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_7131113
_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                 125.433(15)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   26.861(3)
_cell_length_b                   15.6451(9)
_cell_length_c                   14.6838(17)
_cell_measurement_reflns_used    11656
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      74.0990
_cell_measurement_theta_min      3.4730
_cell_volume                     5027.9(13)
_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      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.953
_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     18.00  44.00   0.50    0.20    --   42.11  77.00   0.00   52
  2  \w     21.00 114.00   0.50    0.20    --   42.11  57.00 -30.00  186
  3  \w     67.00 111.00   0.50    0.20    --   42.11  57.00  30.00   88
  4  \w     16.00  52.00   0.50    0.20    --   42.11  77.00  60.00   72
  5  \w     24.00  49.00   0.50    0.20    --   42.11  57.00  90.00   50
  6  \w     26.00  62.00   0.50    0.20    --   42.11  57.00  30.00   72
  7  \w     12.00  85.00   0.50    0.20    --   42.11  21.00 -78.00  146
  8  \w     20.00  73.00   0.50    0.20    --   42.11  38.00 -60.00  106
  9  \w     78.00 112.00   0.50    0.20    --   42.11  38.00 -60.00   68
 10  \w      2.00  39.00   0.50    0.20    --  -42.11  19.00 -30.00   74
 11  \w    -49.00 -24.00   0.50    0.50    --  -99.00  45.00  60.00   50
 12  \w    -60.00 -25.00   0.50    0.50    --  -99.00  61.00  60.00   70
 13  \w    -49.00 -24.00   0.50    0.50    --  -99.00  45.00  30.00   50
 14  \w    -49.00 -24.00   0.50    0.50    --  -99.00  45.00   0.00   50
 15  \w    -18.00   7.00   0.50    0.20    --  -42.11  21.00 -78.00   50
 16  \w    119.00 153.00   0.50    0.50    --  108.55  21.00 -78.00   68
 17  \w    146.00 178.00   0.50    0.50    --  108.55  77.00 -30.00   64
 18  \w    115.00 141.00   0.50    0.50    --  108.55  77.00 -30.00   52
 19  \w     80.00 107.00   0.50    0.50    --  108.55  77.00 -30.00   54
 20  \w     80.00 116.00   0.50    0.50    --  108.55  21.00 -78.00   72
 21  \w     56.00 106.00   0.50    0.50    --  108.55 -77.00 -60.00  100
 22  \w     36.00  65.00   0.50    0.50    --  108.55 -61.00-150.00   58
 23  \w     38.00  71.00   0.50    0.50    --  108.55 -61.00 -90.00   66
 24  \w     34.00  84.00   0.50    0.50    --  108.55 -77.00 -30.00  100
 25  \w     35.00  60.00   0.50    0.50    --  108.55 -61.00 -30.00   50
 26  \w    -27.00  30.00   0.50    0.20    --   42.11 -21.00 114.00  114
 27  \w     37.00  73.00   0.50    0.50    --  108.55 -61.00 150.00   72
 28  \w     19.00  94.00   0.50    0.20    --   42.11-125.00  30.00  150
 29  \w     70.00  96.00   0.50    0.50    --  108.55-125.00  60.00   52
 30  \w     41.00  66.00   0.50    0.50    --  108.55-125.00  60.00   50
 31  \w     39.00  91.00   0.50    0.50    --  108.55-125.00 -60.00  104
 32  \w   -111.00 -41.00   0.50    0.50    --  -99.00 125.00  30.00  140
 33  \w    -96.00 -70.00   0.50    0.50    --  -99.00 -77.00  60.00   52
 34  \w   -111.00 -70.00   0.50    0.50    --  -99.00 -77.00  30.00   82
 35  \w    -95.00 -70.00   0.50    0.50    --  -99.00 -77.00   0.00   50
 36  \w    -96.00 -70.00   0.50    0.50    --  -99.00 -77.00 -30.00   52
 37  \w   -169.00-127.00   0.50    0.50    --  -99.00 -77.00  30.00   84
 38  \w   -159.00-133.00   0.50    0.50    --  -99.00 -77.00 -30.00   52
 39  \w   -172.00-104.00   0.50    0.50    --  -99.00 -76.00  20.59  136
 40  \w    -95.00 -70.00   0.50    0.50    --  -99.00 -76.00  20.59   50
 41  \w    -97.00 -72.00   0.50    0.50    --  -99.00 -73.00 -18.50   50
 42  \w    -95.00 -70.00   0.50    0.50    --  -99.00 -77.00  43.49   50
 43  \w    -96.00 -71.00   0.50    0.50    --  -99.00 -75.00  62.84   50
