Highly reducible polyoxometalate-Dy(iii) SMM hybrid materials with exceptional charge stability.
Lowe, Ethan; Rouzières, Mathieu; Dugmore, Sarah K.; Kelly, Christopher; Wilson, Claire; Canaj, Angelos B.; Clérac, Rodolphe; Murrie, Mark; Chemical science 17 (2026) 3248–3258; doi:10.1039/d5sc07950k

data_1576532
_publ_section_title
;
 Highly reducible polyoxometalate-Dy(iii) SMM hybrid materials with
 exceptional charge stability.
;
_journal_issue                   6
_journal_name_full               'Chemical science'
_journal_page_first              3248
_journal_page_last               3258
_journal_paper_doi               10.1039/d5sc07950k
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C36 H76 Dy O7 P2, Mo12 O40 P, 2(C18 H33 O P)'
_chemical_formula_sum            'C72 H142 Dy Mo12 O49 P5'
_chemical_formula_weight         3260.48
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2025-10-10
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-10-14 deposited with the CCDC.	2025-11-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 113.102(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.5974(15)
_cell_length_b                   19.2115(12)
_cell_length_c                   29.5224(19)
_cell_measurement_reflns_used    9369
_cell_measurement_temperature    100
_cell_measurement_theta_max      79.05
_cell_measurement_theta_min      5.95
_cell_volume                     12832.1(14)
_computing_cell_refinement       'SAINT V8.37A (Bruker-AXS, 2016)'
_computing_data_collection       'APEX3 Ver. 2016.9-0 (Bruker-AXS, 2016)'
_computing_data_reduction        'APEX3 Ver. 2016.9-0 (Bruker-AXS, 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
_diffrn_detector                 'charge integrating pixel array detector'
_diffrn_detector_area_resol_mean 7.4074
_diffrn_detector_type            'Bruker PHOTON II'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.975
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  'multilayer mirror optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0499
_diffrn_reflns_av_unetI/netI     0.0537
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            63677
_diffrn_reflns_point_group_measured_fraction_full 0.843
_diffrn_reflns_point_group_measured_fraction_max 0.796
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         79.193
_diffrn_reflns_theta_min         3.018
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           1.1
_diffrn_source_power             0.05500000000000001
_diffrn_source_type              'INCOATEC I\ms 3.0'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    13.521
_exptl_absorpt_correction_T_max  0.7542
_exptl_absorpt_correction_T_min  0.4792
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1404 before and 0.1048 after correction.
The Ratio of minimum to maximum transmission is 0.6354.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.688
_exptl_crystal_description       block
_exptl_crystal_F_000             6444
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.099
_refine_diff_density_min         -2.198
_refine_diff_density_rms         0.171
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.523(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     655
_refine_ls_number_reflns         22126
_refine_ls_number_restraints     75
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0694
_refine_ls_R_factor_gt           0.0686
_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^)+(0.0430P)^2^+300.7137P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1609
_refine_ls_wR_factor_ref         0.1617
_reflns_Friedel_coverage         0.631
_reflns_Friedel_fraction_full    0.695
_reflns_Friedel_fraction_max     0.616
_reflns_number_gt                21840
_reflns_number_total             22126
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07950k2.cif
_cod_data_source_block           cu_dypma_blue_cu_100k_0m
_cod_database_code               1576532
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.477(7)
 0.523(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H,H) groups
3. Restrained distances
 C69-C68 = C68-C67 = C72-C67 = C72-C71 = C71-C70 = C70-C69 = C62-C61 = C66-C61
 = C66-C65 = C65-C64 = C63-C62 = C64-C63 = C60-C55 = C60-C59 = C59-C58 = C58-
 C57 = C57-C56 = C56-C55
 1.51 with sigma of 0.02
 C48-C43 = C48-C47 = C47-C46 = C46-C45 = C45-C44 = C44-C43 = C42-C37 = C42-C41
 = C41-C40 = C40-C39 = C39-C38 = C38-C37
 1.51 with sigma of 0.02
 C18-C13 = C14-C13 = C15-C14 = C16-C15 = C17-C16 = C18-C17 = C6-C1 = C6-C5 =
 C5-C4 = C4-C3 = C3-C2 = C2-C1 = C7-C12 = C8-C7 = C9-C8 = C9-C10 = C11-C10 =
 C12-C11 = C24-C19 = C24-C23 = C23-C22 = C22-C21 = C21-C20 = C20-C19 = C36-C31 =
  C32-C31 = C33-C32 = C34-C33 = C35-C34 = C36-C35 = C26-C25 = C30-C25 = C27-C26
 = C28-C27 = C30-C29 = C29-C28
 1.51 with sigma of 0.02
 C50-C49 = C54-C49 = C53-C54 = C52-C53 = C52-C51 = C51-C50
 1.51 with sigma of 0.02
 Dy1-H5A \\sim Dy1-H5B
 with sigma of 0.02
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
5.a Free rotating group:
 O5(H5A,H5B)
5.b Rotating group:
 O3(H3A,H3B), O4(H4A,H4B), O6(H6A,H6B), O7(H7A,H7B)
5.c Ternary CH refined with riding coordinates:
 C1(H1), C7(H7), C13(H13), C19(H19), C25(H25), C31(H31), C55(H55), C61(H61),
 C67(H67), C37(H37), C43(H43), C49(H49)
5.d Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3C,H3D), C4(H4C,H4D), C5(H5C,H5D), C6(H6C,H6D), C8(H8A,H8B),
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C14(H14A,H14B),
 C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C20(H20A,H20B),
  C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C26(H26A,
 H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B),
 C32(H32A,H32B), C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B),
  C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B), C60(H60A,
 H60B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,H64B), C65(H65A,H65B),
 C66(H66A,H66B), C68(H68A,H68B), C69(H69A,H69B), C70(H70A,H70B), C71(H71A,H71B),
  C72(H72A,H72B), C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,
 H41B), C42(H42A,H42B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B),
 C47(H47A,H47B), C48(H48A,H48B), C50(H50A,H50B), C51(H51A,H51B), C54(H54A,H54B),
  C53(H53A,H53B), C52(H52A,H52B)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              8844
_shelx_fab_checksum              86462
_olex2_submission_special_instructions 'No special instructions were received'