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_1569126
_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
'C119 H102 Ag4 Au6 N26, 1.75(C H2 Cl2), 0.25(C Cl2), 6(B F4), C2 H3 N'
_chemical_formula_sum            'C123 H109 Ag4 Au6 B6 Cl4 F24 N27'
_chemical_formula_weight         4241.30
_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             2019-07-10
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-09-21 deposited with the CCDC.	2023-04-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.2056(9)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   35.5410(3)
_cell_length_b                   15.07664(17)
_cell_length_c                   50.5683(5)
_cell_measurement_reflns_used    35456
_cell_measurement_temperature    93(2)
_cell_measurement_theta_max      73.1410
_cell_measurement_theta_min      2.4940
_cell_volume                     27054.1(5)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      93(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.972
_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     32.00  80.00   0.50    1.80    --    0.00  38.00 -90.00   96
  2  \w    -20.00   6.00   0.50    1.80    --    0.00  38.00 -90.00   52
  3  \w    -33.00  41.00   0.50    1.80    --    0.00  77.00 -30.00  148
  4  \w     11.00  89.00   0.50    1.80    --    0.00  57.00 120.00  156
  5  \w     70.00 170.00   0.50    7.18    --   98.20  61.00-150.00  200
  6  \w     72.00 185.00   0.50    7.18    --   98.20  61.00 150.00  226
  7  \w     89.00 125.00   0.50    7.18    --   98.20 -82.00 -60.00   72
  8  \w     11.00 135.00   0.50    7.18    --   98.20 -82.00 -90.00  248
  9  \w     65.00  91.00   0.50    7.18    --   98.20  77.00  60.00   52
 10  \w    130.00 155.00   0.50    7.18    --   98.20  77.00  60.00   50
 11  \w     10.00 108.00   0.50    7.18    --   98.20 -61.00 -90.00  196
 12  \w     72.00 182.00   0.50    7.18    --   98.20  45.00  90.00  220
;
_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      0.0085395000
_diffrn_orient_matrix_UB_12      0.0995984000
_diffrn_orient_matrix_UB_13      -0.0026164000
_diffrn_orient_matrix_UB_21      0.0359828000
_diffrn_orient_matrix_UB_22      -0.0115464000
_diffrn_orient_matrix_UB_23      0.0180997000
_diffrn_orient_matrix_UB_31      0.0227221000
_diffrn_orient_matrix_UB_32      -0.0192348000
_diffrn_orient_matrix_UB_33      -0.0244822000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0522
_diffrn_reflns_av_unetI/netI     0.0527
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -43
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -62
_diffrn_reflns_number            74304
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.572
_diffrn_reflns_theta_min         2.490
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    17.954
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.09970
_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    2.083
_exptl_crystal_description       block
_exptl_crystal_F_000             16096
_exptl_crystal_preparation       Luminescent
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.05
_refine_diff_density_max         4.377
_refine_diff_density_min         -2.466
_refine_diff_density_rms         0.312
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1908
_refine_ls_number_reflns         26513
_refine_ls_number_restraints     191
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0680
_refine_ls_R_factor_gt           0.0605
_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^)+(0.1150P)^2^+263.0770P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1686
_refine_ls_wR_factor_ref         0.1753
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22778
_reflns_number_total             26513
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01976d2.cif
_cod_data_source_block           4
_cod_depositor_comments
'Adding full bibliography for 1569121--1569126.cif.'
