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_7720812
_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 Cl3 N4 Tb'
_chemical_formula_sum            'C18 H18 Cl3 N4 Tb'
_chemical_formula_weight         555.63
_chemical_name_systematic        MH3-017-TbCl
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-12-19
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-12-04 deposited with the CCDC.	2025-12-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.5110(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.62510(10)
_cell_length_b                   16.23530(10)
_cell_length_c                   14.64480(10)
_cell_measurement_reflns_used    50113
_cell_measurement_temperature    100.0(4)
_cell_measurement_theta_max      80.0530
_cell_measurement_theta_min      4.2010
_cell_volume                     1985.31(3)
_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      100.0(4)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_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    -12.00  16.00   0.50    0.05    --   18.00  97.00-109.74   56
  2  \w    -12.00  21.00   0.50    0.05    --   18.00  96.00 -73.18   66
  3  \w      1.00  28.00   0.50    0.05    --   30.00  93.00  37.29   54
  4  \w    -40.00 -15.00   0.50    0.05    --    6.00 125.00  44.03   50
  5  \w     17.00  42.00   0.50    0.05    --   46.00  90.00  68.33   50
  6  \w     17.00  42.00   0.50    0.05    --   46.00  90.00 124.73   50
  7  \w     17.00  42.00   0.50    0.05    --   46.00  90.00 156.54   50
  8  \w     82.00 108.00   0.50    0.05    --   50.00  74.00 170.14   52
  9  \w     29.00  60.00   0.50    0.05    --   50.00  74.00 170.14   62
 10  \w     91.00 133.00   0.50    0.21    --  113.25  77.00 120.00   84
 11  \w     92.00 125.00   0.50    0.21    --  113.25  77.00  90.00   66
 12  \w    133.00 178.00   0.50    0.21    --  113.25  77.00  90.00   90
 13  \w    137.00 177.00   0.50    0.21    --  113.25  77.00   0.00   80
 14  \w    140.00 178.00   0.50    0.21    --  113.25  77.00 -30.00   76
 15  \w     92.00 135.00   0.50    0.21    --  113.25  77.00 -30.00   86
 16  \w     91.00 119.00   0.50    0.21    --  113.25  77.00   0.00   56
 17  \w    141.00 176.00   0.50    0.21    --  113.25  77.00 -90.00   70
 18  \w    142.00 177.00   0.50    0.21    --  113.25  77.00-120.00   70
 19  \w     92.00 136.00   0.50    0.21    --  113.25  77.00-120.00   88
 20  \w     27.00  52.00   0.50    0.05    --   50.00  77.00 -63.22   50
 21  \w     31.00  83.00   0.50    0.05    --   54.00  77.00 -36.48  104
 22  \w     91.00 118.00   0.50    0.21    --  113.25  77.00  60.00   54
 23  \w    125.00 157.00   0.50    0.21    --  113.25  77.00  60.00   64
 24  \w    153.00 178.00   0.50    0.21    --  113.25  77.00 150.00   50
 25  \w     94.00 178.00   0.50    0.21    --  113.25  77.00 -60.00  168
 26  \w     95.00 133.00   0.50    0.21    --  113.25  77.00 -90.00   76
 27  \w     91.00 121.00   0.50    0.21    --  113.25  77.00-150.00   60
 28  \w     91.00 134.00   0.50    0.21    --  113.25  77.00-180.00   86
 29  \w    130.00 175.00   0.50    0.21    --  113.25  77.00-150.00   90
 30  \w     92.00 178.00   0.50    0.21    --  113.25  77.00  30.00  172
 31  \w    140.00 175.00   0.50    0.21    --  113.25  77.00 120.00   70
 32  \w     91.00 137.00   0.50    0.21    --  113.25  77.00 150.00   92
 33  \w     32.00  58.00   0.50    0.05    --   54.00  76.00  44.88   52
 34  \w     73.00  99.00   0.50    0.05    --   54.00  76.00  44.88   52
 35  \w     32.00  58.00   0.50    0.05    --   54.00  75.00 107.72   52
 36  \w     33.00  58.00   0.50    0.05    --   54.00  75.00-108.19   50
 37  \w     33.00  59.00   0.50    0.05    --   54.00  75.00-124.75   52
 38  \w     63.00  89.00   0.50    0.05    --   54.00  75.00-124.75   52
