Circularly polarized luminescence induction on a Tb(III) complex with a tris(<i>o-tert</i>-butylaryloxide)-functionalized 1,4,7-triazacyclononane ligand coordinating chiral 1-phenylethylamine.
Shirai, Sora; Muratsugu, Satoshi; Matsui, Hisaki; Harada, Kazuhiro; Ehara, Masahiro; Nakai, Hidetaka; Tada, Mizuki; Chemical communications (Cambridge, England) 60 (2024) 14180–14183; doi:10.1039/d4cc05191b

data_7133876
_publ_section_title
;
 Circularly polarized luminescence induction on a Tb(III) complex with a
 tris(<i>o-tert</i>-butylaryloxide)-functionalized 1,4,7-triazacyclononane
 ligand coordinating chiral 1-phenylethylamine.
;
_journal_issue                   96
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              14180
_journal_page_last               14183
_journal_paper_doi               10.1039/d4cc05191b
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         '2(C50 H71 N4 O3 Tb), C8 H11 N'
_chemical_formula_sum            'C108 H153 N9 O6 Tb2'
_chemical_formula_weight         1991.22
_chemical_name_systematic        tBu1Tb_R-PEA
_chemical_properties_physical    Oxygen-sensitive,Light-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
_atom_sites_solution_primary     dual
_audit_creation_date             2024-04-04
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-06-20 deposited with the CCDC.	2024-10-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.8640(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.5520(2)
_cell_length_b                   36.5500(4)
_cell_length_c                   21.8477(3)
_cell_measurement_reflns_used    112982
_cell_measurement_temperature    123
_cell_measurement_theta_max      31.3790
_cell_measurement_theta_min      2.5840
_cell_volume                     9843.5(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_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_temperature      123
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.914
_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     61.00  90.00   0.50   10.68    --    1.50  45.00 165.39   58
  2  \w    -87.00 -51.00   0.50   10.68    --    1.50  45.00 101.10   72
  3  \w     38.00  64.00   0.50   10.68    --    1.50  45.00 101.10   52
  4  \w    -49.00 -24.00   0.50   10.68    --    1.50  45.00 -18.42   50
  5  \w     39.00  65.00   0.50   10.68    --    1.50  45.00 -18.42   52
  6  \w    -82.00 -56.00   0.50   10.68    --    1.50  45.00 143.80   52
  7  \w    -87.00 -46.00   0.50   10.68    --    1.50  45.00  60.00   82
  8  \w    -10.00  37.00   0.50   10.68    --    1.50  45.00  60.00   94
  9  \w    -78.00 -52.00   0.50   10.68    --    1.50  45.00   0.00   52
 10  \w     29.00  55.00   0.50   10.68    --    1.50  45.00   0.00   52
 11  \w    -87.00  90.00   0.50   10.68    --    1.50  45.00  30.00  354
 12  \w    -74.00  53.00   0.50   10.68    --    1.50  45.00 165.39  254
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC10 (RCD3): fixed-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0051855000
_diffrn_orient_matrix_UB_12      0.0120239000
_diffrn_orient_matrix_UB_13      -0.0258901000
_diffrn_orient_matrix_UB_21      -0.0184335000
_diffrn_orient_matrix_UB_22      0.0140452000
_diffrn_orient_matrix_UB_23      0.0178442000
_diffrn_orient_matrix_UB_31      0.0542523000
_diffrn_orient_matrix_UB_32      0.0059150000
_diffrn_orient_matrix_UB_33      0.0101757000
_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  0.0379
_diffrn_reflns_av_unetI/netI     0.0328
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.914
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       51
_diffrn_reflns_limit_k_min       -52
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            272204
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.872
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.297
_diffrn_reflns_theta_min         2.415
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.484
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86552
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.344
_exptl_crystal_description       plate
_exptl_crystal_F_000             4168
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: (R)-1-phenylethylamine/hexane'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.652
_refine_diff_density_min         -0.552
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 21067 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.029(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2293
_refine_ls_number_reflns         56152
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0326
_refine_ls_R_factor_gt           0.0257
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0167P)^2^+5.8849P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0498
_refine_ls_wR_factor_ref         0.0511
_reflns_Friedel_coverage         0.882
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.829
_reflns_number_gt                49545
_reflns_number_total             56152
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc05191b2.cif
_cod_data_source_block           230829_ss215_tbu1tb_r_bnnh2_04
_cod_depositor_comments
'Adding full bibliography for 7133875--7133876.cif.'
