Circularly polarized luminescence and performance modulation of chiral europium-titanium (Eu<sub>2</sub>Ti<sub>4</sub>)-oxo clusters.
Liu, Wei-Dong; Li, Guan-Jun; Xu, Han; Deng, Yong-Kai; Du, Ming-Hao; Long, La-Sheng; Zheng, Lan-Sun; Kong, Xiang-Jian; Chemical communications (Cambridge, England) 59 (2023) 346–349; doi:10.1039/d2cc05816b

data_7131112
_publ_section_title
;
 Circularly polarized luminescence and performance modulation of chiral
 europium-titanium (Eu<sub>2</sub>Ti<sub>4</sub>)-oxo clusters.
;
_journal_issue                   3
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              346
_journal_page_last               349
_journal_paper_doi               10.1039/d2cc05816b
_journal_volume                  59
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C84 H126 Eu2 N4 O26 Ti4'
_chemical_formula_sum            'C84 H126 Eu2 N4 O26 Ti4'
_chemical_formula_weight         2103.40
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-11-28
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-11-29 deposited with the CCDC.	2022-11-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 125.081(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   26.7869(10)
_cell_length_b                   15.6539(4)
_cell_length_c                   14.6425(6)
_cell_measurement_reflns_used    15145
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.1120
_cell_measurement_theta_min      3.4480
_cell_volume                     5024.5(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_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      100.00(10)
_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 0.952
_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     34.00  72.00   0.50    0.05    --   47.62  57.00 -60.00   76
  2  \w     27.00 118.00   0.50    0.05    --   47.62  77.00-150.00  182
  3  \w     58.00  84.00   0.50    0.05    --   47.62  52.00-179.00   52
  4  \w    -12.00  27.00   0.50    0.05    --   47.62 -19.00 -90.00   78
  5  \w    -25.00  11.00   0.50    0.05    --   47.62 -19.00-120.00   72
  6  \w    -23.00  28.00   0.50    0.05    --   47.62 -52.00  35.00  102
  7  \w     89.00 114.00   0.50    0.15    --  107.42  77.00-120.00   50
  8  \w     99.00 136.00   0.50    0.15    --  107.42  52.00-179.00   74
  9  \w    153.00 178.00   0.50    0.15    --  107.42  52.00-179.00   50
 10  \w     38.00  95.00   0.50    0.15    --  107.42 -77.00 -60.00  114
 11  \w     46.00  73.00   0.50    0.15    --  107.42 -61.00   0.00   54
 12  \w     40.00  73.00   0.50    0.15    --  107.42 -61.00  60.00   66
 13  \w     35.00  60.00   0.50    0.15    --  107.42 -52.00  35.00   50
 14  \w     42.00  67.00   0.50    0.15    --  107.42 -61.00 -60.00   50
 15  \w     42.00  68.00   0.50    0.15    --  107.42 -61.00-120.00   52
 16  \w     80.00 105.00   0.50    0.15    --  107.42 -95.00-150.00   50
 17  \w     35.00  73.00   0.50    0.15    --  107.42 -95.00-150.00   76
 18  \w     37.00 112.00   0.50    0.15    --  107.42-125.00-150.00  150
 19  \w    -77.00 -52.00   0.50    0.05    --  -47.62 -52.00  35.00   50
 20  \w   -118.00 -80.00   0.50    0.05    --  -47.62 -38.00-120.00   76
 21  \w    -48.00 -21.00   0.50    0.05    --  -47.62 125.00   0.00   54
 22  \w    -89.00 -50.00   0.50    0.05    --  -47.62 125.00   0.00   78
 23  \w    -69.00 -28.00   0.50    0.15    --  -99.00  61.00 -60.00   82
 24  \w    -56.00  25.00   0.50    0.05    --  -47.62  52.00-179.00  162
 25  \w    -57.00 -31.00   0.50    0.15    --  -99.00  52.00-179.00   52
 26  \w    -68.00 -28.00   0.50    0.15    --  -99.00  61.00  30.00   80
 27  \w    -65.00 -33.00   0.50    0.15    --  -99.00  61.00  90.00   64
 28  \w    -65.00 -28.00   0.50    0.15    --  -99.00  61.00 120.00   74
 29  \w   -171.00-143.00   0.50    0.15    --  -99.00 -15.00   0.00   56
 30  \w   -170.00-113.00   0.50    0.15    --  -99.00 -77.00   0.00  114
 31  \w   -110.00 -78.00   0.50    0.15    --  -99.00 -77.00   0.00   64
 32  \w   -102.00 -77.00   0.50    0.15    --  -99.00 -77.00 -60.00   50