 39  \w     90.00 125.00   0.50    0.05    --   54.00  75.00-108.19   70
 40  \w    101.00 126.00   0.50    0.05    --   54.00  74.00  13.03   50
 41  \w     38.00  64.00   0.50    0.05    --   54.00  74.00 129.26   52
 42  \w     35.00  61.00   0.50    0.05    --   54.00  74.00  72.62   52
 43  \w     33.00  58.00   0.50    0.05    --   54.00  74.00  13.03   50
 44  \w     37.00  62.00   0.50    0.05    --   58.00  73.00 -17.71   50
 45  \w     33.00  59.00   0.50    0.05    --   54.00  74.00-151.32   52
 46  \w     82.00 120.00   0.50    0.21    --  102.00  74.00-126.93   76
 47  \w    146.00 174.00   0.50    0.21    --  102.00  74.00-126.93   56
 48  \w     97.00 122.00   0.50    0.21    --  113.25  61.00 -30.00   50
 49  \w     99.00 150.00   0.50    0.21    --  113.25  61.00  30.00  102
 50  \w     98.00 158.00   0.50    0.21    --  113.25  61.00 120.00  120
 51  \w    100.00 176.00   0.50    0.21    --  113.25  61.00  60.00  152
 52  \w     98.00 174.00   0.50    0.21    --  113.25  61.00   0.00  152
 53  \w    128.00 155.00   0.50    0.21    --  113.25  61.00 -30.00   54
 54  \w    101.00 165.00   0.50    0.21    --  113.25  61.00  90.00  128
 55  \w    133.00 173.00   0.50    0.21    --  113.25  61.00 150.00   80
 56  \w     97.00 129.00   0.50    0.21    --  113.25  61.00 150.00   64
 57  \w     99.00 155.00   0.50    0.21    --  113.25  61.00 -60.00  112
 58  \w     97.00 172.00   0.50    0.21    --  113.25  61.00-180.00  150
 59  \w     98.00 159.00   0.50    0.21    --  113.25  61.00-150.00  122
 60  \w     99.00 162.00   0.50    0.21    --  113.25  61.00 -90.00  126
 61  \w    106.00 131.00   0.50    0.21    --  113.25 139.00  13.00   50
 62  \w     94.00 134.00   0.50    0.21    --  113.25 131.00-161.00   80
 63  \w     45.00  90.00   0.50    0.21    --  113.25 -77.00 -30.00   90
 64  \w     46.00 100.00   0.50    0.21    --  113.25 -77.00  30.00  108
 65  \w     48.00  89.00   0.50    0.21    --  113.25 -77.00 120.00   82
 66  \w     42.00  89.00   0.50    0.21    --  113.25 -77.00 150.00   94
 67  \w     42.00  71.00   0.50    0.21    --  113.25 -77.00-150.00   58
 68  \w     43.00 103.00   0.50    0.21    --  113.25 -94.00 -90.00  120
 69  \w     49.00  74.00   0.50    0.21    --  113.25-139.00 -47.00   50
 70  \w     82.00 121.00   0.50    0.21    --  113.25-139.00 -47.00   78
 71  \w     80.00 110.00   0.50    0.21    --  113.25-125.00 -90.00   60
 72  \w     42.00 102.00   0.50    0.05    --   47.51-139.00 -47.00  120
 73  \w     86.00 111.00   0.50    0.21    --  113.25-125.00-150.00   50
 74  \w     46.00 110.00   0.50    0.21    --  113.25-125.00-120.00  128
 75  \w     45.00  70.00   0.50    0.21    --  113.25-125.00-150.00   50
 76  \w     46.00 111.00   0.50    0.21    --  113.25-125.00  60.00  130
 77  \w     45.00 110.00   0.50    0.21    --  113.25-125.00  90.00  130
 78  \w     67.00 108.00   0.50    0.21    --  113.25-131.00 127.00   82
 79  \w     64.00 107.00   0.50    0.21    --  113.25-105.00 127.00   86
 80  \w     45.00 106.00   0.50    0.21    --  113.25 -94.00 120.00  122
 81  \w     38.00  96.00   0.50    0.05    --   47.51-131.00 127.00  116
 82  \w     45.00 106.00   0.50    0.21    --  113.25 -94.00 -30.00  122
 83  \w     44.00  76.00   0.50    0.21    --  113.25 -94.00 -60.00   64
 84  \w     80.00 106.00   0.50    0.21    --  113.25 -94.00 -60.00   52
 85  \w    -95.00 -34.00   0.50    0.05    --  -47.51 139.00  13.00  122
 86  \w    -82.00 -57.00   0.50    0.21    --  -91.75 139.00  13.00   50
 87  \w    -80.00 -55.00   0.50    0.21    --  -91.75 131.00-161.00   50
 88  \w    -89.00 -16.00   0.50    0.05    --  -47.51 131.00-161.00  146
 89  \w   -117.00 -91.00   0.50    0.05    --  -47.51 -45.00-155.70   52
