Structural Transformation and Luminescence Response of Magic-Size Silver(I) Chalcogenide Clusters via Ligand-Exchange
Wu, Wei-Hong; Zeng, Hui-Min; Yu, Ze-Nan; Wang, Chao; Jiang, Zhan-Guo; Zhan, Cai-Hong; Chemical Communications  (2021) –; doi:10.1039/D1CC06007D

data_7129252
_publ_section_title
;
 Structural Transformation and Luminescence Response of Magic-Size
 Silver(I) Chalcogenide Clusters via Ligand-Exchange
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC06007D
_journal_year                    2021
_chemical_formula_moiety
'F6 Sb, C Cl2, C256 H125 Ag45 Br32 S6, C8 H5 Br'
_chemical_formula_sum            'C265 H130 Ag45 Br33 Cl2 F6 S6 Sb'
_chemical_formula_weight         11303.88
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-08-02
_audit_creation_method
;
Olex2 1.2
(compiled 2016.08.25 svn.r3337 for OlexSys, GUI svn.r5221)
;
_audit_update_record
;
2021-10-19 deposited with the CCDC.	2021-11-16 downloaded from the CCDC.
;
_cell_angle_alpha                77.983(2)
_cell_angle_beta                 87.539(2)
_cell_angle_gamma                63.769(2)
_cell_formula_units_Z            2
_cell_length_a                   18.8242(13)
_cell_length_b                   20.2627(13)
_cell_length_c                   40.783(3)
_cell_measurement_reflns_used    9891
_cell_measurement_temperature    160(2)
_cell_measurement_theta_max      23.33
_cell_measurement_theta_min      2.38
_cell_volume                     13626.7(17)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XH (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      160.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0636
_diffrn_reflns_av_unetI/netI     0.0992
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            104377
_diffrn_reflns_theta_full        23.53
_diffrn_reflns_theta_max         23.53
_diffrn_reflns_theta_min         1.15
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    8.202
_exptl_absorpt_correction_T_max  0.7450
_exptl_absorpt_correction_T_min  0.5913
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0934 before and 0.0573 after correction.
The Ratio of minimum to maximum transmission is 0.7937.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    2.755
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             10450
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         9.837
_refine_diff_density_min         -4.657
_refine_diff_density_rms         0.468
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3238
_refine_ls_number_reflns         40435
_refine_ls_number_restraints     2556
_refine_ls_restrained_S_all      0.994
_refine_ls_R_factor_all          0.1457
_refine_ls_R_factor_gt           0.0927
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1177P)^2^+775.0978P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2332
_refine_ls_wR_factor_ref         0.2692
_reflns_number_gt                25459
_reflns_number_total             40435
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d1cc06007d2.cif
_cod_data_source_block           b
_cod_original_cell_volume        13626.7(16)
_cod_database_code               7129252
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C93-Br25 \\sim C93-Br3
 with sigma of 0.02
3. Rigid bond restraints
 C1, C2, C3, C4, C5, C6, C7, C8, C11, C12, C13, C14, C15, C16, C17A, C18A,
 C17B, C18B, C1A, C1B, C1C, C1D, C1E, C1F, C1G, C1H, C2A, C2B, C2C, C2D, C2E,
 C2F, C2G, C2H, C3A, C3B, C3C, C3D, C3E, C3F, C3G, C3H, C4A, C4B, C4C, C4D, C4E,
  C4G, C4F, C4H, CP1, C02S, C02T, C02V, C02X, C02Y, CP4, C03A, C03B, C03D, C03E,
  C03G, C03H, C03I, C03J, C03K, C03L, C03M, C03N, C03O, C03P, C03Q, C03R, C03S,
