Arylation of gold nanoclusters and insights into structure-related CO2 reduction reaction performances
Zhu, Chen; Li, Bo; Li, Chen; Lu, Luyao; Li, Hao; Yuan, Xinhua; Kang, Xi; Jiang, De-en; Zhu, Manzhou; Chemical Science 16 (2025) 10273–10281; doi:10.1039/D5SC01200G

data_1574607
_publ_section_title
;
 Arylation of gold nanoclusters and insights into structure-related CO2
 reduction reaction performances
;
_journal_issue                   23
_journal_name_full               'Chemical Science'
_journal_page_first              10273
_journal_page_last               10281
_journal_paper_doi               10.1039/D5SC01200G
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C148 H120 Au15 Cl2 O3 P6 S4'
_chemical_formula_sum            'C148 H120 Au15 Cl2 O3 P6 S4'
_chemical_formula_weight         5285.89
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-04-07
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-04-10 deposited with the CCDC.	2025-05-06 downloaded from the CCDC.
;
_cell_angle_alpha                115.818(4)
_cell_angle_beta                 93.462(4)
_cell_angle_gamma                90.360(5)
_cell_formula_units_Z            2
_cell_length_a                   20.4720(11)
_cell_length_b                   21.4293(13)
_cell_length_c                   22.5130(12)
_cell_measurement_reflns_used    19496
_cell_measurement_temperature    120
_cell_measurement_theta_max      69.03
_cell_measurement_theta_min      5.91
_cell_volume                     8868.6(9)
_computing_cell_refinement
;
X-Area Recipe 1.37.0.0 (STOE, 2021)
;
_computing_data_collection       'X-Area Pilatus3_SV 1.31.186.0 (STOE, 2022)'
_computing_data_reduction
;
X-Area Integrate 2.5.3.0 (STOE, 2021)
X-Area LANA 2.7.5.0 (STOE, 2022)
;
_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      120
_diffrn_detector                 Pilatus300K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'DECTRIS PILATUS 300K'
_diffrn_measured_fraction_theta_full 0.969
_diffrn_measured_fraction_theta_max 0.969
_diffrn_measurement_details      '1738 frames, detector distance = 60 mm'
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '1.2 mm, 0.6 diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  270
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.0509
_diffrn_reflns_av_unetI/netI     0.0729
_diffrn_reflns_Laue_measured_fraction_full 0.969
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            65665
_diffrn_reflns_point_group_measured_fraction_full 0.969
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        62.498
_diffrn_reflns_theta_max         62.498
_diffrn_reflns_theta_min         5.940
_diffrn_source                   'GeniX 3D HF Cu'
_diffrn_source_current           0.600
_diffrn_source_power             0.030
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    24.208
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  1.0000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE LANA, absorption correction by scaling of reflection intensities.
J. Koziskova, F. Hahn, J. Richter, J. Kozisek, "Comparison of different
absorption corrections on the model structure of tetrakis(\m~2~-acetato)-
diaqua-di-copper(II)", Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
;
_exptl_crystal_colour            'metallic dark black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.979
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       cube
_exptl_crystal_F_000             4810
_refine_diff_density_max         3.576
_refine_diff_density_min         -2.526
_refine_diff_density_rms         0.200
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.945
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1337
_refine_ls_number_reflns         27410
_refine_ls_number_restraints     1785
_refine_ls_restrained_S_all      0.933
_refine_ls_R_factor_all          0.0886
_refine_ls_R_factor_gt           0.0645
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1086P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1749
_refine_ls_wR_factor_ref         0.1872
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16946
_reflns_number_total             27410
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01200g2.cif
_cod_data_source_block           1_CCDC2
_cod_depositor_comments
'Adding full bibliography for 1574605--1574607.cif.'