 90  \w   -117.00 -47.00   0.50    0.05    --  -47.51 -19.00-120.00  140
 91  \w    -74.00 -47.00   0.50    0.05    --  -47.51 -45.00-155.70   54
 92  \w    -70.00 -37.00   0.50    0.05    --  -47.51 -19.00  60.00   66
 93  \w   -108.00 -83.00   0.50    0.05    --  -47.51 -19.00  60.00   50
 94  \w    -77.00 -51.00   0.50    0.05    --  -74.00 -77.00 -28.83   52
 95  \w    -81.00 -55.00   0.50    0.05    --  -78.00 -77.00 -99.56   52
 96  \w    -85.00 -59.00   0.50    0.21    --  -82.00 -77.00-150.31   52
 97  \w    -96.00 -70.00   0.50    0.21    --  -91.75 -77.00 -90.00   52
 98  \w    -95.00 -69.00   0.50    0.21    --  -91.75 -77.00 -30.00   52
 99  \w    -96.00 -70.00   0.50    0.21    --  -91.75 -77.00  60.00   52
100  \w    -94.00 -69.00   0.50    0.21    --  -91.75 -77.00  90.00   50
101  \w    -95.00 -69.00   0.50    0.21    --  -91.75 -77.00 115.46   52
102  \w   -110.00 -69.00   0.50    0.21    --  -91.75 -77.00 151.46   82
103  \w   -161.00-135.00   0.50    0.21    --  -91.75 -77.00 151.46   52
104  \w    -96.00 -71.00   0.50    0.21    --  -91.75 -77.00 -60.00   50
105  \w    -95.00 -69.00   0.50    0.21    --  -91.75 -77.00-120.00   52
106  \w    -98.00 -70.00   0.50    0.21    --  -91.75 -77.00-150.00   56
107  \w   -163.00-112.00   0.50    0.21    --  -91.75 -77.00-120.00  102
108  \w   -134.00 -69.00   0.50    0.21    --  -91.75 -77.00   0.00  130
109  \w    -77.00 -51.00   0.50    0.05    --  -74.00 -76.00 -74.68   52
110  \w    -85.00 -60.00   0.50    0.21    --  -82.00 -76.00 149.52   50
111  \w    -85.00 -55.00   0.50    0.05    --  -78.00 -76.00 170.72   60
112  \w    -92.00 -67.00   0.50    0.21    --  -90.00 -76.00 175.24   50
113  \w   -162.00-127.00   0.50    0.21    --  -90.00 -76.00 175.24   70
114  \w    -89.00 -64.00   0.50    0.21    --  -86.00 -75.00 123.92   50
115  \w    -90.00 -60.00   0.50    0.21    --  -82.00 -75.00  89.87   60
116  \w   -104.00 -71.00   0.50    0.21    --  -91.75 -72.00  65.85   66
117  \w    -94.00 -69.00   0.50    0.21    --  -91.75 -76.00  15.14   50
118  \w   -100.00 -71.00   0.50    0.21    --  -91.75 -73.00 -54.09   58
119  \w   -102.00 -72.00   0.50    0.21    --  -91.75 -70.00 -20.71   60
120  \w   -104.00 -72.00   0.50    0.21    --  -91.75 -69.00 -34.50   64
121  \w   -108.00 -72.00   0.50    0.21    --  -91.75 -69.00  21.69   72
122  \w    -82.00 -48.00   0.50    0.05    --  -66.00 -68.00  70.02   68
123  \w    -99.00 -73.00   0.50    0.21    --  -91.75 -67.00  31.62   52
124  \w    -98.00 -73.00   0.50    0.21    --  -91.75 -67.00 156.74   50
125  \w   -160.00-135.00   0.50    0.21    --  -91.75 -67.00 156.74   50
126  \w    -73.00 -43.00   0.50    0.05    --  -62.00 -67.00 -18.70   60
127  \w    -98.00 -72.00   0.50    0.21    --  -91.75 -71.00 -78.62   52
128  \w    -97.00 -71.00   0.50    0.21    --  -91.75 -71.00-114.90   52
129  \w    -79.00 -53.00   0.50    0.05    --  -74.00 -75.00-178.69   52
130  \w    -80.00 -46.00   0.50    0.05    --  -62.00 -65.00-171.91   68
131  \w    -79.00 -48.00   0.50    0.05    --  -66.00 -65.00-150.27   62
132  \w    -74.00 -48.00   0.50    0.05    --  -66.00 -65.00-122.85   52
133  \w    -84.00 -58.00   0.50    0.05    --  -74.00 -63.00 -81.04   52
134  \w    -97.00 -57.00   0.50    0.05    --  -74.00 -63.00 -33.54   80
135  \w    -73.00 -48.00   0.50    0.05    --  -66.00 -65.00   0.63   50
136  \w    -89.00 -48.00   0.50    0.05    --  -66.00 -64.00  29.62   82
137  \w    -83.00 -57.00   0.50    0.05    --  -74.00 -62.00  -5.06   52
138  \w    -87.00 -61.00   0.50    0.05    --  -78.00 -62.00 -16.40   52
139  \w    -83.00 -57.00   0.50    0.05    --  -74.00 -62.00  21.51   52
140  \w    -75.00 -49.00   0.50    0.05    --  -66.00 -63.00  96.27   52
141  \w    -75.00 -49.00   0.50    0.05    --  -66.00 -63.00 117.15   52
