Triple-Helical Aggregates of Copper(I) Cyclic Trinuclear Complexes for Circularly Polarized Luminescence
Huang, Guo-Quan; Yang, Hu; Xia, Ri-Qin; Wu, Kun; Huang, Yong-Liang; Hao, De-Bo; Li, Shun-Bo; Lu, Weigang; Zheng, Ji; Zhou, Xiao-Ping; Li, Dan; Chemical Science  (2025) –; doi:10.1039/D5SC04965B

data_1576290
_publ_section_title
;
 Triple-Helical Aggregates of Copper(I) Cyclic Trinuclear Complexes for
 Circularly Polarized Luminescence
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC04965B
_journal_year                    2025
_chemical_absolute_configuration rmad
_chemical_formula_moiety         '3(C36 H36 Cu3 N9 O3), C2 H6 O, C2 H5 O'
_chemical_formula_sum            'C112 H119 Cu9 N27 O11'
_chemical_formula_weight         2591.19
_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             2024-06-04
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-08-19 deposited with the CCDC.	2025-11-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.6660(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.09800(10)
_cell_length_b                   19.5551(3)
_cell_length_c                   33.1683(5)
_cell_measurement_reflns_used    47181
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      78.1810
_cell_measurement_theta_min      2.7360
_cell_volume                     5848.31(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.973
_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      4.00  29.00   0.50    1.15    --   -2.20  66.00   9.00   50
  2  \w    -33.00  -8.00   0.50    1.15    --    2.20 -66.00-124.00   50
  3  \w     -4.00  87.00   0.50    1.15    --    2.20  66.00   9.00  182
  4  \w    118.00 144.00   0.50    4.62    --  106.30  66.00   9.00   52
  5  \w    100.00 131.00   0.50    4.62    --  106.30 -66.00-124.00   62
  6  \w     38.00  76.00   0.50    4.62    --  106.30 -66.00-124.00   76
  7  \w    -37.00  29.00   0.50    1.15    --   -2.20 -82.00 -90.00  132
  8  \w    -35.00  32.00   0.50    1.15    --   -2.20  82.00  60.00  134
  9  \w     -3.00  28.00   0.50    1.15    --   -2.20 -82.00-150.00   62
 10  \w    -41.00 -15.00   0.50    1.15    --   -2.20 -66.00-124.00   52
 11  \w    -38.00  -8.00   0.50    1.15    --   -2.20 -82.00-150.00   60
 12  \w    -14.00  13.00   0.50    1.15    --    2.20  82.00 -90.00   54
 13  \w    -38.00  34.00   0.50    1.15    --    2.20 -82.00 -30.00  144
 14  \w    -39.00  36.00   0.50    1.15    --    2.20 -82.00-180.00  150
 15  \w     18.00  43.00   0.50    4.62    --  106.30 -82.00 120.00   50
 16  \w    105.00 195.00   0.50    4.62    --  106.30  19.00-150.00  180
 17  \w     18.00 138.00   0.50    4.62    --  106.30 -82.00-120.00  240
 18  \w     17.00 128.00   0.50    4.62    --  106.30 -38.00-120.00  222
 19  \w     47.00 133.00   0.50    4.62    --  106.30 -82.00 160.91  172
 20  \w     79.00 180.00   0.50    4.62    --  106.30  19.00 -30.00  202
 21  \w     49.00 136.00   0.50    4.62    --  106.30 -82.00 -60.00  174
 22  \w     91.00 140.00   0.50    4.62    --  106.30 -82.00   0.00   98
 23  \w     82.00 107.00   0.50    4.62    --  106.30 -82.00-150.00   50
 24  \w     33.00  71.00   0.50    4.62    --  106.30 -82.00   0.00   76
 25  \w     47.00  74.00   0.50    4.62    --  106.30 -82.00-150.00   54
 26  \w     19.00 137.00   0.50    4.62    --  106.30 -82.00  30.00  236
 27  \w     49.00 128.00   0.50    4.62    --  106.30 -82.00 120.00  158
 28  \w     21.00 134.00   0.50    4.62    --  106.30 -19.00  90.00  226
 29  \w     22.00  76.00   0.50    4.62    --  106.30 -82.00  60.00  108
 30  \w     83.00 110.00   0.50    4.62    --  106.30 -82.00  60.00   54
 31  \w     22.00  82.50   0.50    4.62    --  106.30 -38.00  30.00  121
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1223170000
_diffrn_orient_matrix_UB_12      -0.0488477000
_diffrn_orient_matrix_UB_13      0.0193312000
_diffrn_orient_matrix_UB_21      -0.0618187000
_diffrn_orient_matrix_UB_22      -0.0568177000