_cod_database_code               1574607
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C32-Au0E
 2.013 with sigma of 0.01
 H175-H22A
 2.5 with sigma of 0.01
3. Rigid bond restraints
 Cl1, C41
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
C00V \\sim C00W \\sim C00X \\sim C00Y \\sim C010 \\sim C013 \\sim C014 \\sim
C016 \\sim C017 \\sim C019 \\sim C01B \\sim C01C \\sim C01D \\sim C01Q \\sim
C023 \\sim C011 \\sim C00Z \\sim C01R \\sim C01E \\sim C01G \\sim C01H \\sim
C01I \\sim C01M \\sim C01N \\sim C01P \\sim C01S \\sim C01U \\sim C01X \\sim
C01Z \\sim C020 \\sim C021 \\sim C50 \\sim C51 \\sim C02C \\sim C01J \\sim C012
\\sim C022 \\sim C024 \\sim C026 \\sim C028 \\sim C01A \\sim C01V \\sim C01Y
\\sim C02P \\sim C02G \\sim C029 \\sim C02U \\sim C02Z \\sim C032 \\sim C033
\\sim C2 \\sim C4 \\sim C9 \\sim C25 \\sim C33 \\sim C60 \\sim C23 \\sim C39
\\sim C11 \\sim C1 \\sim C7 \\sim C13 \\sim C38 \\sim C70 \\sim C78 \\sim C125
\\sim C147 \\sim C56 \\sim C3 \\sim C6 \\sim C5 \\sim C8 \\sim C10 \\sim C12
\\sim C175 \\sim C141 \\sim C22 \\sim C20 \\sim C37 \\sim C66 \\sim C32 \\sim
C36 \\sim C40 \\sim C41 \\sim C42 \\sim C26 \\sim C43 \\sim C24 \\sim C27 \\sim
C132 \\sim C143 \\sim C80 \\sim C63 \\sim C47 \\sim C67 \\sim C34 \\sim C45
\\sim C46 \\sim C49 \\sim C48 \\sim C30 \\sim C29 \\sim C21 \\sim C14 \\sim C53
\\sim C79 \\sim C65 \\sim C54 \\sim C55 \\sim C52 \\sim C68 \\sim C74 \\sim C73
\\sim C71 \\sim C72 \\sim C69 \\sim C85 \\sim C86 \\sim C87 \\sim C88 \\sim C89
\\sim C84 \\sim C75 \\sim C83 \\sim C82 \\sim C81 \\sim C77 \\sim C76 \\sim
C224 \\sim C44 \\sim C15 \\sim C28 \\sim C19 \\sim C18 \\sim C17 \\sim C16
\\sim C91 \\sim C31 \\sim C35 \\sim C59 \\sim C90 \\sim C154: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C57 \\sim C58 \\sim C61 \\sim C216 \\sim C62 \\sim C64: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C00V) \\sim Ueq, Uanis(C00W) \\sim Ueq, Uanis(C00X) \\sim Ueq,
Uanis(C00Y) \\sim Ueq, Uanis(C010) \\sim Ueq, Uanis(C013) \\sim Ueq,
Uanis(C014) \\sim Ueq, Uanis(C016) \\sim Ueq, Uanis(C017) \\sim Ueq,
Uanis(C019) \\sim Ueq, Uanis(C01B) \\sim Ueq, Uanis(C01C) \\sim Ueq,
Uanis(C01D) \\sim Ueq, Uanis(C01Q) \\sim Ueq, Uanis(C023) \\sim Ueq,
Uanis(C011) \\sim Ueq, Uanis(C00Z) \\sim Ueq, Uanis(C01R) \\sim Ueq,
Uanis(C01E) \\sim Ueq, Uanis(C01G) \\sim Ueq, Uanis(C01H) \\sim Ueq,
Uanis(C01I) \\sim Ueq, Uanis(C01M) \\sim Ueq, Uanis(C01N) \\sim Ueq,
Uanis(C01P) \\sim Ueq, Uanis(C01S) \\sim Ueq, Uanis(C01U) \\sim Ueq,
Uanis(C01X) \\sim Ueq, Uanis(C01Z) \\sim Ueq, Uanis(C020) \\sim Ueq,
Uanis(C021) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C02C)
\\sim Ueq, Uanis(C01J) \\sim Ueq, Uanis(C012) \\sim Ueq, Uanis(C022) \\sim Ueq,
Uanis(C024) \\sim Ueq, Uanis(C026) \\sim Ueq, Uanis(C028) \\sim Ueq,
Uanis(C01A) \\sim Ueq, Uanis(C01V) \\sim Ueq, Uanis(C01Y) \\sim Ueq,
Uanis(C02P) \\sim Ueq, Uanis(C02G) \\sim Ueq, Uanis(C029) \\sim Ueq,
Uanis(C02U) \\sim Ueq, Uanis(C02Z) \\sim Ueq, Uanis(C032) \\sim Ueq,
Uanis(C033) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C9)
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C60) \\sim Ueq,
Uanis(C23) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C1)
\\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C38) \\sim Ueq,
