Tailoring the subshell and electronic structure of an atomically precise AuAg alloy nanocluster.
Deng, Guocheng; Ki, Taeyoung; Liu, Xiaolin; Chen, Yuping; Lee, Kangjae; Yoo, Seungwoo; Tang, Qing; Bootharaju, Megalamane S.; Hyeon, Taeghwan; Chemical communications (Cambridge, England) 60 (2024) 1289–1292; doi:10.1039/d3cc04432g

data_7132550
_publ_section_title
;
 Tailoring the subshell and electronic structure of an atomically precise
 AuAg alloy nanocluster.
;
_journal_issue                   10
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              1289
_journal_page_last               1292
_journal_paper_doi               10.1039/d3cc04432g
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C272 H102 Ag27 Au34 F68, C24 H20 P'
_chemical_formula_sum            'C296 H122 Ag27 Au34 F68 P'
_chemical_formula_weight         14610.25
_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             2023-12-01
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.09.11 svn.r3730fd0d for OlexSys, GUI svn.r6159)
;
_audit_update_record
;
2023-12-04 deposited with the CCDC.	2023-12-21 downloaded from the CCDC.
;
_cell_angle_alpha                88.1010(10)
_cell_angle_beta                 74.9280(10)
_cell_angle_gamma                87.3240(10)
_cell_formula_units_Z            2
_cell_length_a                   21.0215(2)
_cell_length_b                   22.1806(2)
_cell_length_c                   35.4832(3)
_cell_measurement_reflns_used    56587
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      70.3120
_cell_measurement_theta_min      2.9200
_cell_volume                     15954.4(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.984
_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     48.00  87.00   0.50   18.00    --   38.00 -82.00  60.00   78
  2  \w    -17.00   9.00   0.50   18.00    --   38.00 -57.00  60.00   52
  3  \w     29.00  79.00   0.50   18.00    --   38.00 -77.00   0.00  100
  4  \w      5.00  70.00   0.50   18.00    --   38.00  57.00   0.00  130
  5  \w     35.00  84.00   0.50   18.00    --   38.00 -57.00  60.00   98
  6  \w    -24.00  84.00   0.50   18.00    --   38.00 -57.00-180.00  216
  7  \w     97.00 124.00   0.50   18.00    --   38.00  38.00  90.00   54
  8  \w    -35.00   2.00   0.50   18.00    --   38.00  38.00  90.00   74
  9  \w      3.00  87.00   0.50   18.00    --   38.00 -82.00-180.00  168
 10  \w    -47.00 -10.00   0.50   18.00    --   38.00 -82.00  60.00   74
 11  \w    -50.00 -24.00   0.50   18.00    --   38.00 -82.00-180.00   52
 12  \w    -50.00  23.00   0.50   18.00    --   38.00 -77.00   0.00  146
 13  \w    -10.00 126.00   0.50   18.00    --   38.00  82.00  60.00  272
 14  \w     24.00  49.00   0.50   18.00    --   38.00  38.00  90.00   50
 15  \w     10.00  40.00   0.50   18.00    --   38.00  82.00 -90.00   60
 16  \w     36.00 193.00   0.50   42.00    --  103.80  12.00  30.00  314
 17  \w     29.00 122.00   0.50   42.00    --  103.80 -82.00 -90.00  186
 18  \w     61.00  87.00   0.50   42.00    --  103.80 -82.00-120.00   52
 19  \w     26.00 150.00   0.50   42.00    --  103.80 -82.00  90.00  248
 20  \w    162.00 193.00   0.50   42.00    --  103.80  50.00  30.00   62
 21  \w     15.00  42.00   0.50   42.00    --  103.80 -77.00-180.00   54
 22  \w     83.00 108.00   0.50   42.00    --  103.80 -82.00-180.00   50
 23  \w     14.00 128.00   0.50   42.00    --  103.80 -63.00 -60.00  228
 24  \w     25.00  51.00   0.50   42.00    --  103.80 -82.00-120.00   52
 25  \w     17.00  43.00   0.50   42.00    --  103.80 -82.00-180.00   52
 26  \w     84.00 109.00   0.50   42.00    --  103.80 -82.00 150.00   50
 27  \w    107.00 193.00   0.50   42.00    --  103.80 -12.00 120.00  172
 28  \w    102.00 138.00   0.50   42.00    --  103.80 -82.00 -60.00   72