_diffrn_orient_matrix_UB_23      -0.0297126000
_diffrn_orient_matrix_UB_31      0.1020754000
_diffrn_orient_matrix_UB_32      0.0242613000
_diffrn_orient_matrix_UB_33      -0.0306764000
_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  0.1268
_diffrn_reflns_av_unetI/netI     0.0755
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            60856
_diffrn_reflns_point_group_measured_fraction_full 0.944
_diffrn_reflns_point_group_measured_fraction_max 0.897
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.922
_diffrn_reflns_theta_min         3.513
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    2.305
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72603
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.33c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.471
_exptl_crystal_description       block
_exptl_crystal_F_000             2658
_refine_diff_density_max         1.063
_refine_diff_density_min         -0.980
_refine_diff_density_rms         0.139
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.05(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1257
_refine_ls_number_reflns         22685
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0924
_refine_ls_R_factor_gt           0.0845
_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^)+(0.0955P)^2^+28.0543P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1946
_refine_ls_wR_factor_ref         0.2024
_reflns_Friedel_coverage         0.790
_reflns_Friedel_fraction_full    0.889
_reflns_Friedel_fraction_max     0.817
_reflns_number_gt                20781
_reflns_number_total             22685
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04965b2.cif
_cod_data_source_block           R_1
_cod_database_code               1576290
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Cu C H N O'
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.95(4)
 0.05(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
3.a Ternary CH refined with riding coordinates:
 C14(H14), C46(H46), C52(H52), C56(H56), C62(H62), C68(H68), C78(H78),
 C96(H96), C67(H67)
3.b Secondary CH2 refined with riding coordinates:
 C99(H99A,H99B)
3.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N4(H4), N6(H6), N8(H8), N10(H10), N12(H12), N14(H14A), N16(H16),
 C84(H84), C42(H42), N26(H26), C32(H32), C31(H31), C24(H24), C12(H12A),
 C25(H25), C5(H5), C41(H41), C57(H57), C40(H40), C35(H35), C94(H94), C22(H22),
 C86(H86), C36(H36), C72(H72), C48(H48), C11(H11), C66(H66), C69(H69), C89(H89),
  C83(H83), C53(H53), C7(H7), C47(H47), C95(H95), C79(H79), C90(H90), C29(H29),
 C50(H50), C59(H59), C19(H19), C2(H2), C33(H33), C82(H82), C37(H37), C110(H110),
  C87(H87), C21(H21), C65(H65), C112(H112), C108(H108), C45(H45), C55(H55),
 C109(H109), C27(H27), C23(H23), C91(H91), C13(H13), C49(H49), C39(H39),
 C76(H76), C101(H101), C93(H93), C97(H97), C61(H61), C81(H81), C103(H103),
 C51(H51), C43(H43), C100(H100), C85(H85), C105(H105)
3.d Fitted pentagon refined as free rotating group:
 N20(N27,C84,C20,C42), N2(C32,C26,C31,N11), N17(C24,C4,C12,N25), N9(N13,C25,
 C58,C5), C28(C41,N23,N18,C57), C44(C36,N5,N24,C72), C48(N22,N7,C11,C17),
 C29(N3,N19,C50,C30), C37(C77,C110,N15,N21)
3.e Fitted hexagon refined as free rotating group:
 C40(C35,C94,C22,C92,C86), C66(C69,C89,C74,C83,C53), C7(C71,C47,C95,C79,C90),
 C59(C19,C2,C33,C63,C82), C87(C21,C65,C70,C112,C108), C45(C55,C109,C27,C80,C23),
  C91(C13,C49,C39,C76,C106), C101(C93,C97,C61,C34,C81), C103(C51,C43,C104,C100,
 C85)
3.f Idealised Me refined as rotating group:
 C60(H60A,H60B,H60C), C64(H64A,H64B,H64C), C88(H88A,H88B,H88C), C102(H10A,H10B,
 H10C), C15(H15A,H15B,H15C), C9(H9A,H9B,H9C), C73(H73A,H73B,H73C), C75(H75A,
 H75B,H75C), C3(H3A,H3B,H3C), C107(H10D,H10E,H10F), C111(H11A,H11B,H11C)
3.g Idealised tetrahedral OH refined as rotating group:
 O9(H9), O5(H5A)
;
_shelx_res_checksum              72683
_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 3.788
_oxdiff_exptl_absorpt_empirical_full_min 0.175