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_1576531
_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, 2(C18 H33 O P), Mo12 O40 P, 4(C4 H8 O), C4 H10 O, 2(H2 O)'
_chemical_formula_sum            'C92 H188 Dy Mo12 O56 P5'
_chemical_formula_weight         3659.04
_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             2025-03-14
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-07-04 deposited with the CCDC.	2025-11-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 113.233(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.6687(9)
_cell_length_b                   19.2311(9)
_cell_length_c                   29.3029(15)
_cell_measurement_reflns_used    9587
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      27.094
_cell_measurement_theta_min      2.30
_cell_volume                     12774.2(10)
_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      100.0(2)
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0525
_diffrn_reflns_av_unetI/netI     0.0575
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            78217
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.128
_diffrn_reflns_theta_min         1.389
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           0.0
_diffrn_source_power             0.0
_diffrn_source_type              'INCOATEC I\ms 3.0'
_diffrn_source_voltage           0.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.861
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6556
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0970 before and 0.0661 after correction.
The Ratio of minimum to maximum transmission is 0.8794.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.903
_exptl_crystal_description       block
_exptl_crystal_F_000             7332
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         2.300
_refine_diff_density_min         -1.569
_refine_diff_density_rms         0.182
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.349(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.116
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1543
_refine_ls_number_reflns         27833
_refine_ls_number_restraints     2389
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0765
_refine_ls_R_factor_gt           0.0691
_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^)+375.0375P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1423
_refine_ls_wR_factor_ref         0.1461
_reflns_Friedel_coverage         0.974
_reflns_Friedel_fraction_full    0.983
_reflns_Friedel_fraction_max     0.973
_reflns_number_gt                25219
_reflns_number_total             27833
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07950k2.cif
_cod_data_source_block           full_yellow(1)
_cod_original_sg_symbol_H-M      Cc
_cod_database_code               1576531
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.929
_shelx_estimated_absorpt_t_min   0.794
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.651(19)
 0.349(19)
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, All O(H,H) groups
3. Restrained distances
 C42-C37 = C38-C37 = C39-C38 = C40-C39 = C41-C40 = C42-C41 = C54-C49 = C54-C53
 = C53-C52 = C52-C51 = C51-C50 = C50-C49 = C48-C43 = C44-C43 = C45-C44 = C46-
 C45 = C47-C46 = C48-C47
 1.51 with sigma of 0.02
 C51-C50 = C51A-C50 = C52A-C51A = C52-C51 = C53-C52A = C53-C52
 1.51 with sigma of 0.02
 C26-C25 = C30-C25 = C30-C29 = C29-C28 = C28-C27 = C27-C26 = C2-C1 = C6-C1 =
 C6-C5 = C5-C4 = C4-C3 = C3-C2 = C15-C14 = C14-C13 = C16-C15 = C18-C13 = C18-
 C17 = C17-C16 = C7-C12 = C8-C7 = C9-C8 = C9-C10 = C11-C10 = C12-C11 = C33-C32 =
  C34-C33 = C35-C34 = C36-C35 = C36-C31 = C24-C23 = C24-C19 = C20-C19 = C21-C20
 = C23-C22 = C22-C21
 1.51 with sigma of 0.02
 C78-C77 = C80-C79
 1.51 with sigma of 0.02
 C56-C55 = C57-C56 = C58-C57 = C59-C58 = C60-C59 = C60-C55
 1.51 with sigma of 0.02
