Correlating luminescence and single-molecule magnetism for two series of heteroleptic lanthanoid complexes.
González, Jonay; Fagundes, Vinicius K.; Hay, Moya A.; Dallerba, Elena; Massi, Massimiliano; Hall, Christopher R.; Giansiracusa, Marcus J.; Boskovic, Colette; Dalton transactions (Cambridge, England : 2003) 55 (2026) 1792–1805; doi:10.1039/d5dt02364e

data_7720810
_publ_section_title
;
 Correlating luminescence and single-molecule magnetism for two series of
 heteroleptic lanthanoid complexes.
;
_journal_issue                   4
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1792
_journal_page_last               1805
_journal_paper_doi               10.1039/d5dt02364e
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C18 H18 N7 O9 Tm, C2 H3 N'
_chemical_formula_sum            'C20 H21 N8 O9 Tm'
_chemical_formula_weight         686.38
_chemical_name_systematic        MH3-017-TmNO3
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-12-05
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-12-04 deposited with the CCDC.	2025-12-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.6960(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.7771(2)
_cell_length_b                   8.26530(10)
_cell_length_c                   27.1649(2)
_cell_measurement_reflns_used    22795
_cell_measurement_temperature    100.01(11)
_cell_measurement_theta_max      79.7770
_cell_measurement_theta_min      3.2830
_cell_volume                     4819.68(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.01(11)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -78.00 -25.00   0.50    0.55    --  -47.51 -77.00-175.00  106
  2  \w   -117.00 -84.00   0.50    0.55    --  -47.51 -77.00-175.00   66
  3  \w     28.00 119.00   0.50    0.55    --   47.51  77.00 -49.00  182
  4  \w     23.00  49.00   0.50    0.55    --   47.51 -77.00-175.00   52
  5  \w   -140.00-115.00   0.50    2.21    --  -91.75 -77.00-175.00   50
  6  \w    -79.00 -45.00   0.50    2.21    --  -91.75  77.00 -49.00   68
  7  \w     72.00  97.00   0.50    2.21    --  113.25 -77.00-175.00   50
  8  \w    151.00 177.00   0.50    2.21    --  113.25  77.00 -49.00   52
  9  \w    -47.00 -22.00   0.50    0.55    --  -47.51  77.00 -49.00   50
 10  \w    -85.00 -27.00   0.50    0.55    --  -47.51 125.00 -60.00  116
 11  \w    -85.00 -13.00   0.50    0.55    --  -47.51 125.00  90.00  144
 12  \w   -114.00 -46.00   0.50    0.55    --  -47.51 -38.00  30.00  136
 13  \w    -51.00 -21.00   0.50    2.21    --  -91.75  45.00 150.00   60
 14  \w    -46.00 -21.00   0.50    2.21    --  -91.75  45.00 -90.00   50
 15  \w     67.00 105.00   0.50    2.21    --  113.25 -94.00 -60.00   76
 16  \w     84.00 111.00   0.50    2.21    --  113.25-125.00  60.00   54
 17  \w     76.00 105.00   0.50    2.21    --  113.25 -94.00  60.00   58
 18  \w     56.00  82.00   0.50    2.21    --  113.25-125.00  60.00   52
 19  \w     42.00 101.00   0.50    2.21    --  113.25 -77.00  60.00  118
 20  \w     42.00  67.00   0.50    2.21    --  113.25 -94.00-120.00   50
 21  \w     81.00 106.00   0.50    2.21    --  113.25 -94.00-120.00   50
 22  \w    105.00 177.00   0.50    2.21    --  113.25  45.00-180.00  144
 23  \w     85.00 111.00   0.50    2.21    --  113.25-125.00-180.00   52
 24  \w     49.00  75.00   0.50    2.21    --  113.25 -94.00  60.00   52
 25  \w     45.00  83.00   0.50    2.21    --  113.25 -94.00-180.00   76
 26  \w     43.00  69.00   0.50    2.21    --  113.25 -61.00  60.00   52
 27  \w    104.00 139.00   0.50    2.21    --  113.25  15.00 120.00   70
 28  \w     44.00  70.00   0.50    2.21    --  113.25 -61.00-120.00   52
 29  \w     59.00  95.00   0.50    2.21    --  113.25 -77.00   0.00   72
 30  \w    112.00 177.00   0.50    2.21    --  113.25  30.00 -30.00  130
 31  \w     46.00  76.00   0.50    2.21    --  113.25-125.00-180.00   60
 32  \w    101.00 178.00   0.50    2.21    --  113.25  15.00  30.00  154
 33  \w     46.00  74.00   0.50    2.21    --  113.25 -94.00-150.00   56
 34  \w     50.00  76.00   0.50    2.21    --  113.25 -94.00 -90.00   52
 35  \w     81.00 106.00   0.50    2.21    --  113.25 -94.00 -90.00   50
 36  \w    103.00 128.00   0.50    2.21    --  113.25  30.00  60.00   50
 37  \w    133.00 165.00   0.50    2.21    --  113.25  30.00  60.00   64