 33  \w   -124.00 -78.00   0.50    0.15    --  -99.00 -77.00 -30.00   92
 34  \w   -168.00-142.00   0.50    0.15    --  -99.00 -61.00 -30.00   52
 35  \w   -117.00 -85.00   0.50    0.15    --  -99.00 -61.00 -30.00   64
 36  \w   -122.00 -84.00   0.50    0.15    --  -99.00 -61.00 -90.00   76
 37  \w   -121.00 -84.00   0.50    0.15    --  -99.00 -61.00 -60.00   74
 38  \w   -169.00 -86.00   0.50    0.15    --  -99.00 -55.00 -76.35  166
 39  \w   -130.00 -86.00   0.50    0.15    --  -99.00 -56.00 -70.31   88
 40  \w   -166.00 -90.00   0.50    0.15    --  -99.00 -45.00 -60.00  152
 41  \w   -142.00-102.00   0.50    0.15    --  -99.00 -52.00  35.00   80
 42  \w   -115.00 -83.00   0.50    0.15    --  -99.00 -77.00 150.00   64
 43  \w   -170.00 -88.00   0.50    0.15    --  -99.00 -61.00 120.00  164
 44  \w   -158.00-128.00   0.50    0.15    --  -99.00 -45.00 150.00   60
 45  \w   -166.00-136.00   0.50    0.15    --  -99.00 -77.00 150.00   60
 46  \w   -169.00 -94.00   0.50    0.15    --  -99.00 -45.00  90.00  150
 47  \w   -138.00-112.00   0.50    0.15    --  -99.00 -15.00   0.00   52
 48  \w   -172.00-118.00   0.50    0.15    --  -99.00 -30.00-120.00  108
 49  \w   -171.00 -89.00   0.50    0.15    --  -99.00 -30.00-150.00  164
;
_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      -0.0544412000
_diffrn_orient_matrix_UB_12      -0.0186587000
_diffrn_orient_matrix_UB_13      0.0062701000
_diffrn_orient_matrix_UB_21      -0.0405044000
_diffrn_orient_matrix_UB_22      0.0595863000
_diffrn_orient_matrix_UB_23      -0.1003076000
_diffrn_orient_matrix_UB_31      -0.0184079000
_diffrn_orient_matrix_UB_32      -0.0760184000
_diffrn_orient_matrix_UB_33      -0.0802148000
_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  0.0569
_diffrn_reflns_av_unetI/netI     0.0545
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            35765
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.925
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.979
_diffrn_reflns_theta_min         3.469
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.935
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67406
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.110a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.390
_exptl_crystal_description       block
_exptl_crystal_F_000             2160
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.03
_refine_diff_density_max         2.491
_refine_diff_density_min         -1.656
_refine_diff_density_rms         0.090
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.085(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     688
_refine_ls_number_reflns         9962
_refine_ls_number_restraints     415
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0673
_refine_ls_R_factor_gt           0.0576
_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^)+(0.0908P)^2^+13.5922P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1565
_refine_ls_wR_factor_ref         0.1644
_reflns_Friedel_coverage         0.873
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.897
_reflns_number_gt                8424
_reflns_number_total             9962
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc05816b2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7131110--7131117.cif.'
_cod_original_cell_volume        5024.5(4)
_cod_database_code               7131112
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C88H132Eu2N6O26Ti4
_chemical_oxdiff_usercomment     lwd-(+)-PA-Eu2Ti4
_shelx_estimated_absorpt_t_max   0.716
_shelx_estimated_absorpt_t_min   0.382
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.915(13)
 0.085(13)
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
3. Restrained distances
 C44-C23 \\sim C44-C23A
 with sigma of 0.02
 C14-C17 \\sim C14-C17A
 with sigma of 0.02
 C32-C11 \\sim C32A-C11A
 with sigma of 0.02
 C44-C33 \\sim C44-C33A
 with sigma of 0.02
 C14-C30 \\sim C14-C30A
 with sigma of 0.02
 C32-C37 \\sim C32A-C37A
 with sigma of 0.02
 C14-C29 \\sim C14-C29A
 with sigma of 0.02
 C44-C21 \\sim C44-C21A
 with sigma of 0.02
 C32-C43 \\sim C32A-C43A
