Construction of an Au<sub>12</sub>Cd<sub>2</sub> nanocluster with circularly polarized luminescence by a metal- and ligand-exchange strategy.
Zhou, Jun; Yang, Xiaofei; Zheng, Peisen; Li, Qinzhen; Li, Xiaowu; Chai, Jinsong; Huang, Baoyu; Yang, Sha; Zhu, Manzhou; Chemical science 15 (2024) 4853–4859; doi:10.1039/d3sc06810b

data_1571065
_publ_section_title
;
 Construction of an Au<sub>12</sub>Cd<sub>2</sub> nanocluster with
 circularly polarized luminescence by a metal- and ligand-exchange
 strategy.
;
_journal_issue                   13
_journal_name_full               'Chemical science'
_journal_page_first              4853
_journal_page_last               4859
_journal_paper_doi               10.1039/d3sc06810b
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C120 H204 Au12 Cd2 S12'
_chemical_formula_sum            'C120 H204 Au12 Cd2 S12'
_chemical_formula_weight         4619.94
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2023-09-02
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-12-07 deposited with the CCDC.	2024-02-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.8453(3)
_cell_length_b                   23.7930(3)
_cell_length_c                   26.4043(3)
_cell_measurement_reflns_used    95139
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      68.08
_cell_measurement_theta_min      3.82
_cell_volume                     14352.3(3)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.0612
_diffrn_reflns_av_unetI/netI     0.0713
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            115272
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.686
_diffrn_reflns_theta_max         68.166
_diffrn_reflns_theta_min         3.829
_exptl_absorpt_coefficient_mu    26.654
_exptl_crystal_density_diffrn    2.138
_exptl_crystal_description       block
_exptl_crystal_F_000             8640
_refine_diff_density_max         2.217
_refine_diff_density_min         -1.742
_refine_diff_density_rms         0.220
_refine_ls_abs_structure_details
;
 Flack x determined using 6311 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.007(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.974
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1334
_refine_ls_number_reflns         25544
_refine_ls_number_restraints     1751
_refine_ls_restrained_S_all      0.964
_refine_ls_R_factor_all          0.0847
_refine_ls_R_factor_gt           0.0656
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1129P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1691
_refine_ls_wR_factor_ref         0.1769
_reflns_Friedel_coverage         0.828
_reflns_Friedel_fraction_full    0.962
_reflns_Friedel_fraction_max     0.954
_reflns_number_gt                17795
_reflns_number_total             25544
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06810b2.cif
_cod_data_source_block           Au12Cd2-L
_cod_depositor_comments
'Adding full bibliography for 1571065--1571066.cif.'
_cod_database_code               1571065
_shelx_shelxl_version_number     2017/1
_olex2_refinement_description
;
1. 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
2. Restrained distances
 C59-C62
 1.55 with sigma of 0.01
 C59-C53
 1.55 with sigma of 0.01
 C64-C53 = C71-C64 = C64-C33 = C64-C46 = C93-C46 = C93-C59 = C68-C62 = C88-C62
 = C62-C33
