Hypersensitive dual-function luminescence switching of a silver-chalcogenolate cluster-based metal-organic framework
Ren-Wu Huang; Yong-Sheng Wei; Xi-Yan Dong; Xiao-Hui Wu; Chen-Xia Du; Shuang-Quan Zang; Thomas C. W. Mak; Nature Chemistry 9 (2017) 689–697; doi:10.1038/nchem.2718

data_1551441
_publ_section_title
;
 Hypersensitive dual-function luminescence switching of a
 silver-chalcogenolate cluster-based metal-organic framework
;
_journal_name_full               'Nature Chemistry'
_journal_page_first              689
_journal_page_last               697
_journal_paper_doi               10.1038/nchem.2718
_journal_volume                  9
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C80 H104 Ag12 F12 N8 O8 S8, 2(C8 H10)'
_chemical_formula_sum            'C96 H124 Ag12 F12 N8 O8 S8'
_chemical_formula_weight         3296.94
_space_group_crystal_system      tetragonal
_space_group_IT_number           121
_space_group_name_Hall           'I -4 2'
_space_group_name_H-M_alt        'I -4 2 m'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   17.2529(3)
_cell_length_b                   17.2529(3)
_cell_length_c                   20.6795(7)
_cell_measurement_reflns_used    9101
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      30.0580
_cell_measurement_theta_min      2.8030
_cell_volume                     6155.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.7b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7b (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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_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    -27.00  16.00   0.25    2.00    --   -0.10 -38.00-120.00  172
  2  \w     17.00  88.00   0.25    2.00    --   -0.10  57.00 120.00  284
  3  \w    -13.00  13.00   0.25    2.00    --   -0.10  57.00 120.00  104
  4  \w    -84.00 -40.00   0.25    2.00    --   -0.10 -38.00-120.00  176
;
_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      -0.0321717000
_diffrn_orient_matrix_UB_12      -0.0013551000
_diffrn_orient_matrix_UB_13      -0.0212957000
_diffrn_orient_matrix_UB_21      0.0245746000
_diffrn_orient_matrix_UB_22      0.0097309000
_diffrn_orient_matrix_UB_23      -0.0262810000
_diffrn_orient_matrix_UB_31      0.0071248000
_diffrn_orient_matrix_UB_32      -0.0399372000
_diffrn_orient_matrix_UB_33      -0.0056365000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0297
_diffrn_reflns_av_unetI/netI     0.0185
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            18392
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.235
_diffrn_reflns_theta_min         2.361
_diffrn_source                   MM007HF-DW
_diffrn_source_type              'Microfocus Rotating Anode X-ray Source'
_exptl_absorpt_coefficient_mu    2.066
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.20006
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.779
_exptl_crystal_description       block
_exptl_crystal_F_000             3240
_exptl_crystal_size_max          0.134
_exptl_crystal_size_mid          0.101
_exptl_crystal_size_min          0.069
_refine_diff_density_max         1.783
_refine_diff_density_min         -0.683
_refine_diff_density_rms         0.157
_refine_ls_abs_structure_details
;
 Flack x determined using 1285 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.029(16)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.149
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     196
_refine_ls_number_reflns         2936
_refine_ls_number_restraints     61
_refine_ls_restrained_S_all      3.138
_refine_ls_R_factor_all          0.0446
_refine_ls_R_factor_gt           0.0442
_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^)+(0.0520P)^2^+91.7693P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1201
_refine_ls_wR_factor_ref         0.1204
_reflns_Friedel_coverage         0.816
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                2901
_reflns_number_total             2936
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2718-s24.cif
_cod_data_source_block           ag12bpy_m-xylene
_cod_database_code               1551441
_chemical_oxdiff_formula         'C80 H104 O8 N8 S8 Ag12'
_chemical_oxdiff_usercomment     st
_shelx_estimated_absorpt_t_max   0.871
_shelx_estimated_absorpt_t_min   0.769
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
 C18-C19 = C16-C15 = C16-C19
 1.39 with sigma of 0.01
 C22-C19 = C15-C21
 1.5 with sigma of 0.02
 F2-C9 = C9-F1
 1.34 with sigma of 0.01
 C4-C6 \\sim C4-C7 \\sim C4-C5
 with sigma of 0.01
 C16-C21 \\sim C21-C20 \\sim C18-C22 \\sim C22-C20
 with sigma of 0.01
 F1-C9 \\sim F2-C9
 with sigma of 0.01
3. Restrained planarity
 C20, C15, C19, C21, C22
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(F1) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(O1) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C4) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C7) \\sim
Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
5. Others
 Fixed Sof: Ag3(0.25) H2a(0.5) H2b(0.5) H2c(0.5) C5(0.5) H5a(0.5) H5b(0.5)
 H5c(0.5) C6(0.5) H6a(0.5) H6b(0.5) H6c(0.5) H7b(0.5) H7c(0.5) C15(0.25)
 C16(0.25) H16(0.25) C17(0.25) H17(0.25) C18(0.25) H18(0.25) C19(0.25)
 C20(0.25) H20(0.25) C21(0.25) H21a(0.25) H21b(0.25) H21c(0.25) C22(0.25)
 H22a(0.25) H22b(0.25) H22c(0.25)
 Fixed Uiso: C21(0.15)
6.a Riding coordinates:
 C21(H21a,H21b,H21c), C22(H22a,H22b,H22c)
6.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C13(H13), C14(H14), C16(H16), C17(H17), C18(H18), C20(H20)
6.c Fitted hexagon refined as free rotating group:
 C15(C16,C17,C18,C19,C20)
6.d Idealised Me refined as rotating group:
 C2(H2a,H2b,H2c), C3(H3a,H3b,H3c), C5(H5a,H5b,H5c), C6(H6a,H6b,H6c), C7(H7a,
 H7b,H7c)
Comments: The trifluoroacetate, the t-butyl mercaptan anions and the 
m-xylene molecules were found to be disordered. For the anions, 
only half of each was shown in the asymmetric unit, where the 
disordered atoms were not split but treated with strict 
geometrical and thermal vibrational restraints. The guest m-xylene 
was highly disordered due to the high lattice symmetry, geometry 
and rotation. Therefore, only the main part was assigned, which 
can be clearly observed from the difference Fourier map. However, 
because of the serious disorder, the molecule was modelled with 
fixed occupancy of 0.25. "AFIX 66" and "FLAT 0.1" were used 
to constrain the benzene ring. The methyl groups were also 
introduced with geometry restraints. One of the methyl carbon 
groups was refined with a fixed isotropic displacement 
parameter at 0.15 because the free refinement would give a high 
value of approximately 0.4.
;
_shelx_res_checksum              33263
_shelx_hkl_checksum              53474