Uanis(C70) \\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C125) \\sim Ueq, Uanis(C147)
\\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C6) \\sim Ueq,
Uanis(C5) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C12)
\\sim Ueq, Uanis(C175) \\sim Ueq, Uanis(C141) \\sim Ueq, Uanis(C22) \\sim Ueq,
Uanis(C20) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C32)
\\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41) \\sim Ueq,
Uanis(C42) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C24)
\\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C132) \\sim Ueq, Uanis(C143) \\sim Ueq,
Uanis(C80) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C67)
\\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C46) \\sim Ueq,
Uanis(C49) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C29)
\\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C53) \\sim Ueq,
Uanis(C79) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C55)
\\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C74) \\sim Ueq,
Uanis(C73) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C69)
\\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(C87) \\sim Ueq,
Uanis(C88) \\sim Ueq, Uanis(C89) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C75)
\\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C81) \\sim Ueq,
Uanis(C77) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C224) \\sim Ueq, Uanis(C44)
\\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C19) \\sim Ueq,
Uanis(C18) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C91)
\\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C59) \\sim Ueq,
Uanis(C90) \\sim Ueq, Uanis(C154) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C57) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C216)
\\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C64) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C41) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C41) \\sim Ueq, Uanis(Cl1) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
5. Others
 Fixed Sof: Au0D(0.82) Au0E(0.72) Au1(0.18) Au2(0.28)
6.a Aromatic/amide H refined with riding coordinates:
 C00X(H00X), C016(H016), C01N(H01N), C01G(H01G), C019(H019), C026(H026),
 C01X(H01X), C01B(H01B), C00W(H00W), C01Q(H01Q), C023(H023), C00Z(H00Z),
 C01R(H01R), C01E(H01E), C024(H024), C02U(H02U), C029(H029), C01S(H01S),
 C013(H013), C01H(H01H), C01Z(H01Z), C01U(H01U), C01C(H01C), C020(H020),
 C032(H032), C02Z(H02Z), C021(H021), C50(H50), C51(H51), C02C(H02C), C01J(H01J),
  C01V(H01V), C01Y(H01Y), C02P(H02P), C02G(H02G), C33(H33), C60(H60), C25(H25),
 C9(H9), C4(H4), C23(H23), C39(H39), C11(H11), C13(H13), C56(H56), C38(H38),
 C70(H70), C78(H78), C3(H3), C10(H10), C12(H12), C8(H8), C175(H175), C22(H22),
 C20(H20), C66(H66), C36(H36), C40(H40), C42(H42), C26(H26), C43(H43), C24(H24),
  C27(H27), C143(H143), C80(H80), C63(H63), C47(H47), C67(H67), C34(H34),
 C46(H46), C49(H49), C48(H48), C29(H29), C21(H21), C53(H53), C79(H79), C65(H65),
  C54(H54), C55(H55), C74(H74), C73(H73), C71(H71), C72(H72), C69(H69),
 C86(H86), C87(H87), C88(H88), C89(H89), C84(H84), C83(H83), C82(H82), C81(H81),
  C77(H77), C76(H76), C15(H15), C28(H28), C19(H19), C18(H18), C17(H17),
