Backbone-integrated triplet radicals in linear 2p-3d-4f heterometallic chains and magnetic hysteresis
Tsukii, Shota; Haga, Nagito; Takano, Rina; Ishida, Takayuki; Chemical Communications  (2026) –; doi:10.1039/D6CC01045H

data_7135634
_publ_section_title
;
 Backbone-integrated triplet radicals in linear 2p-3d-4f heterometallic
 chains and magnetic hysteresis.
;
_journal_issue                   28
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              7343
_journal_page_last               7347
_journal_paper_doi               10.1039/d6cc01045h
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         'C55 H47 F36 Mn N4 O14 Tb'
_chemical_formula_sum            'C55 H47 F36 Mn N4 O14 Tb'
_chemical_formula_weight         1885.82
_chemical_name_systematic        TbMn5TFPBN
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-09-19
_audit_creation_method
;
Olex2 1.5-ac5-018
(compiled 2021.09.08 svn.r13c46975 for Rigaku Oxford Diffraction, GUI svn.r6396)
;
_audit_update_record
;
2025-12-05 deposited with the CCDC.	2026-03-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.3402(18)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   32.3437(6)
_cell_length_b                   11.4993(2)
_cell_length_c                   20.4873(4)
_cell_measurement_reflns_used    12769
_cell_measurement_temperature    99.9(2)
_cell_measurement_theta_max      30.6950
_cell_measurement_theta_min      2.6810
_cell_volume                     7573.2(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 42.72a 64-bit (release 07-10-2022))'
_computing_data_reduction        'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac5-018 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-018 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.807
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     -7.00  21.00   0.50   11.32    --    4.68 -99.00 150.00   56
  2  \w     -2.00  34.00   0.50   11.32    --    4.68 -99.00 -90.00   72
  3  \w      2.00  71.00   0.50   11.32    --    4.68  57.00-180.00  138
  4  \w    -76.00  14.00   0.50   11.32    --   -5.46 -77.00  30.00  180
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0030338000
_diffrn_orient_matrix_UB_12      -0.0337046000
_diffrn_orient_matrix_UB_13      0.0280659000
_diffrn_orient_matrix_UB_21      0.0001024000
_diffrn_orient_matrix_UB_22      -0.0514457000
_diffrn_orient_matrix_UB_23      -0.0190857000
_diffrn_orient_matrix_UB_31      0.0218559000
_diffrn_orient_matrix_UB_32      -0.0044792000
_diffrn_orient_matrix_UB_33      0.0078820000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0333
_diffrn_reflns_av_unetI/netI     0.0379
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.807
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -46
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            30469
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.807
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.975
_diffrn_reflns_theta_min         2.247
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.240
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66924
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.105a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark brown'
_exptl_crystal_density_diffrn    1.654
_exptl_crystal_description       block
_exptl_crystal_F_000             3724
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: heptane-dichloromethane'
_exptl_crystal_size_max          0.194
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.082
_refine_diff_density_max         1.158
_refine_diff_density_min         -0.952
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     565
_refine_ls_number_reflns         10587
_refine_ls_number_restraints     84
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0718
_refine_ls_R_factor_gt           0.0417
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0489P)^2^+21.6103P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0980
_refine_ls_wR_factor_ref         0.1118
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7278
_reflns_number_total             10587
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc01045h2.cif
_cod_data_source_block           20250804_tbmnmtfmpbn
_cod_depositor_comments
'Adding full bibliography for 7135632--7135638.cif.'
_cod_original_cell_volume        7573.2(3)
_cod_database_code               7135634
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C55 H47 F36 Mn N4 O14 Tb'
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.795
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C21, F13, C21, F14, C21, F15, C21, C21, C21, C24, F16, C24, F17, C24, F18,
 C24, F16A, C24, F17A, C24, F18A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3. Uiso/Uaniso restraints and constraints
F13 \\sim F14 \\sim F15 \\sim F16 \\sim F17 \\sim F18 \\sim F16A \\sim F17A
\\sim F18A: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
within 2A
4. Rigid body (RIGU) restrains
 C21, F13, C21, F14, C21, F15, C21, C21, C21, C24, F16, C24, F17, C24, F18,
 C24, F16A, C24, F17A, C24, F18A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(F3A)=Sof(F2A)=Sof(F1A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
 Sof(F17A)=Sof(F16A)=Sof(F18A)=1-FVAR(2)
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C18(H18), C23(H23), C26(H26)
6.b Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,
 H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              23675
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.290
_oxdiff_exptl_absorpt_empirical_full_min 0.768