Structural relaxation chirality transfer enhanced circularly polarized luminescence in heteronuclear Ce<sup>III</sup>-Mn<sup>II</sup> complexes.
Liu, Huanyu; Yu, Gang; Huo, Peihao; Guo, Ruoyao; Li, Yujia; Qi, Hao; Zheng, Jiayin; Jin, Tong; Zhao, Zifeng; Bian, Zuqiang; Liu, Zhiwei; Materials horizons 12 (2025) 2650–2655; doi:10.1039/d4mh01760a

data_1573610
_publ_section_title
;
 Structural relaxation chirality transfer enhanced circularly polarized
 luminescence in heteronuclear Ce<sup>III</sup>-Mn<sup>II</sup> complexes.
;
_journal_issue                   8
_journal_name_full               'Materials horizons'
_journal_page_first              2650
_journal_page_last               2655
_journal_paper_doi               10.1039/d4mh01760a
_journal_volume                  12
_journal_year                    2025
_chemical_formula_moiety         '	C28 H58.39 Br1.61 La2 O14.39, Br4 Mn'
_chemical_formula_sum            'C28 H58.39 Br5.61 La2 Mn O14.39'
_chemical_formula_weight         1406.27
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-06-19
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-08-27 deposited with the CCDC.	2025-01-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.5414(4)
_cell_length_b                   15.5635(4)
_cell_length_c                   21.4150(6)
_cell_measurement_reflns_used    8615
_cell_measurement_temperature    180.01(11)
_cell_measurement_theta_max      29.2630
_cell_measurement_theta_min      1.6070
_cell_volume                     5179.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      180.01(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -27.00   8.00   0.50   24.00    --   17.32 -96.00 -78.00   70
  2  \w      5.00  30.00   0.50   24.00    --   17.32  96.00  31.00   50
  3  \w     44.00  87.00   0.50   24.00    --   17.32 178.00 -90.00   86
  4  \w     14.00  44.00   0.50   24.00    --   17.32  85.00 137.00   60
  5  \w    -26.00  27.00   0.50   24.00    --  -18.41 -96.00 -78.00  106
  6  \w    -21.00  12.00   0.50   24.00    --  -18.41 -99.00 120.00   66
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0388145000
_diffrn_orient_matrix_UB_12      -0.0085407000
_diffrn_orient_matrix_UB_13      -0.0162608000
_diffrn_orient_matrix_UB_21      -0.0173013000
_diffrn_orient_matrix_UB_22      -0.0395198000
_diffrn_orient_matrix_UB_23      -0.0107723000
_diffrn_orient_matrix_UB_31      -0.0166168000
_diffrn_orient_matrix_UB_32      0.0210596000
_diffrn_orient_matrix_UB_33      -0.0267663000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0334
_diffrn_reflns_av_unetI/netI     0.0538
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            20157
_diffrn_reflns_point_group_measured_fraction_full 0.967
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        25.026
_diffrn_reflns_theta_max         25.026
_diffrn_reflns_theta_min         1.617
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    6.234
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59120
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.803
_exptl_crystal_description       needle
_exptl_crystal_F_000             2707
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.462
_refine_diff_density_min         -1.019
_refine_diff_density_rms         0.164
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.12(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     483
_refine_ls_number_reflns         8868
_refine_ls_number_restraints     257
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0640
_refine_ls_R_factor_gt           0.0514
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0844P)^2^+8.3119P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1328
_refine_ls_wR_factor_ref         0.1391
_reflns_Friedel_coverage         0.753
_reflns_Friedel_fraction_full    0.930
_reflns_Friedel_fraction_max     0.930
_reflns_number_gt                7477
_reflns_number_total             8868
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4mh01760a2.cif
_cod_data_source_block           1_sq_CCDC1
_cod_depositor_comments
'Adding full bibliography for 1573609--1573612.cif.'