 1.55 with sigma of 0.01
 C64-C59
 2.25 with sigma of 0.01
 C93-C64
 2.5 with sigma of 0.01
 C86-C32
 1.55 with sigma of 0.01
 C86-C60 = C63-C60 = C63-C30 = C32-C30 = C30-C0AA = C114-C0AA = C60-C114 = C30-
 C2AA
 1.55 with sigma of 0.01
 C262-C180
 2.5 with sigma of 0.01
 C36-C34 = C7AA-C36 = C7AA-C50
 1.55 with sigma of 0.01
 C41-C141 = C141-C00U = C4AA-C00U = C4AA-C37 = C5AA-C4AA = C4AA-C113 = C67-
 C113 = C67-C41 = C5AA-C41 = C6AA-C141 = C141-C105
 1.55 with sigma of 0.01
 C4AA-C41
 2.25 with sigma of 0.01
 C80-C216 = C8AA-C80 = C8AA-C1BA = C85-C1BA = C85-C216 = C216-C0BA = C8AA-C011
 = C0BA-C011
 1.55 with sigma of 0.01
 C54-C49
 2.5 with sigma of 0.01
 C49-C29
 2.5 with sigma of 0.01
 C3BA-C117 = C94-C3BA
 1.55 with sigma of 0.01
 C6BA-C4BA = C5BA-C4BA = C5BA-C2BA = C2BA-C013 = C4BA-C3BA = C3BA-C013
 1.55 with sigma of 0.01
 C1BA-C216
 2.5 with sigma of 0.01
 C216-C8BA
 2.5 with sigma of 0.01
 C216-C8AA
 2.25 with sigma of 0.01
 C5BA-C110
 2.5 with sigma of 0.01
 C6BA-C5BA
 2.5 with sigma of 0.01
 C6AA-C105
 2.5 with sigma of 0.01
 C114-C86
 2.5 with sigma of 0.01
 C0AA-C32
 2.5 with sigma of 0.01
 C60-C30
 2.25 with sigma of 0.01
 C9CA-C205 = C205-C142 = C205-C1DA = C205-C156 = C92-C156 = C92-C0DA = C1DA-C0DA
 1.55 with sigma of 0.01
 C3DA-C290
 2.5 with sigma of 0.01
 C290-C5DA
 2.5 with sigma of 0.01
 C99-C111
 2.5 with sigma of 0.01
 C2DA-C99
 2.5 with sigma of 0.01
 C2DA-C38
 2.5 with sigma of 0.01
 C6CA-C2CA = C2CA-C123 = C75-C2CA = C65-C2CA = C65-C4CA = C57-C4CA = C4CA-C3CA
 = C5CA-C4CA = C5CA-C52 = C75-C52 = C75-C3CA
 1.55 with sigma of 0.01
 C8DA-C7DA = C7DA-C7CA
 1.55 with sigma of 0.01
 C9DA-C8DA
 2.5 with sigma of 0.01
 C9DA-C9AA
 2.5 with sigma of 0.01
 C7DA-C0CA
 2.5 with sigma of 0.01
 C7DA-C1CA
 2.25 with sigma of 0.01
 C124-C9CA
 1.55 with sigma of 0.01
 C124-C0DA
 1.55 with sigma of 0.01
 C98-C124 = C126-C124
 1.55 with sigma of 0.01
 C1DA-C124
 2.5 with sigma of 0.01
 C92-C205
 2.5 with sigma of 0.01
 C0DA-C156
 2.5 with sigma of 0.01
 C98-C126
 2.5 with sigma of 0.01
 C1DA-C142
 2.5 with sigma of 0.01
 C142-C9CA
 2.5 with sigma of 0.01
 C156-C142
 2.5 with sigma of 0.01
 C205-C124
 2.5 with sigma of 0.01
 C92-C1DA
 2.5 with sigma of 0.01
 C156-C1DA
 2.5 with sigma of 0.01
 C52-C3CA
 2.5 with sigma of 0.01
 C5CA-C3CA
 2.5 with sigma of 0.01
 C3CA-C2CA
 2.5 with sigma of 0.01
 C3CA-C65
 2.5 with sigma of 0.01
 C75-C4CA
 2.25 with sigma of 0.01
 C8DA-C83 = C9BA-C8DA
 1.55 with sigma of 0.01
 C9BA-C83
 2.5 with sigma of 0.01
 C49-C36
 2.5 with sigma of 0.01
 C7AA-C49
 2.5 with sigma of 0.01
 C78-C56
 2.5 with sigma of 0.01
 C74-C271
 1.55 with sigma of 0.01
 C74-C3AA
 2.5 with sigma of 0.01
 C56-C74
 2.5 with sigma of 0.01
 C97-C271
 2.5 with sigma of 0.01
 C8AA-C31
 1.55 with sigma of 0.01
 C6CA-C123
 2.5 with sigma of 0.01
 S00O-C8CA
 1.8 with sigma of 0.01
 C290-C4DA
 2.5 with sigma of 0.01
 C8DA-C9AA
 1.55 with sigma of 0.01
 C8CA-C7EA
 2.5 with sigma of 0.01
 C1EA-C8CA
 2.5 with sigma of 0.01
 C2EA-C8CA
 2.5 with sigma of 0.01
 C164-C3EA
 2.5 with sigma of 0.01
 C6EA-C1EA
 2.5 with sigma of 0.01
 C6EA-C7EA
 2.5 with sigma of 0.01
 C2EA-C5EA
 2.5 with sigma of 0.01
 C5EA-C8CA
 2.5 with sigma of 0.01
 C44-C2EA
 2.5 with sigma of 0.01
 C6EA-C44 = C7EA-C44 = C8CA-C44 = C8CA-C3EA = C44-C1EA = C2EA-C1EA = C3EA-C2EA
