Efficient circularly polarized luminescence from zero-dimensional terbium- and europium-based hybrid metal halides.
Zhang, Yan; Wei, Yi; Li, Chen; Wang, Yuxuan; Liu, Yulian; He, Meiying; Luo, Zhishan; Chang, Xiaoyong; Kuang, Xiaojun; Quan, Zewei; Chemical communications (Cambridge, England) 61 (2024) 85–88; doi:10.1039/d4cc05206d

data_7134026
_publ_section_title
;
 Efficient circularly polarized luminescence from zero-dimensional
 terbium- and europium-based hybrid metal halides.
;
_journal_issue                   1
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              85
_journal_page_last               88
_journal_paper_doi               10.1039/d4cc05206d
_journal_volume                  61
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(Cl6 Tb), 6(C5 H12 N O)'
_chemical_formula_sum            'C30 H72 Cl12 N6 O6 Tb2'
_chemical_formula_weight         1356.17
_chemical_properties_physical    Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-09-18
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-09-20 deposited with the CCDC.	2024-11-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.982(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.2751(7)
_cell_length_b                   11.9418(7)
_cell_length_c                   16.8205(10)
_cell_measurement_reflns_used    9305
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      27.43
_cell_measurement_theta_min      2.51
_cell_volume                     2640.7(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Apex3 (Bruker 2018)'
_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  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT 2014'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Bruker PHOTON III area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0557
_diffrn_reflns_av_unetI/netI     0.0415
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            73907
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.545
_diffrn_reflns_theta_min         1.549
_diffrn_source                   'microfocus Metaljet'
_diffrn_source_type              'Incoatec Metaljet'
_exptl_absorpt_coefficient_mu    3.305
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6446
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0913 before and 0.0762 after correction.
The Ratio of minimum to maximum transmission is 0.8645.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.706
_exptl_crystal_description       block
_exptl_crystal_F_000             1352
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.21
_refine_diff_density_max         2.161
_refine_diff_density_min         -1.712
_refine_diff_density_rms         0.164
_refine_ls_abs_structure_details
;
 Flack x determined using 4174 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.015(6)
_refine_ls_extinction_coef       0.00138(14)
_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   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     574
_refine_ls_number_reflns         12139
_refine_ls_number_restraints     451
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0663
_refine_ls_R_factor_gt           0.0476
_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^)+(0.0154P)^2^+21.9091P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0908
_refine_ls_wR_factor_ref         0.1017
_reflns_Friedel_coverage         0.904
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                9903
_reflns_number_total             12139
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc05206d2.cif
_cod_data_source_block           mo_r_bdtbcl_0m
_cod_depositor_comments
'Adding full bibliography for 7134023--7134026.cif.'
_cod_database_code               7134026
_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, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C6A-C7A \\sim C6-C7
 with sigma of 0.02
 O2A-C8A \\sim O2-C8
 with sigma of 0.02
 C8A-C7A \\sim C8-C7
 with sigma of 0.02
 C10-C7A \\sim C10A-C7
 with sigma of 0.04