 C65-C64 = C64-C63 = C63-C62 = C62-C61 = C66-C61 = C66-C65
 1.51 with sigma of 0.02
 C85-O15 \\sim O15-C86 \\sim O16-C89 \\sim O16-C92 \\sim O10-C81 \\sim O10-C84
 with sigma of 0.02
 C88-C87 \\sim C85-C88 \\sim C90-C89 \\sim C92-C91 \\sim C84-C83 \\sim C74-C73
\\sim C76-C74A
 with sigma of 0.02
 C50-C51 \\sim C50-C51A
 with sigma of 0.02
 C51-C52 \\sim C51A-C52A
 with sigma of 0.02
 O14-C76A \\sim O14-C76 \\sim O14-C73A \\sim O14-C73
 with sigma of 0.02
 C84-C83 \\sim C82-C81
 with sigma of 0.02
 C52-C53 \\sim C52A-C53
 with sigma of 0.02
 C91-C90 \\sim C87-C88 \\sim C74A-C74
 with sigma of 0.02
 C50-C52 \\sim C50-C52A
 with sigma of 0.04
 C75A-C76A \\sim C76-C75 \\sim C74-C73 \\sim C74A-C73A
 with sigma of 0.02
 C51-C53 \\sim C51A-C53
 with sigma of 0.04
 C82-C83 \\sim C90-C91 \\sim C88-C87
 with sigma of 0.02
 C75A-C74A \\sim C74-C75
 with sigma of 0.02
 O12-C78 \\sim O12-C79
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim
C45 \\sim C46 \\sim C47 \\sim C48 \\sim C50: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 1.7A
C49 \\sim C50 \\sim C51: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 1.7A
C51 \\sim C51A \\sim C52 \\sim C52A: within 1.7A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 1.7A
O10 \\sim C81 \\sim C82 \\sim C83 \\sim C84: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 1.7A
O15 \\sim C85 \\sim C86 \\sim C87 \\sim C88: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 1.7A
C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33
\\sim C34 \\sim C35 \\sim C36: within 1.7A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 1.7A
C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim
C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim
C71 \\sim C72: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 1.7A
O16 \\sim C89 \\sim C90 \\sim C91 \\sim C92: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 1.7A
O12 \\sim C77 \\sim C78 \\sim C79 \\sim C80: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 1.7A
C73 \\sim C73A \\sim C74 \\sim C74A \\sim C75 \\sim C75A \\sim C76 \\sim C76A:
within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
Uanis(O35) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H50C(0.5) H50D(0.5) H50A(0.5) H50B(0.5) C51(0.5) H51A(0.5)
 H51B(0.5) C51A(0.5) H51C(0.5) H51D(0.5) C52(0.5) H52A(0.5) H52B(0.5) C52A(0.5)
 H52C(0.5) H52D(0.5) H53A(0.5) H53B(0.5) H53C(0.5) H53D(0.5) C73(0.5) H73A(0.5)
 H73B(0.5) C73A(0.5) H73C(0.5) H73D(0.5) C74(0.5) H74A(0.5) H74B(0.5) C74A(0.5)
 H74C(0.5) H74D(0.5) C75(0.5) H75A(0.5) H75B(0.5) C75A(0.5) H75C(0.5) H75D(0.5)
 C76(0.5) H76A(0.5) H76B(0.5) C76A(0.5) H76C(0.5) H76D(0.5)
7.a Free rotating group:
 O11(H11C,H11D), O13(H13A,H13B)
7.b Rotating group:
 O3(H3C,H3D), O4(H4C,H4D), O5(H5C,H5D), O6(H6C,H6D), O7(H7A,H7B)
7.c Ternary CH refined with riding coordinates:
 C1(H1), C7(H7), C13(H13), C19(H19), C25(H25), C31(H31), C37(H37), C43(H43),
 C49(H49), C55(H55), C61(H61), C67(H67)
7.d Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), 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),
  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(H50C,H50D), C50(H50A,H50B), C51(H51A,H51B), C51A(H51C,
 H51D), C52(H52A,H52B), C52A(H52C,H52D), C53(H53A,H53B), C53(H53C,H53D),
 C54(H54A,H54B), 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), C73(H73A,H73B), C73A(H73C,H73D), C74(H74A,
 H74B), C74A(H74C,H74D), C75(H75A,H75B), C75A(H75C,H75D), C76(H76A,H76B),
 C76A(H76C,H76D), C78(H78A,H78B), C79(H79A,H79B), C85(H85A,H85B), C86(H86A,
 H86B), C87(H87A,H87B), C88(H88A,H88B), C89(H89A,H89B), C90(H90A,H90B),
 C91(H91A,H91B), C92(H92A,H92B), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B),
  C84(H84A,H84B)
7.e Idealised Me refined as rotating group:
 C77(H77A,H77B,H77C), C80(H80A,H80B,H80C)
;
_shelx_res_checksum              37435
_olex2_submission_special_instructions 'No special instructions were received'