 38  \w     42.00  98.00   0.50    2.21    --  113.25 -77.00 -30.00  112
 39  \w     65.00 103.00   0.50    2.21    --  113.25 -94.00 120.00   76
 40  \w     42.00  68.00   0.50    2.21    --  113.25 -61.00  90.00   52
 41  \w    103.00 177.00   0.50    2.21    --  113.25  30.00 -90.00  148
 42  \w     80.00 106.00   0.50    2.21    --  113.25 -94.00-150.00   52
 43  \w    103.00 168.00   0.50    2.21    --  113.25  45.00 -60.00  130
 44  \w     46.00  71.00   0.50    2.21    --  113.25 -61.00 -90.00   50
 45  \w     79.00 104.00   0.50    2.21    --  113.25 -94.00  30.00   50
 46  \w     81.00 106.00   0.50    2.21    --  113.25 -94.00 150.00   50
 47  \w    106.00 156.00   0.50    2.21    --  113.25  15.00-120.00  100
 48  \w    103.00 152.00   0.50    2.21    --  113.25  45.00 120.00   98
 49  \w     46.00  71.00   0.50    2.21    --  113.25 -61.00-150.00   50
 50  \w     42.00  67.00   0.50    2.21    --  113.25 -61.00  30.00   50
 51  \w     44.00  69.00   0.50    2.21    --  113.25 -61.00 120.00   50
 52  \w     70.00  95.00   0.50    2.21    --  113.25 -77.00-120.00   50
 53  \w     58.00  91.00   0.50    2.21    --  113.25 -77.00 -60.00   66
 54  \w     44.00  71.00   0.50    2.21    --  113.25 -61.00 -30.00   54
;
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0630057000
_diffrn_orient_matrix_UB_12      0.0043097000
_diffrn_orient_matrix_UB_13      0.0186176000
_diffrn_orient_matrix_UB_21      0.0263037000
_diffrn_orient_matrix_UB_22      -0.1141392000
_diffrn_orient_matrix_UB_23      0.0433201000
_diffrn_orient_matrix_UB_31      0.0220949000
_diffrn_orient_matrix_UB_32      0.1473496000
_diffrn_orient_matrix_UB_33      0.0329463000
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0335
_diffrn_reflns_av_unetI/netI     0.0194
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            31169
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.205
_diffrn_reflns_theta_min         3.301
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    7.508
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.320
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear whiteish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.892
_exptl_crystal_description       needle
_exptl_crystal_F_000             2704
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Acetonitrile/diisopropyl ether'
_exptl_crystal_size_max          0.982
_exptl_crystal_size_mid          0.057
_exptl_crystal_size_min          0.048
_refine_diff_density_max         0.949
_refine_diff_density_min         -1.186
_refine_diff_density_rms         0.116
_refine_ls_extinction_coef       0.000073(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     345
_refine_ls_number_reflns         5211
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0278
_refine_ls_R_factor_gt           0.0272
_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^)+(0.0533P)^2^+10.0979P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0779
_refine_ls_wR_factor_ref         0.0784
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5067
_reflns_number_total             5211
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02364e2.cif
_cod_data_source_block           tmno3_redabs
_cod_database_code               7720810
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C20H21O9N8Tm
_chemical_oxdiff_usercomment     '100 K'
_shelx_estimated_absorpt_t_max   0.715
_shelx_estimated_absorpt_t_min   0.051
_diffrn_oxdiff_ac3_digest_hkl    01d3a396fe6ec49b64a4260c546f930b7ebc85
_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 C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C7(H7A,H7B), C13(H13A,H13B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C15(H15), C16(H16), C17(H17), C18(H18)
2.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
;
_shelx_res_checksum              53813
_ins_header
;
TITL TmNO3_REDABS in C2/c 
REM C2/c (#15 in standard setting)
CELL 1.54184  21.777098   8.265319  27.164864  90.0000  99.6959  90.0000
ZERR    8.00   0.000180   0.000061   0.000214   0.0000   0.0008   0.0000
LATT  7
SYMM -x, y,-z+1/2 
SFAC C H N O Tm
UNIT 160.00 168.00 64.00 72.00 8.00
REM  CrysAlisPro recorded range (K): Min=99.9; max=100.1; aver:100.0
TEMP -173
SIZE 0.05 0.06 0.98
TREF
HKLF 4
END
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.332
_oxdiff_exptl_absorpt_empirical_full_min 0.697