Crystal and Solution Photoluminescence of MAg24(SR)18 (M = Ag/Pd/Pt/Au) Nanoclusters and Some Implications for the Photoluminescence Mechanisms
Liu, Xu; Yuan, Jinyun; Yao, Chuanhao; Chen, Jishi; Li, Lingling; Bao, Xiaoli; Yang, Jinlong; Wu, Zhikun; The Journal of Physical Chemistry C 121 (2017) 13848–; doi:10.1021/acs.jpcc.7b01730

data_1546361
_publ_section_title
;
 Crystal and Solution Photoluminescence of MAg24(SR)18 (M = Ag/Pd/Pt/Au)
 Nanoclusters and Some Implications for the Photoluminescence Mechanisms
;
_journal_issue                   25
_journal_name_full               'The Journal of Physical Chemistry C'
_journal_page_first              13848
_journal_paper_doi               10.1021/acs.jpcc.7b01730
_journal_volume                  121
_journal_year                    2017
_chemical_formula_moiety         'C144 H159 Ag24 Pd S18, C24 H20 P, C24 P'
_chemical_formula_sum            'C168 H202 Ag24 P2 Pd S18'
_chemical_formula_weight         5555.58
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-10-10
_audit_creation_method
;
Olex2 1.2
(compiled 2016.08.31 svn.r3340 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                84.483(3)
_cell_angle_beta                 72.593(3)
_cell_angle_gamma                63.990(2)
_cell_formula_units_Z            2
_cell_length_a                   19.5843(10)
_cell_length_b                   20.1047(10)
_cell_length_c                   31.3508(18)
_cell_measurement_reflns_used    9893
_cell_measurement_temperature    173
_cell_measurement_theta_max      68.403
_cell_measurement_theta_min      2.447
_cell_volume                     10576.8(10)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 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      173.01
_diffrn_measured_fraction_theta_full 0.562
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0718
_diffrn_reflns_av_unetI/netI     0.0555
_diffrn_reflns_Laue_measured_fraction_full 0.562
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            146850
_diffrn_reflns_point_group_measured_fraction_full 0.562
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         49.996
_diffrn_reflns_theta_min         2.621
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    20.128
_exptl_absorpt_correction_T_max  0.0405
_exptl_absorpt_correction_T_min  0.0009
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1436 before and 0.0955 after correction.
The Ratio of minimum to maximum transmission is 0.0222.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.744
_exptl_crystal_description       block
_exptl_crystal_F_000             5404
_refine_diff_density_max         2.592
_refine_diff_density_min         -3.904
_refine_diff_density_rms         0.351
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.861
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           fullcycle
_refine_ls_number_parameters     1837
_refine_ls_number_reflns         21509
_refine_ls_number_restraints     1548
_refine_ls_restrained_S_all      1.878
_refine_ls_R_factor_all          0.1680
_refine_ls_R_factor_gt           0.1465
_refine_ls_shift/su_max          0.097
_refine_ls_shift/su_mean         0.003
_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          0.4139
_refine_ls_wR_factor_ref         0.4417
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16066
_reflns_number_total             21509
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jp7b01730_si_003.cif
_cod_data_source_block           160525lx3_0m
_cod_depositor_comments          'Adding full bibliography for 1546361.cif.'
_cod_database_code               1546361
_shelxl_version_number           2014-3
_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
 P47-C91 = P47-C2BA = P47-C69
 1.8 with sigma of 0.02
 P47-C1BA
 1.8 with sigma of 0.02
 C64-C60
 1.54 with sigma of 0.02
 C1AA-C100
 1.54 with sigma of 0.02
 C55-C54 = C56-C52 = C68-C72 = C71-C70 = C0AA-C102 = C62-C63 = C31-C30 = C32-
 C28 = C132-C136 = C135-C134 = C108-C112 = C111-C110 = C120-C116 = C118-C119 =
 C9AA-C126 = C124-C128 = C140-C144 = C88-C84 = C86-C87 = C79-C78 = C80-C76 =
 C23-C22 = C20-C24 = C39-C38 = C36-C40 = C44-C48 = C47-C46 = C16-C12 = C15-C14 =
  C143-C142 = C7-C6 = C4-C8 = C94-C95 = C96-C92