 29  \w     16.00 109.00   0.50   42.00    --  103.80 -82.00  30.00  186
 30  \w     14.00 153.00   0.50   42.00    --  103.80  12.00-180.00  278
 31  \w     59.00  93.00   0.50   42.00    --  103.80 -82.00 -60.00   68
 32  \w     17.00  90.00   0.50   42.00    --  103.80 -12.00 120.00  146
 33  \w    109.00 134.00   0.50   42.00    --  103.80  50.00  30.00   50
 34  \w     29.00  54.00   0.50   42.00    --  103.80 -82.00 -60.00   50
 35  \w     88.00 114.00   0.50   42.00    --  103.80 -82.00 -30.00   52
 36  \w     67.00 138.00   0.50   42.00    --  103.80 -82.00-150.00  142
 37  \w     73.00 150.00   0.50   42.00    --  103.80 -82.00 120.00  154
 38  \w     18.00 146.00   0.50   42.00    --  103.80 -63.00  90.00  256
 39  \w     76.00 101.00   0.50   42.00    --  103.80 -82.00   0.00   50
 40  \w     68.00 104.00   0.50   42.00    --  103.80  50.00  30.00   72
 41  \w    111.00 149.00   0.50   42.00    --  103.80 -50.00   0.00   76
 42  \w     53.00  79.00   0.50   42.00    --  103.80 -50.00   0.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0138660000
_diffrn_orient_matrix_UB_12      0.0232947000
_diffrn_orient_matrix_UB_13      0.0373961000
_diffrn_orient_matrix_UB_21      0.0072969000
_diffrn_orient_matrix_UB_22      0.0641360000
_diffrn_orient_matrix_UB_23      -0.0182266000
_diffrn_orient_matrix_UB_31      -0.0743213000
_diffrn_orient_matrix_UB_32      0.0134471000
_diffrn_orient_matrix_UB_33      0.0170875000
_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  0.1144
_diffrn_reflns_av_unetI/netI     0.1066
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            156980
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        66.598
_diffrn_reflns_theta_max         66.598
_diffrn_reflns_theta_min         2.912
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    42.251
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.08102
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    3.041
_exptl_crystal_description       block
_exptl_crystal_F_000             12960
_exptl_crystal_size_max          0.532
_exptl_crystal_size_mid          0.187
_exptl_crystal_size_min          0.152
_refine_diff_density_max         7.732
_refine_diff_density_min         -6.177
_refine_diff_density_rms         0.611
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.120
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3151
_refine_ls_number_reflns         55473
_refine_ls_number_restraints     2578
_refine_ls_restrained_S_all      1.111
_refine_ls_R_factor_all          0.1213
_refine_ls_R_factor_gt           0.1081
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1120P)^2^+1027.8569P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2649
_refine_ls_wR_factor_ref         0.2746
_reflns_Friedel_coverage         0.000
_reflns_number_gt                43687
_reflns_number_total             55473
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc04432g2.cif
_cod_data_source_block           Au34Ag27
_cod_depositor_comments          'Adding full bibliography for 7132550.cif.'
_cod_database_code               7132550
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C296H122Ag27Au34F68P
_shelx_estimated_absorpt_t_max   0.060
_shelx_estimated_absorpt_t_min   0.017
_reflns_odcompleteness_completeness 98.37
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 F32-C148
 1.4 with sigma of 0.01
 C221-C191
 1.25 with sigma of 0.01
 C46-C220
 1.28 with sigma of 0.01
 Au34-C221
 2.05 with sigma of 0.01
 F55-C227
 1.35 with sigma of 0.01
 C220-C223
 2.6 with sigma of 0.01
 Au34-C220
 2.05 with sigma of 0.01
 C223-C46
 1.44 with sigma of 0.01
 F52-C226
 1.4 with sigma of 0.01
 P1-C279
 1.8 with sigma of 0.01
 F31-C117
 1.4 with sigma of 0.01
