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_7250343
_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 H74 Cl Gd O6 P2, 1.8(C4 H8 O), 2(Cl1)'
_chemical_formula_sum            'C61.2 H96.4 Cl3 Gd O7.8 P2'
_chemical_formula_weight         1282.52
_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   geom
_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                   24.2107(8)
_cell_length_b                   24.2107(8)
_cell_length_c                   12.1822(6)
_cell_measurement_reflns_used    9797
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      30.585
_cell_measurement_theta_min      2.517
_cell_volume                     7140.7(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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.992
_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  0.0359
_diffrn_reflns_av_unetI/netI     0.0363
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            79006
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.652
_diffrn_reflns_theta_min         1.881
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.130
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.6185
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0989 before and 0.0662 after correction.
The Ratio of minimum to maximum transmission is 0.6185.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.193
_exptl_crystal_description       prismatic
_exptl_crystal_F_000             2684
_exptl_crystal_size_max          0.304
_exptl_crystal_size_mid          0.232
_exptl_crystal_size_min          0.156
_refine_diff_density_max         2.158
_refine_diff_density_min         -0.869
_refine_diff_density_rms         0.146
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.039(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     749
_refine_ls_number_reflns         21479
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0474
_refine_ls_R_factor_gt           0.0445
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0676P)^2^+9.2242P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1212
_refine_ls_wR_factor_ref         0.1242
_reflns_Friedel_coverage         0.880
_reflns_Friedel_fraction_full    0.963
_reflns_Friedel_fraction_max     0.951
_reflns_number_gt                20458
_reflns_number_total             21479
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cp04862h2.cif
_cod_data_source_block           compound_3
_cod_original_cell_volume        7140.7(6)
_cod_original_formula_sum        'C61.20 H96.40 Cl3 Gd O7.80 P2'
_cod_database_code               7250343
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.961(11)
 0.039(11)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Others
 Fixed Sof: O7(0.75) C60(0.75) H60A(0.75) H60B(0.75) O8(0.75) C55(0.75)
 H55A(0.75) H55B(0.75) C59(0.75) H59A(0.75) H59B(0.75) C61(0.75) H61A(0.75)
 H61B(0.75) C58(0.75) H58A(0.75) H58B(0.75) O9(0.3) C63(0.3) H63A(0.3)
 H63B(0.3) C66(0.3) H66A(0.3) H66B(0.3) C64(0.3) H64A(0.3) H64B(0.3) C65(0.3)
 H65A(0.3) H65B(0.3) Cl2A(0.7) Cl3A(0.7) Cl2(0.3) Cl3(0.3) C57(0.75) H57A(0.75)
 H57B(0.75) C56(0.75) H56A(0.75) H56B(0.75) C62(0.75) H62A(0.75) H62B(0.75)
4.a Ternary CH refined with riding coordinates:
 C4(H4), C41(H41), C16(H16), C31(H31), C43(H43), C39(H39), C2(H2), C8(H8),
 C14(H14), C29(H29), C35(H35), C12(H12)
4.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C46(H46A,H46B), C40(H40A,H40B), C10(H10A,H10B), C1(H1A,H1B),
 C3(H3A,H3B), C28(H28A,H28B), C38(H38A,H38B), C13(H13A,H13B), C42(H42A,H42B),
 C36(H36A,H36B), C20(H20A,H20B), C47(H47A,H47B), C30(H30A,H30B), C37(H37A,H37B),
  C7(H7A,H7B), C32(H32A,H32B), C5(H5A,H5B), C44(H44A,H44B), C34(H34A,H34B),
 C11(H11A,H11B), C17(H17A,H17B), C19(H19A,H19B), C15(H15A,H15B), C48(H48A,H48B),
  C60(H60A,H60B), C21(H21A,H21B), C55(H55A,H55B), C59(H59A,H59B), C61(H61A,
 H61B), C58(H58A,H58B), C63(H63A,H63B), C66(H66A,H66B), C64(H64A,H64B),
 C65(H65A,H65B), C57(H57A,H57B), C56(H56A,H56B), C62(H62A,H62B)
4.c Aromatic/amide H refined with riding coordinates:
 C50(H50), C54(H54), C23(H23), C27(H27), C24(H24), C51(H51), C52(H52),
 C25(H25), C53(H53), C26(H26)
;
_shelx_res_checksum              17015
_olex2_submission_special_instructions 'No special instructions were received'