 44  \w    -95.00 -70.00   0.50    0.50    --  -99.00 -77.00  90.00   50
 45  \w   -100.00 -74.00   0.50    0.50    --  -99.00 -68.00  64.12   52
 46  \w   -116.00 -72.00   0.50    0.50    --  -99.00 -72.00  42.73   88
 47  \w   -163.00-137.00   0.50    0.50    --  -99.00 -77.00  90.00   52
 48  \w   -172.00-125.00   0.50    0.50    --  -99.00 -73.00 -18.50   94
 49  \w    -99.00 -74.00   0.50    0.50    --  -99.00 -66.00 -21.30   50
 50  \w   -102.00 -77.00   0.50    0.50    --  -99.00 -62.00 -10.38   50
 51  \w   -103.00 -76.00   0.50    0.50    --  -99.00 -61.00 -30.00   54
 52  \w   -108.00 -75.00   0.50    0.50    --  -99.00 -61.00 -44.57   66
 53  \w   -100.00 -75.00   0.50    0.50    --  -99.00 -61.00 -60.00   50
 54  \w   -173.00-115.00   0.50    0.50    --  -99.00 -61.00 -44.57  116
 55  \w   -162.00-136.00   0.50    0.50    --  -99.00 -61.00 -60.00   52
 56  \w   -104.00 -78.00   0.50    0.50    --  -99.00 -57.00  -9.89   52
 57  \w   -100.00 -75.00   0.50    0.50    --  -99.00 -61.00  30.00   50
 58  \w   -172.00 -75.00   0.50    0.50    --  -99.00 -61.00  60.00  194
 59  \w   -173.00 -75.00   0.50    0.50    --  -99.00 -61.00  90.00  196
 60  \w   -101.00 -76.00   0.50    0.50    --  -99.00 -57.00  71.68   50
 61  \w   -124.00 -77.00   0.50    0.50    --  -99.00 -46.00  14.50   94
 62  \w   -101.00 -76.00   0.50    0.50    --  -99.00 -57.00 -15.63   50
 63  \w   -147.00 -78.00   0.50    0.50    --  -99.00 -52.00 -20.20  138
 64  \w   -172.00-146.00   0.50    0.50    --  -99.00 -57.00  -9.89   52
 65  \w   -151.00 -77.00   0.50    0.50    --  -99.00 -45.00  60.00  148
 66  \w   -102.00 -77.00   0.50    0.50    --  -99.00 -56.00   6.05   50
 67  \w    -92.00 -67.00   0.50    0.20    --  -42.11 -21.00 114.00   50
 68  \w   -124.00 -99.00   0.50    0.50    --  -99.00 -21.00 114.00   50
;
_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      -0.0049242000
_diffrn_orient_matrix_UB_12      -0.0246811000
_diffrn_orient_matrix_UB_13      0.0959663000
_diffrn_orient_matrix_UB_21      -0.0698612000
_diffrn_orient_matrix_UB_22      -0.0079839000
_diffrn_orient_matrix_UB_23      -0.0839977000
_diffrn_orient_matrix_UB_31      0.0072424000
_diffrn_orient_matrix_UB_32      -0.0949501000
_diffrn_orient_matrix_UB_33      -0.0182604000
_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  0.0784
_diffrn_reflns_av_unetI/netI     0.0522
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            37152
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.900
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.003
_diffrn_reflns_theta_min         3.473
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.927
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64435
_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    1.389
_exptl_crystal_description       block
_exptl_crystal_F_000             2160
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.187
_refine_diff_density_min         -1.947
_refine_diff_density_rms         0.086
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.069(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     696
_refine_ls_number_reflns         9428
_refine_ls_number_restraints     657
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0884
_refine_ls_R_factor_gt           0.0687
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1296P)^2^+2.2112P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1871
_refine_ls_wR_factor_ref         0.2042
_reflns_Friedel_coverage         0.820
_reflns_Friedel_fraction_full    0.925
_reflns_Friedel_fraction_max     0.843
_reflns_number_gt                7098
_reflns_number_total             9428
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc05816b2.cif
_cod_data_source_block           2
_cod_depositor_comments
'Adding full bibliography for 7131110--7131117.cif.'