_cod_original_cell_volume        27054.0(5)
_cod_database_code               1569126
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.87
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 B7-F71 = B7-F72 = B7-F73 = B7-F74
 1.45 with sigma of 0.01
 F71-F72 = F71-F73 = F71-F74 = F72-F73 = F72-F74 = F73-F74
 2.35 with sigma of 0.01
 Cl7-C17 \\sim Cl8-C17
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl7 \\sim Cl8 \\sim C17: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002
Cl1 \\sim Cl2 \\sim C14: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002
F71 \\sim F72 \\sim F73 \\sim F74 \\sim B7: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002
F11 \\sim F12 \\sim F13 \\sim F14 \\sim B1: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002
Cl3 \\sim Cl4 \\sim C15: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002
N316 \\sim C310 \\sim C311 \\sim C312 \\sim C313 \\sim C314 \\sim C315: within
2A with sigma of 0.001 and sigma for terminal atoms of 0.002
N322 \\sim C310 \\sim C317 \\sim C318 \\sim C319 \\sim C320 \\sim C321: within
2A with sigma of 0.001 and sigma for terminal atoms of 0.002
N10 \\sim C8 \\sim C9: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002
4. Others
 Fixed Sof: H31C(0.5) H31D(0.5) H31A(0.5) H31B(0.5) C311(0.5) N316(0.5)
 C315(0.5) H315(0.5) C314(0.5) H314(0.5) C313(0.5) H313(0.5) C312(0.5)
 H312(0.5) C317(0.5) N322(0.5) C321(0.5) H321(0.5) C320(0.5) H320(0.5)
 C319(0.5) H319(0.5) C318(0.5) H318(0.5) Cl1(0.25) Cl2(0.25) C14(0.25)
 H14A(0.25) H14B(0.25) Cl3(0.25) Cl4(0.25) C15(0.25) H15A(0.25) H15B(0.25)
 Cl7(0.25) Cl8(0.25) C17(0.25) Cl9(0.5) C18(0.25) H18A(0.25) H18B(0.25)
 F61(0.5) F62(0.5) F63(0.5) F64(0.5) B6(0.5) F71(0.5) F72(0.5) F73(0.5)
 F74(0.5) B7(0.5) N10(0.5) C8(0.5) H8A(0.5) H8B(0.5) H8C(0.5) C9(0.5) N13(0.5)
 C11(0.5) H11E(0.5) H11F(0.5) H11G(0.5) C12(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C110(H11A,H11B), C117(H11C,H11D), C210(H21A,H21B), C217(H21C,H21D), C310(H31C,
 H31D), C310(H31A,H31B), C323(H32A,H32B), C410(H41A,H41B), C417(H41C,H41D),
 C510(H51A,H51B), C517(H51C,H51D), C610(H61A,H61B), C617(H61C,H61D), C14(H14A,
 H14B), C15(H15A,H15B), C16(H16A,H16B), C18(H18A,H18B)
5.b Aromatic/amide H refined with riding coordinates:
 C104(H104), C105(H105), C106(H106), C107(H107), C112(H112), C113(H113),
 C114(H114), C115(H115), C119(H119), C120(H120), C121(H121), C122(H122),
 C204(H204), C205(H205), C206(H206), C207(H207), C212(H212), C213(H213),
 C214(H214), C215(H215), C219(H219), C220(H220), C221(H221), C222(H222),
 C304(H304), C305(H305), C306(H306), C307(H307), C315(H315), C314(H314),
 C313(H313), C312(H312), C321(H321), C320(H320), C319(H319), C318(H318),
 C325(H325), C326(H326), C327(H327), C328(H328), C404(H404), C405(H405),
 C406(H406), C407(H407), C412(H412), C413(H413), C414(H414), C415(H415),
 C419(H419), C420(H420), C421(H421), C422(H422), C504(H504), C505(H505),
 C506(H506), C507(H507), C512(H512), C513(H513), C514(H514), C515(H515),
 C519(H519), C520(H520), C521(H521), C522(H522), C604(H604), C605(H605),
 C606(H606), C607(H607), C612(H612), C613(H613), C614(H614), C615(H615),
 C619(H619), C620(H620), C621(H621), C622(H622)
5.c Fitted hexagon refined as free rotating group:
 C311(N316,C315,C314,C313,C312), C317(N322,C321,C320,C319,C318)
5.d Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C5(H5A,H5B,H5C), C8(H8A,H8B,H8C), C11(H11E,H11F,H11G)
;
_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 5.115
_oxdiff_exptl_absorpt_empirical_full_min 0.491