 C91(H91), C35(H35), C59(H59), C90(H90), C154(H154), C64(H64), C62(H62),
 C216(H216), C61(H61)
6.b Fitted hexagon refined as free rotating group:
 C00V(C00X,C016,C017,C01N,C01G), C019(C026,C01X,C01B,C00W,C00Y), C01D(C01Q,
 C023,C011,C00Z,C01R), C01I(C010,C01E,C024,C02U,C029), C01S(C014,C013,C01H,C01P,
 C01Z), C01U(C01C,C01M,C020,C032,C02Z), C021(C50,C51,C02C,C01J,C012), C028(C01A,
 C01V,C01Y,C02P,C02G), C2(C33,C60,C25,C9,C4), C23(C39,C11,C1,C7,C13), C125(C147,
 C56,C38,C70,C78), C5(C6,C3,C10,C12,C8), C175(C141,C22,C20,C37,C66), C32(C36,
 C40,C41,C42,C26), C43(C24,C27,C132,C143,C80), C63(C47,C67,C34,C45,C46),
 C49(C48,C30,C29,C21,C14), C53(C79,C65,C54,C55,C52), C68(C74,C73,C71,C72,C69),
 C85(C86,C87,C88,C89,C84), C75(C83,C82,C81,C77,C76), C16(C15,C28,C19,C18,C17),
 C91(C31,C35,C59,C90,C154), C64(C62,C216,C61,C58,C57)
6.c Idealised Me refined as rotating group:
 C022(H02A,H02B,H02D), C033(H03A,H03B,H03C), C224(H22A,H22B,H22C), C44(H44A,
 H44B,H44C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              86719
_shelx_fab_checksum              13636
_olex2_submission_special_instructions 'No special instructions were received'
_stoe_detector_distance          '60.0 mm'
_stoe_detector_pixelsize_x       '0.172 mm'
_stoe_detector_pixelsize_y       '0.172 mm'
_stoe_detector_size_x            '8.4 cm'
_stoe_detector_size_y            '10.6 cm'
_stoe_evaluation_integration_a   5.5
_stoe_evaluation_integration_b   -0.6
_stoe_evaluation_integration_ems 0.010
_stoe_evaluation_lana_bis_l_even_max -
_stoe_evaluation_lana_bis_l_odd_max -
_stoe_evaluation_lana_bos_l_even_max 4
_stoe_evaluation_lana_bos_l_odd_max 1
_stoe_evaluation_lana_completeness 92.9
_stoe_evaluation_lana_dxs_max_order 3
_stoe_evaluation_lana_dys_max_order 3
_stoe_evaluation_lana_fs_max_order 3
_stoe_evaluation_lana_max_2theta_available 140.5
_stoe_evaluation_lana_max_2theta_desired 140.5
_stoe_evaluation_lana_mean_redundancy 2.4
_stoe_evaluation_lana_number_refls_after_or 73743
_stoe_evaluation_lana_number_refls_outliers 3800
_stoe_evaluation_lana_number_refls_total 77543
_stoe_evaluation_lana_number_refls_unique 31347
_stoe_evaluation_lana_number_refls_written 73743
_stoe_evaluation_lana_or_c1      0.035
_stoe_evaluation_lana_or_c2      0
_stoe_evaluation_lana_or_c3      0
_stoe_evaluation_lana_or_c4      0.7
_stoe_evaluation_lana_point_group -1
_stoe_evaluation_lana_table
;
2Theta          18.5   32.9   47.3   61.7   76.1   90.5  104.9  119.3  133.7
<Resolution>    4.29   2.64   1.90   1.50   1.24   1.08   0.97   0.89   0.85
N(total)         708   2347   4086   5121  15494  15007  14755  12842   7183
<Redundancy>     1.7    1.8    1.7    1.6    3.1    2.7    2.5    2.3    2.0
Complet. [%%]    95.9   97.5   96.7   91.8   97.8   99.2   98.3   96.2   68.7
<I/sigma>       29.7   32.9   19.0    7.8    5.1    3.4    2.1    2.2    1.3
R(int)         0.039  0.035  0.040  0.060  0.049  0.062  0.092  0.098  0.200
;
_stoe_measurement_identifier     1
_stoe_measurement_max_exposure_per_frame '15.0 s'
_stoe_measurement_mean_exposure_per_frame '11.5 s'
_stoe_measurement_min_exposure_per_frame '2.0 s'
_stoe_measurement_total_exposure_time '5.5 h'
_stoe_measurement_total_frame_number 1738
_stoe_measurement_total_run_number 32
_stoe_measurement_tube_power     '30.0 W'