_cod_database_code               7133876
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C50H71N4O3Tb1
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.708
_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
 C06S-C202
 1.55 with sigma of 0.02
 N10A-C202
 2.39 with sigma of 0.04
 N10A-H06S
 1.97 with sigma of 0.04
 H06S-C202
 1.99 with sigma of 0.04
 H06S-C063
 2.06 with sigma of 0.04
3.a Ternary CH refined with riding coordinates:
 C43(H43), C93(H93), C143(H143), C193(H193), C06S(H06S), C070(H070)
3.b Secondary CH2 refined with riding coordinates:
 C137(H13C,H13D), C87(H87A,H87B), C191(H19A,H19B), C88(H88A,H88B), C38(H38A,
 H38B), C163(H16A,H16B), C91(H91A,H91B), C138(H13E,H13F), C13(H13A,H13B),
 C151(H15A,H15B), C37(H37A,H37B), C51(H51A,H51B), C90(H90A,H90B), C175(H17A,
 H17B), C192(H19C,H19D), C187(H18A,H18B), C75(H75A,H75B), C41(H41A,H41B),
 C139(H13J,H13K), C92(H92A,H92B), N12(H12R,H12S), C42(H42A,H42B), C140(H14A,
 H14B), C101(H10G,H10H), C39(H39A,H39B), C188(H18C,H18D), C1(H1A,H1B),
 C141(H14C,H14D), C40(H40A,H40B), C63(H63A,H63B), C89(H89A,H89B), N16(H16I,
 H16J), C142(H14E,H14F), C125(H12M,H12N), C113(H11M,H11N), N4(H4A,H4B),
 C25(H25A,H25B), C189(H18H,H18I), N8(H8A,H8B), C190(H19E,H19F)
3.c Aromatic/amide H refined with riding coordinates:
 C169(H169), C55(H55), C81(H81), C107(H107), C155(H155), C117(H117), C57(H57),
 C131(H131), C19(H19), C5(H5), C181(H181), C148(H148), C79(H79), C129(H129),
 C146(H146), C46(H46), C179(H179), C49(H49), C69(H69), C17(H17), C167(H167),
 C149(H149), C105(H105), C04B(H04B), C7(H7), C157(H157), C119(H119), C67(H67),
 C197(H197), C31(H31), C47(H47), C195(H195), C145(H145), C199(H199), C147(H147),
  C29(H29), C05Q(H05Q), C45(H45), C48(H48), C06T(H06T), C05S(H05S), C04R(H04R),
 C054(H054), C05N(H05N), C067(H067), C068(H068), C196(H196), C06J(H06J),
 C198(H198), C97(H97), C99(H99), C96(H96), C95(H95), C98(H98)
3.d Fitted hexagon refined as free rotating group:
 C063(C06T,C05S,C04R,C054,C05N)
3.e X=CH2 refined with riding coordinates:
 N17(H17O,H17P), N10A(H10L,H10M)
3.f Idealised Me refined as rotating group:
 C59(H59A,H59B,H59C), C122(H12D,H12E,H12F), C35(H35A,H35B,H35C), C134(H13G,
 H13H,H13I), C159(H15C,H15D,H15E), C112(H11D,H11E,H11F), C85(H85A,H85B,H85C),
 C21(H21A,H21B,H21C), C160(H16C,H16D,H16E), C72(H72A,H72B,H72C), C34(H34A,H34B,
 H34C), C171(H17C,H17D,H17E), C100(H10A,H10B,H10C), C110(H11G,H11H,H11I),
 C161(H16F,H16G,H16H), C111(H11J,H11K,H11L), C123(H12G,H12H,H12I), C9(H9A,H9B,
 H9C), C121(H12J,H12K,H12L), C84(H84A,H84B,H84C), C36(H36A,H36B,H36C), C50(H50A,
 H50B,H50C), C172(H17F,H17G,H17H), C183(H18E,H18F,H18G), C86(H86A,H86B,H86C),
 C162(H16K,H16L,H16M), C124(H12O,H12P,H12Q), C11(H11A,H11B,H11C), C136(H13L,
 H13M,H13N), C12(H12A,H12B,H12C), C174(H17I,H17J,H17K), C133(H13O,H13P,H13Q),
 C24(H24A,H24B,H24C), C83(H83A,H83B,H83C), C135(H13R,H13S,H13T), C62(H62A,H62B,
 H62C), C33(H33A,H33B,H33C), C200(H20A,H20B,H20C), C109(H10I,H10J,H10K),
 C150(H15F,H15G,H15H), C10(H10D,H10E,H10F), C61(H61A,H61B,H61C), C173(H17L,H17M,
 H17N), C22(H22A,H22B,H22C), C74(H74A,H74B,H74C), C23(H23A,H23B,H23C), C73(H73A,
 H73B,H73C), C184(H18J,H18K,H18L), C186(H18M,H18N,H18O), C60(H60A,H60B,H60C),
 C185(H18P,H18Q,H18R), C71(H71A,H71B,H71C), C201(H20D,H20E,H20F), C202(H20G,
 H20H,H20I)
;
_shelx_res_checksum              60737
_shelx_hkl_checksum              17892
_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 1.328
_oxdiff_exptl_absorpt_empirical_full_min 0.839