142  \w   -106.00 -75.00   0.50    0.21    --  -91.75 -61.00  60.00   62
143  \w    -91.00 -63.00   0.50    0.05    --  -78.00 -60.00-169.03   56
144  \w   -116.00 -91.00   0.50    0.05    --  -47.51-139.00 -47.00   50
145  \w   -135.00-109.00   0.50    0.21    --  -91.75-139.00 -47.00   52
146  \w   -140.00-115.00   0.50    0.21    --  -91.75-131.00 127.00   50
147  \w   -118.00 -93.00   0.50    0.05    --  -47.51-131.00 127.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0093919000
_diffrn_orient_matrix_UB_12      0.0907596000
_diffrn_orient_matrix_UB_13      -0.0316604000
_diffrn_orient_matrix_UB_21      -0.0480901000
_diffrn_orient_matrix_UB_22      -0.0275781000
_diffrn_orient_matrix_UB_23      -0.1039497000
_diffrn_orient_matrix_UB_31      -0.1778318000
_diffrn_orient_matrix_UB_32      0.0026485000
_diffrn_orient_matrix_UB_33      0.0015583000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0861
_diffrn_reflns_av_unetI/netI     0.0243
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            73355
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.333
_diffrn_reflns_theta_min         4.140
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    21.305
_exptl_absorpt_correction_T_max  0.653
_exptl_absorpt_correction_T_min  0.052
_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    1.859
_exptl_crystal_description       needle
_exptl_crystal_F_000             1080
_exptl_crystal_preparation       'Magnetic properties,Luminescent'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Acetonitrile/Diisopropylether'
_exptl_crystal_size_max          0.51
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.075
_refine_diff_density_max         0.834
_refine_diff_density_min         -0.970
_refine_diff_density_rms         0.111
_refine_ls_extinction_coef       0.00057(6)
_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   0.838
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     236
_refine_ls_number_reflns         4304
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.838
_refine_ls_R_factor_all          0.0273
_refine_ls_R_factor_gt           0.0266
_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^)+(0.0643P)^2^+3.2726P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0749
_refine_ls_wR_factor_ref         0.0758
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4193
_reflns_number_total             4304
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02364e2.cif
_cod_data_source_block           exp_962
_cod_database_code               7720812
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C18H18Cl3N4Tb
_chemical_oxdiff_usercomment
'TbCl3 needle crystallized straight out of solution'
_shelx_estimated_absorpt_t_max   0.298
_shelx_estimated_absorpt_t_min   0.033
_olex2_refinement_description
;
1.a Secondary CH2 refined with riding coordinates:
 C009(H00A,H00B), C00J(H00F,H00J), C00O(H00O,H00P)
1.b Aromatic/amide H refined with riding coordinates:
 C00A(H00C), C00C(H00D), C00E(H00E), C00G(H00G), C00H(H00H), C00I(H00I),
 C00K(H00K), C00L(H00L), C00M(H00M), C00N(H00N), C00P(H00Q), C00Q(H00R)
;
_shelx_res_checksum              54330
_ins_header
;
TITL exp_962 in P2(1)/c 
REM P2(1)/c (#14 in standard setting)
CELL 1.54184   8.625083  16.235337  14.644795  90.0000 104.5113  90.0000
ZERR    4.00   0.000058   0.000084   0.000086   0.0000   0.0006   0.0000
LATT  1
SYMM -x, y+1/2,-z+1/2 
SFAC C H N Cl Tb
UNIT 72.00 72.00 16.00 12.00 4.00
REM  CrysAlisPro recorded range (K): Min=99.7; max=100.2; aver:100.0
TEMP -173
SIZE 0.07 0.09 0.51
TREF
HKLF 4
END
;
_olex2_submission_original_sample_id MH3-017-TbCl
_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 1.832
_oxdiff_exptl_absorpt_empirical_full_min 0.591