 1.54 with sigma of 0.02
 P47-C7BA \\sim P47-C85
 with sigma of 0.02
 P47-C305 \\sim P47-C127
 with sigma of 0.02
 P47-C141 \\sim P47-C4AA
 with sigma of 0.02
 C1BA-C91 \\sim C1BA-C2BA \\sim C1BA-C69 \\sim C69-C91 \\sim C91-C2BA \\sim
C69-C2BA
 with sigma of 0.02
 P47-C731 \\sim P47-C294
 with sigma of 0.02
 C64-C59 \\sim C64-C61
 with sigma of 0.02
 C1AA-C101 \\sim C1AA-C99
 with sigma of 0.02
 C47-C41 \\sim C47-C45
 with sigma of 0.02
3. Restrained planarity
 P47, C91, C127, C305, C246, C215, C386
 with sigma of 0.05
 P47, C69, C7BA, C4BA, C5BA, C81, C85
 with sigma of 0.1
 P47, C2BA, C4AA, C7AA, C104, C103, C141
 with sigma of 0.1
 C55, C54, C53, C52, C56, C51, C49
 with sigma of 0.1
 C47, C46, C45, C44, C48, C43, C42, C41, S6
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
P47 \\sim C1BA \\sim C731 \\sim C670 \\sim C199 \\sim C181 \\sim C294 \\sim
C2BA \\sim C4AA \\sim C7AA \\sim C104 \\sim C103 \\sim C141 \\sim C69 \\sim
C7BA \\sim C4BA \\sim C5BA \\sim C81 \\sim C85 \\sim C91 \\sim C127 \\sim C215
\\sim C386 \\sim C246 \\sim C305: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C89 \\sim C90 \\sim C0BA \\sim C92 \\sim C93 \\sim C94 \\sim C95 \\sim C96:
within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
C49 \\sim C54 \\sim C53 \\sim C52 \\sim C51 \\sim C50 \\sim C56 \\sim C55:
within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
C57 \\sim C62 \\sim C61 \\sim C60 \\sim C59 \\sim C5AA \\sim C63 \\sim C64:
within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
C41 \\sim C46 \\sim C45 \\sim C44 \\sim C43 \\sim C42 \\sim C48 \\sim C47:
within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
C97 \\sim C98 \\sim C99 \\sim C100 \\sim C101 \\sim C102 \\sim C0AA \\sim C1AA:
within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
C65 \\sim C66 \\sim C67 \\sim C68 \\sim C6AA \\sim C70 \\sim C71 \\sim C72:
within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C33) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C36)
\\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C145) \\sim Ueq,
Uanis(C146) \\sim Ueq, Uanis(C147) \\sim Ueq, Uanis(C148) \\sim Ueq,
Uanis(C149) \\sim Ueq, Uanis(C150) \\sim Ueq, Uanis(C163) \\sim Ueq,
Uanis(C168) \\sim Ueq, Uanis(C167) \\sim Ueq, Uanis(C166) \\sim Ueq,
Uanis(C165) \\sim Ueq, Uanis(C164) \\sim Ueq, Uanis(C157) \\sim Ueq,
Uanis(C162) \\sim Ueq, Uanis(C161) \\sim Ueq, Uanis(C160) \\sim Ueq,
Uanis(C159) \\sim Ueq, Uanis(C158) \\sim Ueq, Uanis(C135) \\sim Ueq,
Uanis(C151) \\sim Ueq, Uanis(C156) \\sim Ueq, Uanis(C155) \\sim Ueq,
Uanis(C154) \\sim Ueq, Uanis(C153) \\sim Ueq, Uanis(C152) \\sim Ueq, Uanis(C9)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq,
Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C137) \\sim Ueq, Uanis(C138)
\\sim Ueq, Uanis(C139) \\sim Ueq, Uanis(C140) \\sim Ueq, Uanis(C2AA) \\sim Ueq,
Uanis(C142) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C27)
\\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30) \\sim Ueq,
Uanis(C113) \\sim Ueq, Uanis(C114) \\sim Ueq, Uanis(C115) \\sim Ueq,
Uanis(C116) \\sim Ueq, Uanis(C117) \\sim Ueq, Uanis(C118) \\sim Ueq,
Uanis(C105) \\sim Ueq, Uanis(C106) \\sim Ueq, Uanis(C107) \\sim Ueq,
Uanis(C108) \\sim Ueq, Uanis(C109) \\sim Ueq, Uanis(C110) \\sim Ueq,
Uanis(C121) \\sim Ueq, Uanis(C122) \\sim Ueq, Uanis(C123) \\sim Ueq,
Uanis(C124) \\sim Ueq, Uanis(C125) \\sim Ueq, Uanis(C126) \\sim Ueq, Uanis(C1)
\\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim Ueq,
Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C129) \\sim Ueq, Uanis(C130)
\\sim Ueq, Uanis(C131) \\sim Ueq, Uanis(C132) \\sim Ueq, Uanis(C133) \\sim Ueq,
Uanis(C134) \\sim Ueq, Uanis(C143) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18)
\\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq,
Uanis(C22) \\sim Ueq, Uanis(C3AA) \\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C83)
\\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C8AA) \\sim Ueq, Uanis(C86) \\sim Ueq,
Uanis(C15) \\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C73)
\\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C76) \\sim Ueq,
Uanis(C77) \\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C119) \\sim Ueq, Uanis(C80)