 F22-C169
 1.4 with sigma of 0.01
 F37-C181
 1.4 with sigma of 0.01
 C171-C205
 1.25 with sigma of 0.01
 C205-C178
 1.45 with sigma of 0.01
 F38-C112
 1.4 with sigma of 0.01
 F39-C113
 1.4 with sigma of 0.01
 F41-C56
 1.4 with sigma of 0.01
 F40-C57
 1.4 with sigma of 0.01
 F15-C51
 1.35 with sigma of 0.01
 F18-C50
 1.35 with sigma of 0.01
 F34-C70
 1.35 with sigma of 0.01
 F42-C84
 1.35 with sigma of 0.01
 C222-C138
 1.25 with sigma of 0.01
 C254-C191
 1.45 with sigma of 0.01
 F56-C246
 1.35 with sigma of 0.01
 F58-C258
 1.35 with sigma of 0.01
 F57-C241
 1.35 with sigma of 0.01
 F61-C259
 1.35 with sigma of 0.01
 F62-C260
 1.35 with sigma of 0.01
 F60-C269
 1.35 with sigma of 0.01
 F59-C270
 1.35 with sigma of 0.01
 C266-C265
 1.5 with sigma of 0.01
 F64-C216
 1.35 with sigma of 0.01
 F65-C198
 1.35 with sigma of 0.01
 F63-C217
 1.35 with sigma of 0.01
 F66-C238
 1.35 with sigma of 0.01
 F68-C42
 1.35 with sigma of 0.01
 F47-C251
 1.35 with sigma of 0.01
 F67-C239
 1.35 with sigma of 0.01
 C235-C126
 1.5 with sigma of 0.01
 C278-C265
 1.28 with sigma of 0.01
 P1-C277
 1.75 with sigma of 0.01
 C129-C40
 1.5 with sigma of 0.01
 Au24-C123
 1.9 with sigma of 0.01
 P1-C285
 1.75 with sigma of 0.01
 C129-C123
 1.3 with sigma of 0.01
 Au32-C17
 1.9 with sigma of 0.01
 C124-C17
 1.3 with sigma of 0.01
 C72-C28
 1.48 with sigma of 0.01
 P1-C296
 1.8 with sigma of 0.01
 C124-C54
 1.52 with sigma of 0.01
 C109-C28
 1.28 with sigma of 0.01
 C137-C136
 1.2 with sigma of 0.01
 F55-C228
 2.25 with sigma of 0.01
 P1-C280
 2.75 with sigma of 0.01
 C227-F52
 2.25 with sigma of 0.01
 F31-C118
 2.3 with sigma of 0.01
 F57-C242
 2.25 with sigma of 0.01
 F56-C241
 2.25 with sigma of 0.01
 F61-C260
 2.25 with sigma of 0.01
 F63-C216
 2.25 with sigma of 0.01
 F65-C197
 2.25 with sigma of 0.01
 C238-F67
 2.25 with sigma of 0.01
 C237-F66
 2.25 with sigma of 0.01
 C252-F47
 2.25 with sigma of 0.01
 C126-C236
 2.31 with sigma of 0.01
 F66-C239
 2.25 with sigma of 0.01
 F32-C149
 2.25 with sigma of 0.01
 F68-C41
 2.26 with sigma of 0.01
 C41-C129
 2.55 with sigma of 0.01
 F17-F68_$1
 2.51 with sigma of 0.01
3. Restrained planarity
 C279, P1, C280, C281, C282, C283, C284
 with sigma of 0.1
 C117, C122, C121, C120, C119, C118, F27, F31
 with sigma of 0.1
 C41, C40, C45, C44, C43, F50, F68
 with sigma of 0.1
 F34, C70, C69, C68, C67, C72, C71, F33
 with sigma of 0.1
 F66, C237, C238, C239, C240, C235, C236, F67
 with sigma of 0.1
 C296, C291, C292, C293, C294, C295
 with sigma of 0.1
 C263, C264, C259, F61, F62, C261, C262
 with sigma of 0.1
 F65, C193, C198, C197, C196, C195, C194
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Uanis(C220) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C223) \\sim Ueq, Uanis(C224)
\\sim Ueq, Uanis(C228) \\sim Ueq, Uanis(C227) \\sim Ueq, Uanis(C226) \\sim Ueq,
Uanis(C225) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C46) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C223) \\sim Ueq, Uanis(C224) \\sim Ueq, Uanis(C228) \\sim Ueq,
Uanis(C227) \\sim Ueq, Uanis(C226) \\sim Ueq, Uanis(C225) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(F52) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C128) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C96) \\sim Ueq, Uanis(C101)
\\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C98) \\sim Ueq, Uanis(C99) \\sim Ueq,
Uanis(C100) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C66) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C244) \\sim Ueq, Uanis(C245)
\\sim Ueq, Uanis(C246) \\sim Ueq, Uanis(C241) \\sim Ueq, Uanis(C242) \\sim Ueq,
Uanis(C243) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Au34) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C11) = Uanis(C37) = Uanis(C154) = Uanis(C153) = Uanis(C152) = Uanis(C151)