 C10-N2A \\sim C10A-N2
 with sigma of 0.02
 O2A-C9 \\sim O2-C9A
 with sigma of 0.02
 C9-N2A \\sim C9A-N2
 with sigma of 0.04
 C7A-N2A \\sim C7-N2
 with sigma of 0.02
 C10-C9 \\sim C10A-C9A
 with sigma of 0.02
 O2A-C10 \\sim O2-C10A
 with sigma of 0.04
 O2A-C7A \\sim O2-C7
 with sigma of 0.04
 C6A-C8A \\sim C6-C8
 with sigma of 0.04
 C6A-N2A \\sim C6-N2
 with sigma of 0.04
 C8A-C9 \\sim C8-C9A
 with sigma of 0.04
 C8A-N2A \\sim C8-N2
 with sigma of 0.04
 N6A-C28A \\sim N6-C28
 with sigma of 0.04
 C29A-N6A \\sim C29-N6
 with sigma of 0.04
 O6A-C27A \\sim O6-C27
 with sigma of 0.04
 C29A-C28A \\sim C29-C28
 with sigma of 0.04
 C28A-C26A \\sim C28-C26
 with sigma of 0.04
 C27A-C30A \\sim C27-C30
 with sigma of 0.04
 C27A-C26A \\sim C27-C26
 with sigma of 0.02
 C29A-O6A \\sim C29-O6
 with sigma of 0.02
 O6A-C30A \\sim O6-C30
 with sigma of 0.04
 N6A-C30A \\sim N6-C30
 with sigma of 0.02
 O6A-C28A \\sim O6-C28
 with sigma of 0.02
 C29A-C30A \\sim C29-C30
 with sigma of 0.02
 C27A-C28A \\sim C27-C28
 with sigma of 0.02
 C27A-N6A \\sim C27-N6
 with sigma of 0.02
 N6A-C26A \\sim N6-C26
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O2 \\sim N2 \\sim C6 \\sim C7 \\sim C8 \\sim C9A \\sim C10A \\sim O2A \\sim N2A
\\sim C6A \\sim C7A \\sim C8A \\sim C9 \\sim C10: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
O6 \\sim N6 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim O6A \\sim
N6A \\sim C26A \\sim C27A \\sim C28A \\sim C29A \\sim C30A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(Cl9) = Uanis(Cl9A)
Uanis(Cl8) = Uanis(Cl8A)
Uanis(Cl10) = Uanis(Cl11)
Uanis(Cl12) = Uanis(Cl13)
Uanis(Cl14) = Uanis(Cl15)
Uanis(C8A) = Uanis(C8)
Uanis(N2) = Uanis(N2A)
Uanis(C6) = Uanis(C6A)
Uanis(C9A) = Uanis(C9)
Uanis(C7A) = Uanis(C7)
Uanis(C10A) = Uanis(C10)
Uanis(O2A) = Uanis(O2)
Uanis(O6A) = Uanis(O6)
Uanis(C28A) = Uanis(C28)
Uanis(C26) = Uanis(C26A)
Uanis(N6A) = Uanis(N6)
Uanis(C29A) = Uanis(C29)
Uanis(C27) = Uanis(C27A)
Uanis(C30A) = Uanis(C30)
4. Others
 Sof(Cl9A)=Sof(Cl11)=Sof(Cl13)=Sof(Cl15)=Sof(Cl8A)=1-FVAR(1)
 Sof(Cl8)=Sof(Cl9)=Sof(Cl10)=Sof(Cl12)=Sof(Cl14)=FVAR(1)
 Sof(O2)=Sof(N2)=Sof(H2A)=Sof(H2B)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C7)=
 Sof(H7)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(C10A)=
 Sof(H10A)=Sof(H10B)=1-FVAR(2)
 Sof(O2A)=Sof(N2A)=Sof(H2AA)=Sof(H2AB)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=
 Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(C9)=Sof(H9A)=Sof(H9B)=
 Sof(C10)=Sof(H10C)=Sof(H10D)=FVAR(2)
 Sof(O6)=Sof(N6)=Sof(H6D)=Sof(H6E)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=
 Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(C29)=Sof(H29A)=Sof(H29B)=
 Sof(C30)=Sof(H30A)=Sof(H30B)=1-FVAR(3)
 Sof(O6A)=Sof(N6A)=Sof(H6AD)=Sof(H6AE)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=
 Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(H28C)=Sof(H28D)=Sof(C29A)=Sof(H29C)=
 Sof(H29D)=Sof(C30A)=Sof(H30C)=Sof(H30D)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C2(H2), C7(H7), C7A(H7A), C12(H12), C17(H17), C22(H22), C27(H27), C27A(H27A)
5.b Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), N2(H2A,H2B), C8(H8A,H8B),
 C9A(H9AA,H9AB), C10A(H10A,H10B), N2A(H2AA,H2AB), C8A(H8AA,H8AB), C9(H9A,H9B),
 C10(H10C,H10D), N3(H3C,H3D), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B),
 N4(H4C,H4D), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), N5(H5C,H5D),
 C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), N6(H6D,H6E), C28(H28A,H28B),
 C29(H29A,H29B), C30(H30A,H30B), N6A(H6AD,H6AE), C28A(H28C,H28D), C29A(H29C,
 H29D), C30A(H30C,H30D)
5.c Idealised Me refined as rotating group:
 C1(H1C,H1D,H1E), C6(H6A,H6B,H6C), C6A(H6AA,H6AB,H6AC), C11(H11A,H11B,H11C),
 C16(H16A,H16B,H16C), C21(H21A,H21B,H21C), C26(H26A,H26B,H26C), C26A(H26D,H26E,
 H26F)
;
_shelx_res_checksum              6955
_shelx_hkl_checksum              2450
_olex2_submission_special_instructions 'No special instructions were received'