 = C1EA-C164 = C4EA-C164 = C5EA-C3EA = C4EA-C3EA
 1.55 with sigma of 0.01
 C4EA-C1EA
 2.5 with sigma of 0.01
 C8CA-C4EA
 2.5 with sigma of 0.01
 C5EA-C4EA
 2.5 with sigma of 0.01
 C69-C56
 2.5 with sigma of 0.01
 C97-C56
 1.55 with sigma of 0.01
 C51-C3AA
 1.55 with sigma of 0.01
 C86-C1AA
 1.55 with sigma of 0.01
 C60-C1AA
 2.5 with sigma of 0.01
 C1AA-C39
 2.5 with sigma of 0.01
 H6CB-H6EB
 2.2 with sigma of 0.01
 C5DA-C2DA = C99-C5DA = C5DA-C111 = C5DA-C42 = C4DA-C42 = C6DA-C4DA = C4DA-C38
 = C38-C290 = C4DA-C3DA = C2DA-C290 = C3DA-C2DA
 1.55 with sigma of 0.01
 C42-C3DA
 2.5 with sigma of 0.01
 C56-C271
 1.55 with sigma of 0.01
 C78-C97
 1.54 with sigma of 0.01
 C42-C111
 2.5 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C62 \\sim C68 \\sim C33 \\sim C88 \\sim C59 \\sim C53 \\sim C46 \\sim C64 \\sim
C71 \\sim C93: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.008 within 1.7A
Uanis(C00U) \\sim Ueq, Uanis(C011) \\sim Ueq, Uanis(C013) \\sim Ueq, Uanis(C29)
\\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C36) \\sim Ueq,
Uanis(C47) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C54)
\\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C33) \\sim Ueq,
Uanis(C2AA) \\sim Ueq, Uanis(C0AA) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C46)
\\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C60) \\sim Ueq,
Uanis(C62) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C86)
\\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(C68) \\sim Ueq,
Uanis(C3AA) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C69)
\\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C63) \\sim Ueq,
Uanis(C132) \\sim Ueq, Uanis(C180) \\sim Ueq, Uanis(C262) \\sim Ueq,
Uanis(C1AA) \\sim Ueq, Uanis(C114) \\sim Ueq, Uanis(C7AA) \\sim Ueq, Uanis(C42)
\\sim Ueq, Uanis(C271) \\sim Ueq, Uanis(C4AA) \\sim Ueq, Uanis(C37) \\sim Ueq,
Uanis(C41) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C5AA) \\sim Ueq, Uanis(C6AA)
\\sim Ueq, Uanis(C105) \\sim Ueq, Uanis(C113) \\sim Ueq, Uanis(C141) \\sim Ueq,
Uanis(C0BA) \\sim Ueq, Uanis(C8AA) \\sim Ueq, Uanis(C1BA) \\sim Ueq, Uanis(C80)
\\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(C128) \\sim Ueq, Uanis(C216) \\sim Ueq,
Uanis(C2BA) \\sim Ueq, Uanis(C4BA) \\sim Ueq, Uanis(C5BA) \\sim Ueq,
Uanis(C7BA) \\sim Ueq, Uanis(C3BA) \\sim Ueq, Uanis(C94) \\sim Ueq, Uanis(C6BA)
\\sim Ueq, Uanis(C117) \\sim Ueq, Uanis(C8BA) \\sim Ueq, Uanis(C110) \\sim Ueq,
Uanis(C65) \\sim Ueq, Uanis(C0DA) \\sim Ueq, Uanis(C1DA) \\sim Ueq, Uanis(C92)
\\sim Ueq, Uanis(C126) \\sim Ueq, Uanis(C9CA) \\sim Ueq, Uanis(C142) \\sim Ueq,
Uanis(C156) \\sim Ueq, Uanis(C205) \\sim Ueq, Uanis(C2DA) \\sim Ueq,
Uanis(C5DA) \\sim Ueq, Uanis(C4DA) \\sim Ueq, Uanis(C3DA) \\sim Ueq, Uanis(C38)
\\sim Ueq, Uanis(C6DA) \\sim Ueq, Uanis(C99) \\sim Ueq, Uanis(C111) \\sim Ueq,
Uanis(C290) \\sim Ueq, Uanis(C3CA) \\sim Ueq, Uanis(C5CA) \\sim Ueq, Uanis(C52)
\\sim Ueq, Uanis(C4CA) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C75) \\sim Ueq,
Uanis(C2CA) \\sim Ueq, Uanis(C6CA) \\sim Ueq, Uanis(C123) \\sim Ueq,
Uanis(C9AA) \\sim Ueq, Uanis(C0CA) \\sim Ueq, Uanis(C1CA) \\sim Ueq,
Uanis(C8DA) \\sim Ueq, Uanis(C7CA) \\sim Ueq, Uanis(C0EA) \\sim Ueq,
Uanis(C9DA) \\sim Ueq, Uanis(C7DA) \\sim Ueq, Uanis(C98) \\sim Ueq, Uanis(C124)