_cod_original_cell_volume        5027.9(11)
_cod_database_code               7131113
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C82Eu2N4O26Ti4
_chemical_oxdiff_usercomment     lwd-PA-(-)-Eu2Ti4
_shelx_estimated_absorpt_t_max   0.587
_shelx_estimated_absorpt_t_min   0.382
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.931(12)
 0.069(12)
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
 C13A-C15A
 2.51 with sigma of 0.04
 C15A-C34A
 2.51 with sigma of 0.04
 C34A-C13A
 2.51 with sigma of 0.04
 C41A-C35A
 2.51 with sigma of 0.04
 C35A-C22A
 2.51 with sigma of 0.04
 C22A-C41A
 2.51 with sigma of 0.04
 C1-C24 \\sim C1-C24A
 with sigma of 0.02
 C26-C13A \\sim C26-C15A \\sim C34A-C26
 with sigma of 0.01
 C24-C44 \\sim C24A-C44A
 with sigma of 0.02
 C36-C23 \\sim C36-C23A
 with sigma of 0.02
 C24-C39 \\sim C24A-C39A
 with sigma of 0.02
 C24-C45 \\sim C24A-C45A
 with sigma of 0.02
 C36-C29 \\sim C36-C29A
 with sigma of 0.04
 C23-C37 \\sim C23A-C37A
 with sigma of 0.02
 C1-C39 \\sim C1-C39A
 with sigma of 0.04
 C1-C45 \\sim C1-C45A
 with sigma of 0.04
 C36-C43 \\sim C36-C43A
 with sigma of 0.04
 C29-C37 \\sim C29A-C37A
 with sigma of 0.04
 C44-C39 \\sim C44A-C39A
 with sigma of 0.04
 C44-C45 \\sim C44A-C45A
 with sigma of 0.04
 C1-C44 \\sim C1-C44A
 with sigma of 0.04
 C39-C45 \\sim C39A-C45A
 with sigma of 0.04
 C23-C29 \\sim C23A-C29A
 with sigma of 0.02
 C23-C43 \\sim C23A-C43A
 with sigma of 0.02
 C36-C37 \\sim C36-C37A
 with sigma of 0.04
 C29-C43 \\sim C29A-C43A
 with sigma of 0.04
 C37-C43 \\sim C37A-C43A
 with sigma of 0.04
 C41A-C32 \\sim C35A-C32 \\sim C32-C22A
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
5. Others
 Sof(C24A)=Sof(C45A)=Sof(H45D)=Sof(H45E)=Sof(H45F)=Sof(C39A)=Sof(H39D)=
 Sof(H39E)=Sof(H39F)=Sof(C44A)=Sof(H44D)=Sof(H44E)=Sof(H44F)=1-FVAR(1)
 Sof(C24)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(C39)=Sof(H39A)=Sof(H39B)=
 Sof(H39C)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=FVAR(1)
 Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C15A)=Sof(H15D)=Sof(H15E)=
 Sof(H15F)=Sof(C34A)=Sof(H34D)=Sof(H34E)=Sof(H34F)=1-FVAR(2)
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(2)
 Sof(C35A)=Sof(H35D)=Sof(H35E)=Sof(H35F)=Sof(C41A)=Sof(H41D)=Sof(H41E)=
 Sof(H41F)=Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=1-FVAR(3)
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=FVAR(3)
 Sof(C43A)=Sof(H43D)=Sof(H43E)=Sof(H43F)=Sof(C23A)=Sof(C37A)=Sof(H37D)=
 Sof(H37E)=Sof(H37F)=Sof(C29A)=Sof(H29D)=Sof(H29E)=Sof(H29F)=1-FVAR(4)
 Sof(C23)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(C37)=Sof(H37A)=Sof(H37B)=
 Sof(H37C)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C19(H19)
6.b Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C3(H3A,H3B)
6.c Me refined with riding coordinates:
 C34(H34A,H34B,H34C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C13A(H13D,H13E,
 H13F), C15A(H15D,H15E,H15F), C34A(H34D,H34E,H34F)
6.d Aromatic/amide H refined with riding coordinates:
 C12(H12), C14(H14), C18(H18), C20(H20), C30(H30), C38(H38)
6.e Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C22(H22A,H22B,H22C), C44(H44A,H44B,H44C), C25(H25A,H25B,
 H25C), C29(H29A,H29B,H29C), C9(H9A,H9B,H9C), C33(H33A,H33B,H33C), C17(H17A,
 H17B,H17C), C35(H35A,H35B,H35C), C37(H37A,H37B,H37C), C39(H39A,H39B,H39C),
 C41(H41A,H41B,H41C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C), C45A(H45D,H45E,
 H45F), C39A(H39D,H39E,H39F), C44A(H44D,H44E,H44F), C35A(H35D,H35E,H35F),
 C41A(H41D,H41E,H41F), C22A(H22D,H22E,H22F), C43A(H43D,H43E,H43F), C37A(H37D,
 H37E,H37F), C29A(H29D,H29E,H29F)
;
_shelx_res_checksum              22083
_shelx_hkl_checksum              99974
_shelx_fab_checksum              9182
_platon_squeeze_special_details
;
A solvent mask was calculated and 84 electrons were 
found in a volume of 348\%A^3^ in 1 void per unit cell. 
3[C2H3N], 2[H2O] per Unit Cell 
which account for 86 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 2.166
_oxdiff_exptl_absorpt_empirical_full_min 0.390