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_7250341
_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 H62 Cl3 Eu O3 P2, 1.35(C4 H8 O)'
_chemical_formula_sum            'C59.4 H72.8 Cl3 Eu O4.35 P2'
_chemical_formula_weight         1176.62
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_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                99.2160(10)
_cell_angle_beta                 101.3970(10)
_cell_angle_gamma                101.4720(10)
_cell_formula_units_Z            2
_cell_length_a                   12.2190(5)
_cell_length_b                   15.2856(5)
_cell_length_c                   15.8953(5)
_cell_measurement_reflns_used    9696
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      28.281
_cell_measurement_theta_min      2.462
_cell_volume                     2790.01(17)
_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 0.999
_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  0.1297
_diffrn_reflns_av_unetI/netI     0.0570
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            157019
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.389
_diffrn_reflns_theta_min         1.934
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.371
_exptl_absorpt_correction_T_max  0.9220
_exptl_absorpt_correction_T_min  0.7429
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1054 before and 0.0474 after correction.
The Ratio of minimum to maximum transmission is 0.8057.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'pale pink'
_exptl_crystal_density_diffrn    1.401
_exptl_crystal_description       needle
_exptl_crystal_F_000             1216
_exptl_crystal_size_max          0.346
_exptl_crystal_size_mid          0.135
_exptl_crystal_size_min          0.093
_refine_diff_density_max         1.818
_refine_diff_density_min         -0.839
_refine_diff_density_rms         0.132
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     774
_refine_ls_number_reflns         13941
_refine_ls_number_restraints     23
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0750
_refine_ls_R_factor_gt           0.0415
_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^)+(0.0446P)^2^+7.1164P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0993
_refine_ls_wR_factor_ref         0.1090
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11306
_reflns_number_total             13941
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cp04862h2.cif
_cod_data_source_block           compound_5
_cod_original_formula_sum        'C59.40 H72.80 Cl3 Eu O4.35 P2'
_cod_database_code               7250341
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. 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
2. Restrained distances
 C22A-C23A = C23A-C24A = C24A-C25A = C25A-C26A = C26A-C27A = C27A-C22A
 1.39 with sigma of 0.01
 C49A-C50A = C50A-C51A = C51A-C52A = C52A-C53A = C53A-C54A = C54A-C49A
 1.39 with sigma of 0.01
 C59-C60A = C60-C59A = C60A-C59A
 1.52 with sigma of 0.01
 C59-O5 = C60-O5
 1.43 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
: with sigma of 0.003 and sigma for terminal atoms of 0.02
Uanis(C10) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.06
Uanis(C51A) = Uanis(C26)
Uanis(C24A) = Uanis(C53)
4. Others
 Fixed Sof: O3(0.65) H3C(0.65) H3D(0.65) Cl3(0.65) O3A(0.35) H3AA(0.35)
 H3AB(0.35) Cl3A(0.35) C22(0.65) C23(0.65) C24(0.65) C25(0.65) C26(0.65)
 C27(0.65) C49(0.65) C50(0.65) C51(0.65) C52(0.65) C53(0.65) C54(0.65)
 C22A(0.35) C23A(0.35) C24A(0.35) C25A(0.35) C26A(0.35) C27A(0.35) C49A(0.35)
 C50A(0.35) C51A(0.35) C52A(0.35) C53A(0.35) C54A(0.35) O5(0.35) C60(0.35)
 H60A(0.35) H60B(0.35) C59(0.35) H59A(0.35) H59B(0.35) C60A(0.35) H60C(0.35)
 H60D(0.35) C59A(0.35) H59C(0.35) H59D(0.35)
5.a Rotating group:
 O3(H3C,H3D), O3A(H3AA,H3AB)
5.b Ternary CH refined with riding coordinates:
 C14(H14), C12(H12), C16(H16), C4(H4), C8(H8), C2(H2), C39(H39), C41(H41),
 C33(H33), C43(H43), C29(H29), C31(H31)
5.c Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C20(H20A,H20B), C11(H11A,H11B), C15(H15A,H15B), C13(H13A,
 H13B), C19(H19A,H19B), C3(H3A,H3B), C5(H5A,H5B), C9(H9A,H9B), C1(H1A,H1B),
 C10(H10A,H10B), C7(H7A,H7B), C42(H42A,H42B), C44(H44A,H44B), C38(H38A,H38B),
 C36(H36A,H36B), C34(H34A,H34B), C30(H30A,H30B), C46(H46A,H46B), C37(H37A,H37B),
  C47(H47A,H47B), C40(H40A,H40B), C32(H32A,H32B), C28(H28A,H28B), C55(H55A,
 H55B), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C60(H60A,H60B),
 C59(H59A,H59B), C60A(H60C,H60D), C59A(H59C,H59D)
;
_shelx_res_checksum              77569
_olex2_submission_special_instructions 'No special instructions were received'