= Uanis(C156) = Uanis(C155) = Uanis(C7) = Uanis(C18) = Uanis(C115) =
Uanis(C114) = Uanis(C113) = Uanis(C112) = Uanis(C111) = Uanis(C110) =
Uanis(C31) = Uanis(C35) = Uanis(C65) = Uanis(C63) = Uanis(C62) = Uanis(C61) =
Uanis(C60) = Uanis(C1) = Uanis(C8) = Uanis(C146) = Uanis(C145) = Uanis(C150) =
Uanis(C149) = Uanis(C148) = Uanis(C147) = Uanis(C220) = Uanis(C46) =
Uanis(C223) = Uanis(C224) = Uanis(C225) = Uanis(C226) = Uanis(C227) =
Uanis(C228)
5.a Aromatic/amide H refined with riding coordinates:
 C20(H20), C23(H23), C24(H24), C41(H41), C44(H44), C45(H45), C49(H49),
 C52(H52), C53(H53), C55(H55), C58(H58), C59(H59), C60(H60), C61(H61), C64(H64),
  C67(H67), C68(H68), C71(H71), C79(H79), C82(H82), C83(H83), C85(H85),
 C86(H86), C88(H88), C91(H91), C92(H92), C95(H95), C97(H97), C98(H98),
 C101(H101), C103(H103), C106(H106), C107(H107), C110(H110), C111(H111),
 C114(H114), C119(H119), C120(H120), C122(H122), C132(H132), C134(H134),
 C135(H135), C139(H139), C142(H142), C143(H143), C145(H145), C147(H147),
 C150(H150), C153(H153), C155(H155), C156(H156), C160(H160), C161(H161),
 C164(H164), C166(H166), C167(H167), C170(H170), C173(H173), C174(H174),
 C176(H176), C179(H179), C180(H180), C183(H183), C184(H184), C185(H185),
 C188(H188), C193(H193), C195(H195), C196(H196), C199(H199), C202(H202),
 C204(H204), C207(H207), C208(H208), C211(H211), C215(H215), C218(H218),
 C219(H219), C224(H224), C225(H225), C228(H228), C229(H229), C232(H232),
 C234(H234), C236(H236), C237(H237), C240(H240), C242(H242), C243(H243),
 C245(H245), C247(H247), C249(H249), C250(H250), C253(H253), C255(H255),
 C256(H256), C261(H261), C262(H262), C264(H264), C267(H267), C268(H268),
 C271(H271), C272(H272), C273(H273), C274(H274), C275(H275), C276(H276),
 C280(H280), C281(H281), C282(H282), C283(H283), C284(H284), C286(H286),
 C287(H287), C288(H288), C289(H289), C290(H290), C291(H291), C292(H292),
 C293(H293), C294(H294), C295(H295)
5.b Fitted hexagon refined as free rotating group:
 C19(C20,C21,C22,C23,C24), C40(C41,C42,C43,C44,C45), C48(C49,C50,C51,C52,C53),
 C54(C55,C56,C57,C58,C59), C60(C61,C62,C63,C64,C65), C67(C68,C69,C70,C71,C72),
 C78(C79,C80,C81,C82,C83), C84(C85,C86,C87,C88,C89), C90(C91,C92,C93,C94,C95),
 C96(C97,C98,C99,C100,C101), C103(C104,C105,C106,C107,C108), C110(C111,C112,
 C113,C114,C115), C117(C118,C119,C120,C121,C122), C130(C131,C132,C133,C134,
 C135), C139(C140,C141,C142,C143,C144), C145(C146,C147,C148,C149,C150),
 C151(C152,C153,C154,C155,C156), C159(C160,C161,C162,C163,C164), C165(C166,C167,
 C168,C169,C170), C172(C173,C174,C175,C176,C177), C178(C179,C180,C181,C182,
 C183), C184(C185,C186,C187,C188,C189), C193(C194,C195,C196,C197,C198),
 C199(C200,C201,C202,C203,C204), C206(C207,C208,C209,C210,C211), C214(C215,C216,
 C217,C218,C219), C224(C225,C226,C227,C228,C223), C229(C230,C231,C232,C233,
 C234), C235(C236,C237,C238,C239,C240), C241(C242,C243,C244,C245,C246),
 C247(C248,C249,C250,C251,C252), C253(C254,C255,C256,C257,C258), C259(C260,C261,
 C262,C263,C264), C266(C267,C268,C269,C270,C271), C272(C273,C274,C275,C276,
 C277), C279(C280,C281,C282,C283,C284), C285(C286,C287,C288,C289,C290),
 C291(C292,C293,C294,C295,C296)
;
_shelx_res_checksum              84572
_shelx_hkl_checksum              74251
_shelx_fab_checksum              65295
_platon_squeeze_special_details
;
A solvent mask was calculated and 726 electrons were 
found in a volume of 2791\%A^3^ in 6 voids per unit cell. 
This is consistent with the presence of 
10[CH2Cl2], 6[C6H14], per Asymmetric Unit 
which account for 720 electrons 
per unit cell.
;
_platon_squeeze_void_probe_radius 1.20
_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 5.577
_oxdiff_exptl_absorpt_empirical_full_min 0.273