Different mechanisms for lanthanide(III) sensitization and Yb-field-induced single-molecule magnet behaviour in a series of pentagonal bipyramidal and octahedral lanthanide complexes with axial phosphine oxide ligands.
Allia, Hadjer; Rodríguez Expósito, Ana; Palacios, Maria A.; Jiménez, Juan Ramón; Carneiro Neto, Albano; Moura Jr., Renaldo T.; Piccinelli, Fabio; Navarro, Amparo; Quesada-Moreno, María Mar; Colacio, Enrique; Physical Chemistry Chemical Physics  (2025) –; doi:10.1039/D4CP04862H

data_7250344
_publ_section_title
;
 Different mechanisms for lanthanide(III) sensitization and
 Yb-field-induced single-molecule magnet behaviour in a series of
 pentagonal bipyramidal and octahedral lanthanide complexes with axial
 phosphine oxide ligands.
;
_journal_name_full               'Physical Chemistry Chemical Physics'
_journal_paper_doi               10.1039/D4CP04862H
_journal_year                    2025
_chemical_formula_moiety
'C54 H82 Cl O6 P2 Tb, 2(Cl), 3(C4 H8 O), 1.5(O)'
_chemical_formula_sum            'C66 H109 Cl3 O10.5 P2 Tb'
_chemical_formula_weight         1397.74
_space_group_crystal_system      tetragonal
_space_group_IT_number           78
_space_group_name_Hall           'P 4cw'
_space_group_name_H-M_alt        'P 43'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-19
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-19 deposited with the CCDC.	2025-04-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.1557(6)
_cell_length_b                   24.1557(6)
_cell_length_c                   12.2000(4)
_cell_measurement_reflns_used    9947
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      30.505
_cell_measurement_theta_min      2.667
_cell_volume                     7118.7(3)
_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_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'four-circle diffractometer'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0266
_diffrn_reflns_av_unetI/netI     0.0276
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            112149
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.531
_diffrn_reflns_theta_min         2.385
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.204
_exptl_absorpt_correction_T_max  0.5644
_exptl_absorpt_correction_T_min  0.4825
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0837 before and 0.0663 after correction.
The Ratio of minimum to maximum transmission is 0.8549.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.304
_exptl_crystal_description       prismatic
_exptl_crystal_F_000             2940
_exptl_crystal_size_max          0.419
_exptl_crystal_size_mid          0.310
_exptl_crystal_size_min          0.290
_refine_diff_density_max         2.434
_refine_diff_density_min         -0.706
_refine_diff_density_rms         0.094
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.046(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.185
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     766
_refine_ls_number_reflns         21231
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.185
_refine_ls_R_factor_all          0.0300
_refine_ls_R_factor_gt           0.0297
_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^)+(0.0205P)^2^+10.3132P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0773
_refine_ls_wR_factor_ref         0.0775
_reflns_Friedel_coverage         0.876
_reflns_Friedel_fraction_full    0.945
_reflns_Friedel_fraction_max     0.951
_reflns_number_gt                20992
_reflns_number_total             21231
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cp04862h2.cif
_cod_data_source_block           compound_2
_cod_original_cell_volume        7118.7(4)
_cod_original_formula_sum        'C66 H109 Cl3 O10.50 P2 Tb'
_cod_database_code               7250344
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.954(7)
 0.046(7)
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 O(H,H) groups
3. Restrained distances
 Tb1-H5C \\sim Tb1-H5D
 with sigma of 0.02
 Tb1-H4A \\sim Tb1-H4B
 with sigma of 0.02
 C66-C65 \\sim C66-C65A
 with sigma of 0.02
 C64-C65 \\sim C64-C65A
 with sigma of 0.02
4. Others
 Fixed Sof: H66A(0.7) H66B(0.7) H66C(0.3) H66D(0.3) H64A(0.7) H64B(0.7)
 H64C(0.3) H64D(0.3) C65(0.7) H65A(0.7) H65B(0.7) C65A(0.3) H65C(0.3) H65D(0.3)
 O11(0.5)
5.a Free rotating group:
 O5(H5C,H5D), O4(H4A,H4B)
5.b Rotating group:
 O6(H6A,H6B), O3(H3A,H3B)
5.c Ternary CH refined with riding coordinates:
 C4(H4), C43(H43), C2(H2), C39(H39), C16(H16), C31(H31), C45(H45), C14(H14),
 C8(H8), C35(H35), C12(H12), C29(H29)
5.d Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C42(H42A,H42B), C40(H40A,H40B), C10(H10A,H10B), C32(H32A,H32B),
 C19(H19A,H19B), C1(H1A,H1B), C38(H38A,H38B), C28(H28A,H28B), C46(H46A,H46B),
 C47(H47A,H47B), C3(H3C,H3D), C5(H5A,H5B), C7(H7A,H7B), C34(H34A,H34B),
 C13(H13A,H13B), C36(H36A,H36B), C62(H62A,H62B), C61(H61A,H61B), C44(H44A,H44B),
  C58(H58A,H58B), C20(H20A,H20B), C59(H59A,H59B), C30(H30A,H30B), C17(H17A,
 H17B), C15(H15A,H15B), C48(H48A,H48B), C60(H60A,H60B), C55(H55A,H55B),
 C21(H21A,H21B), C56(H56A,H56B), C11(H11A,H11B), C37(H37A,H37B), C57(H57A,H57B),
  C63(H63A,H63B), C66(H66A,H66B), C66(H66C,H66D), C64(H64A,H64B), C64(H64C,
 H64D), C65(H65A,H65B), C65A(H65C,H65D)
5.e Aromatic/amide H refined with riding coordinates:
 C23(H23), C50(H50), C54(H54), C24(H24), C51(H51), C27(H27), C25(H25),
 C26(H26), C53(H53), C52(H52)
;
_shelx_res_checksum              35191
_olex2_submission_special_instructions 'No special instructions were received'