\\sim Ueq, Uanis(C9BA) \\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(C74) \\sim Ueq,
Uanis(C31) \\sim Ueq, Uanis(C8CA) \\sim Ueq, Uanis(C2EA) \\sim Ueq, Uanis(C3EA)
\\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C1EA) \\sim Ueq, Uanis(C7EA) \\sim Ueq,
Uanis(C4EA) \\sim Ueq, Uanis(C5EA) \\sim Ueq, Uanis(C6EA) \\sim Ueq,
Uanis(C164) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 S00O, C6EA, C8CA, C2EA, C3EA, C44, C1EA, C7EA, C4EA, C5EA, C164
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C74, C271, C97, C56, C69, C51, C3AA, C262, C180, C78, S00G
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 S00N, C65, C3CA, C52, C4CA, C75, C2CA, C6CA, C123, C5CA, C57
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 S00K, C1AA, C39, C86, C32, C30, C2AA, C63, C60, C114, C0AA
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 S00Q, C0DA, C1DA, C92, C142, C156, C205, C9CA, C124, C98, C126
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C013, C2BA, C4BA, C5BA, C7BA, C6BA, C110, C94, C117, S00I, C3BA
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C9AA, C0CA, C1CA, C8DA, C7CA, C0EA, C9DA, C7DA, C9BA, C83, S00J
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 S00P, C42, C4DA, C6DA, C2DA, C111, C99, C3DA, C290, C38, C5DA
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5.a Riding coordinates:
 C132(H13A,H13B,H13C), C262(H26A,H26B,H26C), C1AA(H1AA,H1AB,H1AC), C105(H10A,
 H10B,H10C), C128(H12A,H12B,H12C), C7BA(H7BA,H7BB,H7BC), C117(H11E,H11F,H11G),
 C8BA(H8BA,H8BB,H8BC), C126(H12D,H12E,H12F), C99(H99A,H99B,H99C), C111(H11J,
 H11K,H11L), C123(H12I,H12H,H12G), C98(H98A,H98B,H98C), C83(H83A,H83B,H83C),
 C74(H74A,H74B,H74C), C5EA(H5EA,H5EB,H5EC), C6EA(H6EA,H6EB,H6EC)
5.b Ternary CH refined with riding coordinates:
 C00U(H00U), C011(H011), C013(H013), C29(H29), C50(H50), C32(H32), C33(H33),
 C59(H59), C60(H60), C3AA(H3AA), C78(H78), C42(H42), C41(H41), C216(H216),
 C4BA(H4BA), C65(H65), C0DA(H0DA), C9CA(H9CA), C2DA(H2DA), C75(H75), C9AA(H9AA),
  C7DA(H7DA), C8CA(H8CA), C1EA(H1EA)
5.c Secondary CH2 refined with riding coordinates:
 C36(H36A,H36B), C49(H49A,H49B), C0AA(H0AA,H0AB), C46(H46A,H46B), C53(H53A,
 H53B), C93(H93A,H93B), C56(H56A,H56B), C69(H69A,H69B), C97(H97A,H97B),
 C63(H63A,H63B), C114(H11A,H11B), C7AA(H7AA,H7AB), C67(H67A,H67B), C5AA(H5AA,
 H5AB), C113(H11C,H11D), C1BA(H1BA,H1BB), C80(H80A,H80B), C85(H85A,H85B),
 C5BA(H5BA,H5BB), C6BA(H6BA,H6BB), C110(H11H,H11I), C1DA(H1DA,H1DB), C92(H92A,
 H92B), C156(H15A,H15B), C3DA(H3DA,H3DB), C38(H38A,H38B), C290(H29A,H29B),
 C3CA(H3CA,H3CB), C5CA(H5CA,H5CB), C52(H52A,H52B), C0CA(H0CA,H0CB), C7CA(H7CA,
 H7CB), C9DA(H9DA,H9DB), C2EA(H2EA,H2EB), C4EA(H4EA,H4EB), C164(H16A,H16B)
5.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C47(H47A,H47B,H47C), C2AA(H2AA,H2AB,H2AC), C39(H39A,H39B,
 H39C), C71(H71A,H71B,H71C), C88(H88A,H88B,H88C), C68(H68A,H68B,H68C),
 C180(H18A,H18B,H18C), C37(H37A,H37B,H37C), C6AA(H6AA,H6AB,H6AC), C94(H94A,H94B,
 H94C), C142(H14A,H14B,H14C), C6DA(H6DA,H6DB,H6DC), C57(H57A,H57B,H57C),
 C6CA(H6CA,H6CB,H6CC), C0EA(H0EA,H0EB,H0EC), C9BA(H9BA,H9BB,H9BC), C31(H31A,
 H31B,H31C), C7EA(H7EA,H7EB,H7EC)
;
_shelx_res_checksum              74900
_shelx_fab_checksum              15208
_olex2_submission_special_instructions 'No special instructions were received'