Photoluminescence control by atomically precise surface metallization of C-centered hexagold(i) clusters using N-heterocyclic carbenes.
Lei, Zhen; Zhao, Pei; Pei, Xiao-Li; Ube, Hitoshi; Ehara, Masahiro; Shionoya, Mitsuhiko; Chemical science 14 (2023) 6207–6215; doi:10.1039/d3sc01976d

data_1569125
_publ_section_title
;
 Photoluminescence control by atomically precise surface metallization of
 C-centered hexagold(i) clusters using N-heterocyclic carbenes.
;
_journal_issue                   23
_journal_name_full               'Chemical science'
_journal_page_first              6207
_journal_page_last               6215
_journal_paper_doi               10.1039/d3sc01976d
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C103 H111 Ag3 Au6 N21, 5(B F4)'
_chemical_formula_sum            'C103 H111 Ag3 Au6 B5 F20 N21'
_chemical_formula_weight         3582.58
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-12-30
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2022-09-21 deposited with the CCDC.	2023-04-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.484(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   28.2746(8)
_cell_length_b                   33.2019(8)
_cell_length_c                   29.4805(10)
_cell_measurement_reflns_used    17008
_cell_measurement_temperature    93(2)
_cell_measurement_theta_max      72.2380
_cell_measurement_theta_min      2.6790
_cell_volume                     26537.9(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      93(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.951
_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    -80.00 -32.00   0.50    5.00    --    0.00 -38.00 -90.00   96
  2  \w     16.00  67.00   0.50    5.00    --    0.00  38.00-180.00  102
  3  \w    -88.00  30.00   0.50    5.00    --    0.00 -82.00 150.00  236
  4  \w     69.00 144.00   0.50   30.00    --   98.20  61.00 -90.00  150
  5  \w     72.00 110.00   0.50   30.00    --   98.20  45.00-150.00   76
  6  \w    140.00 170.00   0.50   30.00    --   98.20  45.00-150.00   60
  7  \w     11.00 109.00   0.50   30.00    --   98.20 -61.00 120.00  196
  8  \w     90.00 126.00   0.50   30.00    --   98.20 -82.00 120.00   72
  9  \w     12.00  84.00   0.50   30.00    --   98.20 -82.00 120.00  144
 10  \w     41.00  69.00   0.50   30.00    --   98.20 -45.00-150.00   56
 11  \w     81.00 122.00   0.50   30.00    --   98.20 -45.00-150.00   82
 12  \w     11.00  36.00   0.50   30.00    --   98.20 -82.00  90.00   50
 13  \w     71.00 105.00   0.50   30.00    --   98.20 -82.00  90.00   68
 14  \w    100.00 127.00   0.50   30.00    --   98.20 -82.00 150.00   54
 15  \w    161.00 187.00   0.50   30.00    --   98.20  61.00 -90.00   52
 16  \w     67.00 166.00   0.50   30.00    --   98.20  30.00  30.00  198
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0058422000
_diffrn_orient_matrix_UB_12      0.0460793000
_diffrn_orient_matrix_UB_13      0.0011407000
_diffrn_orient_matrix_UB_21      0.0304901000
_diffrn_orient_matrix_UB_22      0.0005517000
_diffrn_orient_matrix_UB_23      0.0524264000
_diffrn_orient_matrix_UB_31      0.0475875000
_diffrn_orient_matrix_UB_32      0.0053733000
_diffrn_orient_matrix_UB_33      -0.0149910000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0481
_diffrn_reflns_av_unetI/netI     0.0500
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.951
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            62923
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.668
_diffrn_reflns_theta_min         2.053
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    16.252
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.14295
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.20a (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.793
_exptl_crystal_description       block
_exptl_crystal_F_000             13568
_exptl_crystal_preparation       Luminescent
_exptl_crystal_size_max          0.10
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         4.442
_refine_diff_density_min         -1.765
_refine_diff_density_rms         0.273
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.109
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1339
_refine_ls_number_reflns         25505
_refine_ls_number_restraints     576
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.1197
_refine_ls_R_factor_gt           0.0970
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2906
_refine_ls_wR_factor_ref         0.3128
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15540
_reflns_number_total             25505
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01976d2.cif
_cod_data_source_block           3
_cod_depositor_comments
'Adding full bibliography for 1569121--1569126.cif.'