 C03U, C03W, C03X, C03Y, C03Z, C04A, C04B, C04C, C04D, C04E, C04G, C04I, C04K,
 C04N, C04P, C04R, C04Y, C04Z, C05A, C05B, C05D, C05F, C05G, C05H, C05I, C05K,
 C05L, C05M, C05N, C05O, C05P, C05Q, C05R, C05U, C05V, C05W, C05Y, C05Z, C06A,
 C06D, C06E, C06F, C06G, C06H, C06L, C06M, C06N, C06R, C06S, C06U, C06X, C06Y,
 C06Z, C07A, C07B, C07C, C07D, C07E, C07F, C07G, C07H, C07K, C07M, C07O, C07P,
 C07R, C07S, C07U, C07V, C07Y, C07Z, C08A, C08C, C08D, C08F, C08G, C08I, C08K,
 C08L, C08N, C08O, C08P, C08S, C08T, C08V, C08W, C08Y, CP10, C09G, C09O, C09Q,
 C09T, C09W, CP18, CP30, C031, C31, C032, C033, C33, C034, C34, C35, C036, C36,
 C037, C038, C039, C39, C040, C041, C045, C046, C46, C048, C050, C50, C051,
 C052, C52, C053, C53, C55, C056, C57, C59, C060, C60, C61, C62, C063, C63,
 C064, C065, C65, C066, C67, C068, C68, C069, C69, C070, C072, C72, C073, C73,
 C74, C075, C076, C077, C78, C79, C81, C084, C85, C086, C087, C089, C89, C091,
 C91, C092, C093, C93, C094, C94, C095, C098, C99, C105, C106, C107, C110, C119,
  C120, C123, C127, C131, C132, C133, C140, C141, C142, C150, C151, C152, C154,
 C155, C158, C173, C180, C185, C0AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Br3, Br4, Br5, Br6, Br7, Br8, Br9, Br10, Br11, Br12, Br13, Br14, Br15, Br16,
 Br17, Br18, Br19, Br20, Br21, Br22, Br23, Br24, Br25, Br26, Br28, Br31, Br32,
 Br34, Br35, Br1, Br36, Br37, Br30, Br33, Br27, Br29, Br40
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C11
\\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17A \\sim C18A \\sim
C17B \\sim C18B \\sim C1A \\sim C1B \\sim C1C \\sim C1D \\sim C1E \\sim C1F
\\sim C1G \\sim C1H \\sim C2A \\sim C2B \\sim C2C \\sim C2D \\sim C2E \\sim C2F
\\sim C2G \\sim C2H \\sim C3A \\sim C3B \\sim C3C \\sim C3D \\sim C3E \\sim C3F
\\sim C3G \\sim C3H \\sim C4A \\sim C4B \\sim C4C \\sim C4D \\sim C4E \\sim C4G
\\sim C4F \\sim C4H \\sim CP1 \\sim C02S \\sim C02T \\sim C02V \\sim C02X \\sim
C02Y \\sim CP4 \\sim C03A \\sim C03B \\sim C03D \\sim C03E \\sim C03G \\sim
C03H \\sim C03I \\sim C03J \\sim C03K \\sim C03L \\sim C03M \\sim C03N \\sim
C03O \\sim C03P \\sim C03Q \\sim C03R \\sim C03S \\sim C03U \\sim C03W \\sim
C03X \\sim C03Y \\sim C03Z \\sim C04A \\sim C04B \\sim C04C \\sim C04D \\sim
C04E \\sim C04G \\sim C04I \\sim C04K \\sim C04N \\sim C04P \\sim C04R \\sim
C04Y \\sim C04Z \\sim C05A \\sim C05B \\sim C05D \\sim C05F \\sim C05G \\sim
C05H \\sim C05I \\sim C05K \\sim C05L \\sim C05M \\sim C05N \\sim C05O \\sim
C05P \\sim C05Q \\sim C05R \\sim C05U \\sim C05V \\sim C05W \\sim C05Y \\sim
C05Z \\sim C06A \\sim C06D \\sim C06E \\sim C06F \\sim C06G \\sim C06H \\sim
C06L \\sim C06M \\sim C06N \\sim C06R \\sim C06S \\sim C06U \\sim C06X \\sim
C06Y \\sim C06Z \\sim C07A \\sim C07B \\sim C07C \\sim C07D \\sim C07E \\sim
C07F \\sim C07G \\sim C07H \\sim C07K \\sim C07M \\sim C07O \\sim C07P \\sim
C07R \\sim C07S \\sim C07U \\sim C07V \\sim C07Y \\sim C07Z \\sim C08A \\sim
C08C \\sim C08D \\sim C08F \\sim C08G \\sim C08I \\sim C08K \\sim C08L \\sim
C08N \\sim C08O \\sim C08P \\sim C08S \\sim C08T \\sim C08V \\sim C08W \\sim
C08Y \\sim CP10 \\sim C09G \\sim C09O \\sim C09Q \\sim C09T \\sim C09W \\sim
CP18 \\sim CP30 \\sim C031 \\sim C31 \\sim C032 \\sim C033 \\sim C33 \\sim C034
\\sim C34 \\sim C35 \\sim C036 \\sim C36 \\sim C037 \\sim C038 \\sim C039 \\sim
C39 \\sim C040 \\sim C041 \\sim C045 \\sim C046 \\sim C46 \\sim C048 \\sim C050
\\sim C50 \\sim C051 \\sim C052 \\sim C52 \\sim C053 \\sim C53 \\sim C55 \\sim
C056 \\sim C57 \\sim C59 \\sim C060 \\sim C60 \\sim C61 \\sim C62 \\sim C063
\\sim C63 \\sim C064 \\sim C065 \\sim C65 \\sim C066 \\sim C67 \\sim C068 \\sim