 with sigma of 0.02
 C37-C43 \\sim C37A-C43A
 with sigma of 0.04
 C12-C32 \\sim C12-C32A
 with sigma of 0.02
 C12-C11 \\sim C12-C11A
 with sigma of 0.04
 C12-C37 \\sim C12-C37A
 with sigma of 0.04
 C40-C13 \\sim C40A-C13
 with sigma of 0.02
 C12-C43 \\sim C12-C43A
 with sigma of 0.04
 C11-C37 \\sim C11A-C37A
 with sigma of 0.04
 C11-C43 \\sim C11A-C43A
 with sigma of 0.04
 C13-C40A \\sim C13A-C40B
 with sigma of 0.02
 C40-C13 \\sim C42-C13A
 with sigma of 0.02
 C1-C40 \\sim C1-C42
 with sigma of 0.04
 C1-C41A \\sim C1-C41B
 with sigma of 0.04
 C41A-C40A \\sim C41B-C40B
 with sigma of 0.04
 C1-C40A \\sim C1-C40B
 with sigma of 0.04
 C13-C41A \\sim C13A-C41B
 with sigma of 0.02
 C40-C41A \\sim C42-C41B
 with sigma of 0.04
 C40-C40A \\sim C42-C40B
 with sigma of 0.04
 C1-C13 \\sim C1-C13A
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C14 \\sim C29 \\sim C17 \\sim C29A \\sim C17A \\sim C30 \\sim C30A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C14 \\sim C30 \\sim C29 \\sim C17 \\sim C30A \\sim C29A \\sim C17A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C32 \\sim C11 \\sim C37 \\sim C43 \\sim C37A \\sim C32A \\sim C43A \\sim C11A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C44 \\sim C23 \\sim C33 \\sim C21 \\sim C21A \\sim C23A \\sim C33A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C40 \\sim C13 \\sim C41A \\sim C40A \\sim C13A \\sim C41B \\sim C40B \\sim C42:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C27 \\sim C15 \\sim C20A \\sim C25A \\sim C7A \\sim C9A \\sim C19A \\sim C39A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
5. Others
 Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C23A)=Sof(H23D)=Sof(H23E)=
 Sof(H23F)=Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=1-FVAR(1)
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(1)
 Sof(C37A)=Sof(H37D)=Sof(H37E)=Sof(H37F)=Sof(C32A)=Sof(C43A)=Sof(H43D)=
 Sof(H43E)=Sof(H43F)=Sof(C11A)=Sof(H11D)=Sof(H11E)=Sof(H11F)=1-FVAR(2)
 Sof(C32)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C37)=Sof(H37A)=Sof(H37B)=
 Sof(H37C)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=FVAR(2)
 Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C29A)=Sof(H29D)=Sof(H29E)=
 Sof(H29F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=1-FVAR(3)
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=FVAR(3)
 Sof(C13A)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C41B)=Sof(H41D)=
 Sof(H41E)=Sof(H41F)=Sof(C40B)=Sof(H40G)=Sof(H40H)=Sof(H40I)=1-FVAR(4)
 Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C13)=Sof(C41A)=Sof(H41A)=Sof(H41B)=
 Sof(H41C)=Sof(C40A)=Sof(H40D)=Sof(H40E)=Sof(H40F)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C7A(H7A), C19A(H19A)
6.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C9A(H9AA,H9AB)
6.c Me refined with riding coordinates:
 C30(H30A,H30B,H30C), C11(H11A,H11B,H11C), C29(H29A,H29B,H29C), C17(H17A,H17B,
 H17C), C37(H37A,H37B,H37C), C43(H43A,H43B,H43C), C37A(H37D,H37E,H37F),
 C43A(H43D,H43E,H43F), C11A(H11D,H11E,H11F), C41A(H41A,H41B,H41C), C30A(H30D,
 H30E,H30F), C29A(H29D,H29E,H29F), C17A(H17D,H17E,H17F), C41B(H41D,H41E,H41F)
6.d Aromatic/amide H refined with riding coordinates:
 C18(H18), C22(H22), C24(H24), C28(H28), C34(H34), C38(H38)
6.e Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C40(H40A,H40B,H40C), C23(H23A,H23B,H23C), C31(H31A,H31B,
 H31C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C21(H21A,H21B,H21C),
 C21A(H21D,H21E,H21F), C23A(H23D,H23E,H23F), C33A(H33D,H33E,H33F), C40A(H40D,
 H40E,H40F), C42(H42A,H42B,H42C), C40B(H40G,H40H,H40I), C20A(H20A,H20B,H20C),
 C39A(H39A,H39B,H39C)
;
_shelx_res_checksum              41907
_shelx_hkl_checksum              24005
_shelx_fab_checksum              15355
_platon_squeeze_special_details
;
A solvent mask was calculated and 78 electrons were 
found in a volume of 332\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
3[C2H3N], 1[H2O] per Unit Cell 
which account for 76 electrons 
per unit cell.
;
_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 2.413
_oxdiff_exptl_absorpt_empirical_full_min 0.709