_cod_database_code               1569125
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_reflns_odcompleteness_completeness 98.39
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 F43-B4 = F41-B4 = F44-B4 = F42-B4
 1.45 with sigma of 0.01
 F61-B6 = F64-B6 = F63-B6 = F62-B6
 1.45 with sigma of 0.01
 F11-B1 = F14-B1 = F13-B1 = F12-B1
 1.45 with sigma of 0.01
 F21-B2 = F24-B2 = F23-B2 = F22-B2
 1.45 with sigma of 0.01
 F34-B3 = F32-B3 = F33-B3 = F31-B3
 1.45 with sigma of 0.01
 F24-F21 = F24-F23 = F24-F22 = F21-F23 = F21-F22 = F23-F22
 2.35 with sigma of 0.001
 F14-F11 = F14-F13 = F14-F12 = F11-F13 = F11-F12 = F13-F12
 2.35 with sigma of 0.001
 F64-F63 = F64-F62 = F64-F61 = F63-F62 = F63-F61 = F62-F61
 2.35 with sigma of 0.001
 F44-F43 = F44-F42 = F44-F41 = F43-F42 = F43-F41 = F42-F41
 2.35 with sigma of 0.001
 F32-F34 = F32-F33 = F32-F31 = F34-F33 = F34-F31 = F33-F31
 2.35 with sigma of 0.001
 B5-F51 = B5-F52 = B5-F54 = B5-F53
 1.45 with sigma of 0.01
 F51-F52 = F51-F54 = F51-F53 = F52-F54 = F52-F53 = F54-F53
 2.35 with sigma of 0.01
 C9-C8 \\sim C3-C2 \\sim C6-C5
 with sigma of 0.01
 N602-C617 \\sim N102-C117 \\sim N402-C417 \\sim N202-C217 \\sim N502-C517
\\sim N302-C317
 with sigma of 0.01
 Ag1-N4 \\sim Ag3-N10 \\sim Ag2-N7
 with sigma of 0.01
 N7-C6 \\sim N4-C3 \\sim N10-C9
 with sigma of 0.01
 C618-C617 \\sim C619-C617 \\sim C118-C117 \\sim C119-C117 \\sim C519-C517
\\sim C518-C517 \\sim C318-
 C317 \\sim C319-C317 \\sim C419-C417 \\sim C218-C217 \\sim C418-C417 \\sim
C219-C217
 with sigma of 0.01
 C511-C510 \\sim C211-C210 \\sim C111-C110 \\sim C311-C310 \\sim C411-C410
\\sim C611-C610
 with sigma of 0.01
 N209-C210 \\sim N309-C310 \\sim N609-C610 \\sim N409-C410 \\sim N109-C110
\\sim N509-C510
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C8 \\sim C9 \\sim N10: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002 within 2A
C5 \\sim C6 \\sim N7: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002 within 2A
C114 \\sim C115 \\sim N116 \\sim C111 \\sim C112 \\sim C113: within 2A with
sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
C615 \\sim C614 \\sim C613 \\sim C612 \\sim C611 \\sim N616: within 2A with
sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
B5 \\sim F53 \\sim F54 \\sim F51 \\sim F52: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
B5 \\sim F54 \\sim F51 \\sim F53 \\sim F52: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
C605 \\sim C604 \\sim C603 \\sim C608 \\sim C607 \\sim C606: within 2A with
sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
C105 \\sim C104 \\sim C103 \\sim C108 \\sim C107 \\sim C106: within 2A with
sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
C407 \\sim C406 \\sim C405 \\sim C404 \\sim C403 \\sim C408: within 2A with
sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
F52 \\sim F51 \\sim B5 \\sim F54 \\sim F53: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
C514 \\sim C515 \\sim N516 \\sim C511 \\sim C512 \\sim C513: within 2A with
sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
F24 \\sim B2 \\sim F21 \\sim F22 \\sim F23: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
C119 \\sim C118 \\sim C117: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
B6 \\sim F61 \\sim F62 \\sim F63 \\sim F64: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
F14 \\sim B1 \\sim F11 \\sim F13 \\sim F12: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
F33 \\sim B3 \\sim F31 \\sim F32 \\sim F34: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
B4 \\sim F44 \\sim F43 \\sim F42 \\sim F41: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
F42 \\sim B4 \\sim F44 \\sim F43 \\sim F41: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
4. Others
 Fixed Sof: F51(0.5) F52(0.5) F53(0.5) F54(0.5) B5(0.5) F61(0.5) F62(0.5)
 F63(0.5) F64(0.5) B6(0.5)
5.a Ternary CH refined with riding coordinates:
 C117(H117), C217(H217), C317(H317), C417(H417), C517(H517), C617(H617)
5.b Secondary CH2 refined with riding coordinates:
 C110(H11A,H11B), C210(H21A,H21B), C310(H31A,H31B), C410(H41A,H41B), C510(H51A,
 H51B), C610(H61A,H61B)
5.c Aromatic/amide H refined with riding coordinates:
 C104(H104), C105(H105), C106(H106), C107(H107), C213(H213), C212(H212),
 C215(H215), C214(H214), C304(H304), C305(H305), C306(H306), C307(H307),
 C415(H415), C414(H414), C413(H413), C412(H412), C612(H612), C613(H613),
 C614(H614), C615(H615), C112(H112), C113(H113), C114(H114), C115(H115),
 C204(H204), C207(H207), C206(H206), C205(H205), C312(H312), C313(H313),
 C314(H314), C315(H315), C407(H407), C406(H406), C405(H405), C404(H404),
 C507(H507), C506(H506), C505(H505), C504(H504), C514(H514), C513(H513),
 C512(H512), C515(H515), C604(H604), C605(H605), C606(H606), C607(H607)
5.d Fitted hexagon refined as free rotating group:
 C108(C103,C104,C105,C106,C107), C213(C212,C211,N216,C215,C214), C303(C304,
 C305,C306,C307,C308), C411(N416,C415,C414,C413,C412), C611(C612,C613,C614,C615,
 N616), C111(C112,C113,C114,C115,N116), C204(C203,C208,C207,C206,C205),
 C311(C312,C313,C314,C315,N316), C408(C407,C406,C405,C404,C403), C508(C507,C506,
 C505,C504,C503), C514(C513,C512,C511,N516,C515), C603(C604,C605,C606,C607,C608)
5.e Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C5(H5A,H5B,H5C), C8(H8A,H8B,H8C), C118(H11C,H11D,H11E),
 C119(H11F,H11G,H11H), C218(H21C,H21D,H21E), C219(H21F,H21G,H21H), C318(H31C,
 H31D,H31E), C319(H31F,H31G,H31H), C418(H41C,H41D,H41E), C419(H41F,H41G,H41H),
 C518(H51C,H51D,H51E), C519(H51F,H51G,H51H), C618(H61C,H61D,H61E), C619(H61F,
 H61G,H61H)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              92967
_shelx_fab_checksum              61718
_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 3.819
_oxdiff_exptl_absorpt_empirical_full_min 0.495