C68 \\sim C069 \\sim C69 \\sim C070 \\sim C072 \\sim C72 \\sim C073 \\sim C73
\\sim C74 \\sim C075 \\sim C076 \\sim C077 \\sim C78 \\sim C79 \\sim C81 \\sim
C084 \\sim C85 \\sim C086 \\sim C087 \\sim C089 \\sim C89 \\sim C091 \\sim C91
\\sim C092 \\sim C093 \\sim C93 \\sim C094 \\sim C94 \\sim C095 \\sim C098
\\sim C99 \\sim C105 \\sim C106 \\sim C107 \\sim C110 \\sim C119 \\sim C120
\\sim C123 \\sim C127 \\sim C131 \\sim C132 \\sim C133 \\sim C140 \\sim C141
\\sim C142 \\sim C150 \\sim C151 \\sim C152 \\sim C154 \\sim C155 \\sim C158
\\sim C173 \\sim C180 \\sim C185 \\sim C0AA: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
Br3 \\sim Br4 \\sim Br5 \\sim Br6 \\sim Br7 \\sim Br8 \\sim Br9 \\sim Br10
\\sim Br11 \\sim Br12 \\sim Br13 \\sim Br14 \\sim Br15 \\sim Br16 \\sim Br17
\\sim Br18 \\sim Br19 \\sim Br20 \\sim Br21 \\sim Br22 \\sim Br23 \\sim Br24
\\sim Br25 \\sim Br26 \\sim Br28 \\sim Br31 \\sim Br32 \\sim Br34 \\sim Br35
\\sim Br1 \\sim Br36 \\sim Br37 \\sim Br30 \\sim Br33 \\sim Br27 \\sim Br29
\\sim Br40: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
5. Same fragment restrains
{C1, C2, C3, C4, C5, C6, C7, C8, Br1} sigma for 1-2: 0.02, 1-3: 0.04
{C11, C12, C13, C14, C15, C16, C17B, C18B, Br37} sigma for 1-2: 0.02, 1-3: 0.04
as
{C11, C12, C13, C14, C15, C16, C17A, C18A, Br36}
{C1, C2, C3, C4, C5, C6, C7, C8, Br1} sigma for 1-2: 0.02, 1-3: 0.04
as
{C1A, C1B, C1C, C1D, C1E, C1F, C1G, C1H, Br30}
{C1, C2, C3, C4, C5, C6, C7, C8, Br1} sigma for 1-2: 0.02, 1-3: 0.04
as
{C2A, C2B, C2C, C2D, C2E, C2F, C2G, C2H, Br33}
{C1, C2, C3, C4, C5, C6, C7, C8, Br1} sigma for 1-2: 0.02, 1-3: 0.04
as
{C3A, C3B, C3C, C3D, C3E, C3F, C3G, C3H, Br27}
{C1, C2, C3, C4, C5, C6, C7, C8, Br1} sigma for 1-2: 0.02, 1-3: 0.04
as
{C4A, C4B, C4C, C4D, C4E, C4G, C4F, C4H, Br29}
6. Others
 Sof(C17B)=Sof(C18B)=Sof(H18B)=Sof(Br37)=1-FVAR(1)
 Sof(C17A)=Sof(C18A)=Sof(H18A)=Sof(Br36)=FVAR(1)
 Fixed Sof: Br3(0.5) Br4(0.5) Br9(0.5) Br24(0.5) Br25(0.5) Br40(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C8(H8), C14(H14), C15(H15), C18A(H18A), C18B(H18B),
 C1D(H1D), C1E(H1E), C1F(H1F), C1H(H1H), C2D(H2D), C2E(H2E), C2F(H2F), C2H(H2H),
  C3D(H3D), C3E(H3E), C3F(H3F), C3H(H3H), C4D(H4D), C4E(H4E), C4G(H4G),
 C4H(H4H), C02T(H02T), C02X(H02X), C03A(H03A), C03E(H03E), C03M(H03M),
 C03O(H03O), C03P(H03P), C03W(H03W), C03X(H03X), C04D(H04D), C04G(H04G),
 C04K(H04K), C04N(H04N), C04R(H04R), C05A(H05A), C05B(H05B), C05D(H05D),
 C05F(H05F), C05H(H05H), C05I(H05I), C05K(H05K), C05O(H05O), C05V(H05V),
 C05Y(H05Y), C06A(H06A), C06D(H06D), C06E(H06E), C06F(H06F), C06G(H06G),
 C06M(H06M), C06N(H06N), C06S(H06S), C06U(H06U), C06Y(H06Y), C07A(H07A),
 C07B(H07B), C07D(H07D), C07E(H07E), C07K(H07K), C07O(H07O), C07Y(H07Y),
 C08C(H08C), C08I(H08I), C08K(H08K), C08N(H08N), C08P(H08P), C08S(H08S),
 C08T(H08T), C08Y(H08Y), C09G(H09G), C09O(H09O), C09T(H09T), C31(H31), C36(H36),
  C037(H037), C038(H038), C39(H39), C040(H040), C46(H46), C50(H50), C051(H051),
 C052(H052), C52(H52), C53(H53), C57(H57), C61(H61), C064(H064), C065(H065),
 C65(H65), C068(H068), C069(H069), C69(H69), C070(H070), C72(H72), C73(H73),
 C74(H74), C076(H076), C79(H79), C81(H81), C087(H087), C89(H89), C91(H91),
 C092(H092), C093(H093), C094(H094), C098(H098), C105(H105), C107(H107),
 C110(H110), C119(H119), C123(H123), C127(H127), C131(H131), C132(H132),
 C133(H133), C140(H140), C141(H141), C142(H142), C150(H150), C151(H151),
 C152(H152), C154(H154), C158(H158), C173(H173), C180(H180), C185(H185)
7.b :
 CP1(HP1)
;
_olex2_submission_special_instructions 'No special instructions were received'