl_crystal_description       plate
_exptl_crystal_F_000             3324
_exptl_crystal_size_max          0.247
_exptl_crystal_size_mid          0.101
_exptl_crystal_size_min          0.051
_refine_diff_density_max         3.101
_refine_diff_density_min         -1.537
_refine_diff_density_rms         0.180
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     772
_refine_ls_number_reflns         14938
_refine_ls_number_restraints     95
_refine_ls_restrained_S_all      1.140
_refine_ls_R_factor_all          0.0816
_refine_ls_R_factor_gt           0.0611
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0517P)^2^+64.6730P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1406
_refine_ls_wR_factor_ref         0.1540
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11878
_reflns_number_total             14938
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08021a2.cif
_cod_data_source_block           ed1
_cod_depositor_comments
'Adding full bibliography for 1573949--1573951.cif.'
_cod_database_code               1573951
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.886
_shelx_estimated_absorpt_t_min   0.585
_olex2_refinement_description
;
1. 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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C2S-C1SA \\sim C2S-C1SB
 with sigma of 0.02
 O1S-C3SB \\sim O1S-C3SA
 with sigma of 0.02
 F8-C37 \\sim I1B-C3 \\sim I1A-C3
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C3SB) \\sim Ueq, Uanis(C3SA) \\sim Ueq, Uanis(C1SA) \\sim Ueq,
Uanis(C1SB) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.005
Uanis(C1SB) \\sim Ueq, Uanis(C1SA) \\sim Ueq, Uanis(C3SB) \\sim Ueq,
Uanis(C3SA) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(F1) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F2) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(F4) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F6) \\sim
Ueq, Uanis(O5) \\sim Ueq, Uanis(S2) \\sim Ueq, Uanis(O6) \\sim Ueq, Uanis(O4)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Others
 Sof(H4SD)=Sof(H4SE)=Sof(H4SF)=Sof(C3SB)=Sof(H3SC)=Sof(H3SD)=1-FVAR(1)
 Sof(H4SA)=Sof(H4SB)=Sof(H4SC)=Sof(C3SA)=Sof(H3SA)=Sof(H3SB)=FVAR(1)
 Sof(H2SC)=Sof(H2SD)=Sof(C1SB)=Sof(H1SD)=Sof(H1SE)=Sof(H1SF)=1-FVAR(2)
 Sof(H2SA)=Sof(H2SB)=Sof(C1SA)=Sof(H1SA)=Sof(H1SB)=Sof(H1SC)=FVAR(2)
 Sof(I1A)=Sof(I1B)=FVAR(3)
5.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C12(H12A,H12B), C23(H23A,H23B), C29(H29A,H29B), C2S(H2SA,H2SB),
 C2S(H2SC,H2SD), C3SA(H3SA,H3SB), C3SB(H3SC,H3SD)
5.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C25(H25), C26(H26), C27(H27)
5.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C5(H5A,H5B,H5C), C14(H14A,H14B,H14C), C17(H17A,H17B,H17C),
 C18(H18A,H18B,H18C), C22(H22A,H22B,H22C), C31(H31A,H31B,H31C), C34(H34A,H34B,
 H34C), C4S(H4SA,H4SB,H4SC), C4S(H4SD,H4SE,H4SF), C1SA(H1SA,H1SB,H1SC),
 C1SB(H1SD,H1SE,H1SF), C0AA(H0AA,H0AB,H0AC)
;
_shelx_res_checksum              13073
_olex2_submission_special_instructions 'No special instructions were received'