_cod_database_code               1573610
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.789
_shelx_estimated_absorpt_t_min   0.369
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.88(3)
 0.12(3)
2. 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, All O(H) groups
3. Restrained distances
 O10-C20 = O10-C21 = O9-C22 = O9-C23 = O8-C24 = O8-C25 = O7-C26 = O7-C27 = O12-
 C28 = O12-C17 = O11-C16 = O11-C19
 1.45 with sigma of 0.001
 C9-C11 = C9-C10 = C12-C10 = C14-C13 = C2-C1 = C4-C3 = C6-C5 = C8-C7 = C24-C23
 = C24A-C23A = C26-C25 = C28-C27 = C17-C16 = C18-C17 = C16-C15 = C20-C19 = C20A-
 C19A = C22A-C21A = C22-C21
 1.54 with sigma of 0.0001
 H8B-H9_$1
 2.2 with sigma of 0.01
 O11-C19 \\sim O11-C19A
 with sigma of 0.02
 O9-C23 \\sim O9-C24A
 with sigma of 0.02
 O10-C20 \\sim O10-C20A
 with sigma of 0.02
 O8-C24 \\sim O8-C23A
 with sigma of 0.02
 C19-C20 \\sim C19A-C20A
 with sigma of 0.02
 C24-C23 \\sim C23A-C24A
 with sigma of 0.02
 O9-C24 \\sim O9-C23A
 with sigma of 0.04
 O11-C20 \\sim O11-C20A
 with sigma of 0.04
 O10-C19 \\sim O10-C19A
 with sigma of 0.04
 O8-C23 \\sim O8-C24A
 with sigma of 0.04
 O9-C22 \\sim O9-C22A
 with sigma of 0.02
 O10-C21 \\sim O10-C21A
 with sigma of 0.02
 C21-C22 \\sim C21A-C22A
 with sigma of 0.02
 O9-C21 \\sim O9-C21A
 with sigma of 0.04
 O10-C22 \\sim O10-C22A
 with sigma of 0.04
4. Rigid bond restraints
 C23, C24, C25, O8, C26, O7, C27, C28, O12, C17, C16, C15, C18, O11, C19, C20,
 O10, C21, C22, O9
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Uiso/Uaniso restraints and constraints
Uanis(O5B) \\sim Ueq, Uanis(O6B) \\sim Ueq, Uanis(O7B) \\sim Ueq, Uanis(O8B)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C15) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C19) \\sim Ueq, Uanis(C19A) \\sim Ueq, Uanis(C20A) \\sim Ueq, Uanis(C20)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C24A) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C23A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C26) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C27)
\\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq,
Uanis(C1) \\sim Ueq, Uanis(C4) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C21A) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C22A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O7B) = Uanis(O8B) = Uanis(O6B) = Uanis(O5B)
Uanis(O6B) = Uanis(Br6A)
Uanis(C23A) = Uanis(C24) = Uanis(C24A) = Uanis(C23)
Uanis(C20A) = Uanis(C20) = Uanis(C19A) = Uanis(C19)
Uanis(C22) = Uanis(C22A) = Uanis(C21) = Uanis(C21A)
6. Rigid body (RIGU) restrains
 C24, C23
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C19, C20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C19A, C20A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C23A, C24A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, C22
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21A, C22A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(C24A)=Sof(H24C)=Sof(H24D)=Sof(C23A)=Sof(H23C)=Sof(H23D)=1-FVAR(1)
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(C23)=Sof(H23A)=Sof(H23B)=FVAR(1)
 Sof(C19A)=Sof(H19C)=Sof(H19D)=Sof(C20A)=Sof(H20C)=Sof(H20D)=1-FVAR(2)
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(H20A)=Sof(H20B)=FVAR(2)
 Sof(O5B)=Sof(H5B)=1-FVAR(3)
 Sof(Br5A)=FVAR(3)
 Sof(O6B)=Sof(H6B)=1-FVAR(4)
 Sof(Br6A)=FVAR(4)
 Sof(O7B)=Sof(H7B)=1-FVAR(5)
 Sof(Br7A)=FVAR(5)
 Sof(O8B)=Sof(H8B)=1-FVAR(6)
 Sof(Br8A)=FVAR(6)
 Sof(C22A)=Sof(H22C)=Sof(H22D)=Sof(C21A)=Sof(H21C)=Sof(H21D)=1-FVAR(7)
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(H22A)=Sof(H22B)=FVAR(7)
8.a Riding coordinates:
 O8B(H8B), O5B(H5B), O7B(H7B), O6B(H6B), C18(H18A,H18B,H18C)
8.b Ternary CH refined with riding coordinates:
 C9(H9), C10(H10), C16(H16), C17(H17)
8.c Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C7(H7A,H7C), C8(H8A,H8C), C13(H13A,H13B), C6(H6A,H6C),
 C28(H28A,H28B), C5(H5A,H5C), C2(H2A,H2B), C4(H4A,H4B), C27(H27A,H27B),
 C26(H26A,H26B), C25(H25A,H25B), C19(H19A,H19B), C1(H1A,H1B), C3(H3A,H3B),
 C20(H20A,H20B), C24(H24A,H24B), C23(H23A,H23B), C21(H21A,H21B), C22(H22A,H22B),
  C24A(H24C,H24D), C23A(H23C,H23D), C19A(H19C,H19D), C20A(H20C,H20D), C22A(H22C,
 H22D), C21A(H21C,H21D)
8.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C11(H11A,H11B,H11C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              41283
_shelx_fab_checksum              47025
_platon_squeeze_void_probe_radius 1.20
_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 1.374
_oxdiff_exptl_absorpt_empirical_full_min 0.832