pH-Switching of the luminescent, redox, and magnetic properties in a spin crossover cobalt(ii) molecular nanomagnet.
Rabelo, Renato; Toma, Luminita; Moliner, Nicolás; Julve, Miguel; Lloret, Francesc; Inclán, Mario; García-España, Enrique; Pasán, Jorge; Ruiz-García, Rafael; Cano, Joan; Chemical science 14 (2023) 8850–8859; doi:10.1039/d3sc02777e

data_1569587
_publ_section_title
;
 pH-Switching of the luminescent, redox, and magnetic properties in a spin
 crossover cobalt(ii) molecular nanomagnet.
;
_journal_issue                   33
_journal_name_full               'Chemical science'
_journal_page_first              8850
_journal_page_last               8859
_journal_paper_doi               10.1039/d3sc02777e
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety
'(C44 H29 Co N6 O4), (C44 H30 Co N6 O4), 3(Cl O4), 8.5(H2 O)'
_chemical_formula_sum            'C88 H76 Cl3 Co2 N12 O28.5'
_chemical_formula_weight         1981.83
_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   geom
_audit_creation_date             2023-06-21
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-06-29 deposited with the CCDC.	2023-07-26 downloaded from the CCDC.
;
_cell_angle_alpha                85.759(15)
_cell_angle_beta                 77.184(15)
_cell_angle_gamma                89.430(15)
_cell_formula_units_Z            1
_cell_length_a                   9.224(4)
_cell_length_b                   12.380(5)
_cell_length_c                   19.363(7)
_cell_measurement_reflns_used    46699
_cell_measurement_temperature    120.03
_cell_measurement_theta_max      25.228
_cell_measurement_theta_min      2.264
_cell_volume                     2150.1(15)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 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 2015 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.980
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0526
_diffrn_reflns_av_unetI/netI     0.0318
_diffrn_reflns_Laue_measured_fraction_full 0.980
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            46691
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        25.228
_diffrn_reflns_theta_max         25.228
_diffrn_reflns_theta_min         2.264
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.570
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.517
_exptl_crystal_description       plate
_exptl_crystal_F_000             1004
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          0.276
_exptl_crystal_size_mid          0.158
_exptl_crystal_size_min          0.020
_refine_diff_density_max         1.881
_refine_diff_density_min         -0.627
_refine_diff_density_rms         0.119
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     668
_refine_ls_number_reflns         7614
_refine_ls_number_restraints     59
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0790
_refine_ls_R_factor_gt           0.0704
_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^)+(0.1290P)^2^+6.5114P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2028
_refine_ls_wR_factor_ref         0.2120
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6578
_reflns_number_total             7617
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02777e2.cif
_cod_data_source_block           compound_1_protonated
_cod_depositor_comments
'Adding full bibliography for 1569587--1569588.cif.'
_cod_original_cell_volume        2150.0(14)
_cod_original_formula_sum        'C88 H76 Cl3 Co2 N12 O28.50'
_cod_database_code               1569587
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 Cl1-O5 = Cl1-O6 = Cl1-O7 = Cl1-O8
 1.41 with sigma of 0.02
 Cl1A-O5A = Cl1A-O6A = Cl1A-O7A = Cl1A-O8A
 1.41 with sigma of 0.02
 O5A-O6A \\sim O5A-O7A \\sim O5A-O8A \\sim O6A-O7A \\sim O6A-O8A \\sim O7A-O8A
 with sigma of 0.02
 O5-O6 \\sim O5-O7 \\sim O5-O8 \\sim O6-O7 \\sim O6-O8 \\sim O7-O8
 with sigma of 0.02
 Cl2A-O11A \\sim Cl2A-O9A \\sim Cl2A-O10A \\sim Cl2A-O12A
 with sigma of 0.02
 O11A-O9A \\sim O11A-O10A \\sim O11A-O12A \\sim O9A-O10A \\sim O9A-O12A \\sim
O10A-O12A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uiso(O5) = Uiso(O5A)
Uiso(O6) = Uiso(O6A)
4. Others
 Sof(Cl2A)=Sof(O9A)=Sof(O10A)=Sof(O11A)=Sof(O12A)=1-FVAR(1)
 Sof(Cl2)=Sof(O9)=Sof(O10)=Sof(O11)=Sof(O12)=FVAR(1)
 Sof(Cl1A)=Sof(O5A)=Sof(O6A)=Sof(O7A)=Sof(O8A)=0.5*(1-FVAR(3))
 Sof(Cl1)=Sof(O5)=Sof(O6)=Sof(O7)=Sof(O8)=0.5*FVAR(3)
 Fixed Sof: H2(0.75) H4(0.75) O14(0.5) O16(0.5) O16A(0.25) O17(0.5) O17A(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2A), C3(H3), C4(H4A), C7(H7), C9(H9), C12(H12), C13(H13),
 C14(H14), C15(H15), C17(H17), C18(H18), C20(H20), C21(H21), C23(H23), C24(H24),
  C25(H25), C26(H26), C29(H29), C31(H31), C34(H34), C35(H35), C36(H36),
 C37(H37), C39(H39), C40(H40), C42(H42), C43(H43)
5.b Idealised tetrahedral OH refined as rotating group:
 O2(H2), O4(H4)
;
_shelx_res_checksum              71412
_olex2_submission_special_instructions 'No special instructions were received'