\\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C111) \\sim Ueq, Uanis(C9AA) \\sim Ueq,
Uanis(C87) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C66)
\\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C6AA) \\sim Ueq,
Uanis(C70) \\sim Ueq, Uanis(C136) \\sim Ueq, Uanis(C95) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C128) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C96) \\sim Ueq,
Uanis(C89) \\sim Ueq, Uanis(C90) \\sim Ueq, Uanis(C0BA) \\sim Ueq, Uanis(C92)
\\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(C94) \\sim Ueq, Uanis(C32) \\sim Ueq,
Uanis(C31) \\sim Ueq, Uanis(C112) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C88)
\\sim Ueq, Uanis(C144) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C24) \\sim Ueq,
Uanis(C0AA) \\sim Ueq, Uanis(C120) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C5AA)
\\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C61) \\sim Ueq,
Uanis(C62) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C51)
\\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C54) \\sim Ueq,
Uanis(C97) \\sim Ueq, Uanis(C98) \\sim Ueq, Uanis(C99) \\sim Ueq, Uanis(C100)
\\sim Ueq, Uanis(C101) \\sim Ueq, Uanis(C102) \\sim Ueq, Uanis(C41) \\sim Ueq,
Uanis(C42) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C45)
\\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C72) \\sim Ueq,
Uanis(C55) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C47)
\\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C1AA) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
5.a Me refined with riding coordinates:
 C7(H7A,H7B,H7C), C16(H16A,H16B,H16C), C39(H39A,H39B,H39C), C47(H47A,H47B,
 H47C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C63(H63A,H63B,H63C), C64(H64A,
 H64B,H64C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C79(H79A,H79B,H79C),
 C80(H80A,H80B,H80C), C96(H96A,H96B,H96C), C0AA(H0AA,H0AB,H0AC), C1AA(H1AA,H1AB,
 H1AC), C111(H11A,H11B,H11C), C112(H11D,H11E,H11F), C119(H11G,H11H,H11I),
 C136(H13D,H13E,H13F), C144(H14D,H14E,H14F)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C10(H10), C11(H11), C13(H13), C18(H18), C19(H19),
 C21(H21), C26(H26), C27(H27), C29(H29), C34(H34), C35(H35), C37(H37), C42(H42),
  C43(H43), C45(H45), C50(H50), C51(H51), C53(H53), C5AA(H5AA), C59(H59),
 C61(H61), C66(H66), C67(H67), C6AA(H6AA), C74(H74), C75(H75), C77(H77),
 C82(H82), C83(H83), C8AA(H8AA), C90(H90), C0BA(H0BA), C93(H93), C98(H98),
 C99(H99), C101(H101), C106(H106), C107(H107), C109(H109), C114(H114),
 C115(H115), C117(H117), C122(H122), C123(H123), C125(H125), C130(H130),
 C131(H131), C133(H133), C138(H138), C139(H139), C2AA(H2AA), C146(H146),
 C147(H147), C148(H148), C149(H149), C150(H150), C156(H156), C155(H155),
 C154(H154), C153(H153), C152(H152), C162(H162), C161(H161), C160(H160),
 C159(H159), C158(H158), C168(H168), C167(H167), C166(H166), C165(H165),
 C164(H164)
5.c Fitted hexagon refined as free rotating group:
 C1(C2,C3,C4,C5,C6), C9(C10,C11,C12,C13,C14), C17(C18,C19,C20,C21,C22),
 C25(C26,C27,C28,C29,C30), C33(C34,C35,C36,C37,C38), C41(C42,C43,C44,C45,C46),
 C49(C50,C51,C52,C53,C54), C57(C5AA,C59,C60,C61,C62), C65(C66,C67,C68,C6AA,C70),
  C73(C74,C75,C76,C77,C78), C3AA(C82,C83,C84,C8AA,C86), C89(C90,C0BA,C92,C93,
 C94), C97(C98,C99,C100,C101,C102), C105(C106,C107,C108,C109,C110), C113(C114,
 C115,C116,C117,C118), C121(C122,C123,C124,C125,C126), C129(C130,C131,C132,C133,
 C134), C137(C138,C139,C140,C2AA,C142), C145(C146,C147,C148,C149,C150),
 C151(C156,C155,C154,C153,C152), C157(C162,C161,C160,C159,C158), C163(C168,C167,
 C166,C165,C164), C1BA(C731,C670,C199,C181,C294), C91(C127,C215,C386,C246,C305),
  C2BA(C4AA,C7AA,C104,C103,C141), C7BA(C4BA,C5BA,C81,C85,C69)
5.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C15(H15A,H15B,H15C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C40(H40A,H40B,H40C), C87(H87A,
 H87B,H87C), C88(H88A,H88B,H88C), C95(H95A,H95B,H95C), C120(H12A,H12B,H12C),
 C9AA(H9AA,H9AB,H9AC), C128(H12D,H12E,H12F), C135(H13A,H13B,H13C), C143(H14A,
 H14B,H14C)
;
_shelx_res_checksum              84011
_shelx_hkl_checksum              99282
_shelx_fab_checksum              51665
_olex2_submission_special_instructions 'No special instructions were received'