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_1551433
_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, 4(C4 H8 O2)'
_chemical_formula_sum            'C96 H136 Ag12 F12 N8 O16 S8'
_chemical_formula_weight         3437.04
_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   geom
_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                   17.1785(2)
_cell_length_b                   17.1785(2)
_cell_length_c                   20.8487(5)
_cell_measurement_reflns_used    18363
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      32.8170
_cell_measurement_theta_min      2.5890
_cell_volume                     6152.47(18)
_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 0.997
_diffrn_measured_fraction_theta_max 0.998
_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    -16.00  54.20   0.30    3.00    --    7.30  38.00-120.00  234
  2  \w    -33.00  12.00   0.30    3.00    --   -7.10 -82.00  60.00  150
  3  \w    -25.00  23.00   0.30    3.00    --   -7.10 -77.00-150.00  160
  4  \w    -75.00  22.50   0.30    3.00    --    7.30 -57.00  90.00  325
;
_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      -0.0214515000
_diffrn_orient_matrix_UB_12      -0.0011282000
_diffrn_orient_matrix_UB_13      -0.0290373000
_diffrn_orient_matrix_UB_21      -0.0311896000
_diffrn_orient_matrix_UB_22      -0.0186060000
_diffrn_orient_matrix_UB_23      0.0161645000
_diffrn_orient_matrix_UB_31      -0.0164738000
_diffrn_orient_matrix_UB_32      0.0368589000
_diffrn_orient_matrix_UB_33      0.0072500000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0324
_diffrn_reflns_av_unetI/netI     0.0170
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            25528
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.250
_diffrn_reflns_theta_min         2.575
_diffrn_source                   MM007HF-DW
_diffrn_source_type              'Microfocus Rotating Anode X-ray Source'
_exptl_absorpt_coefficient_mu    2.076
_exptl_absorpt_correction_T_max  0.885
_exptl_absorpt_correction_T_min  0.752
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7b (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
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    1.855
_exptl_crystal_description       plate
_exptl_crystal_F_000             3392
_exptl_crystal_size_max          0.197
_exptl_crystal_size_mid          0.131
_exptl_crystal_size_min          0.073
_refine_diff_density_max         1.419
_refine_diff_density_min         -0.635
_refine_diff_density_rms         0.126
_refine_ls_abs_structure_details
;
 Flack x determined using 1301 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.030(12)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.251
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     212
_refine_ls_number_reflns         2927
_refine_ls_number_restraints     76
_refine_ls_restrained_S_all      1.272
_refine_ls_R_factor_all          0.0360
_refine_ls_R_factor_gt           0.0359
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0204P)^2^+77.5666P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0925
_refine_ls_wR_factor_ref         0.0925
_reflns_Friedel_coverage         0.811
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                2919
_reflns_number_total             2927
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2718-s16.cif
_cod_data_source_block           ag12bpy_dioxane
_cod_original_cell_volume        6152.4(2)
_cod_database_code               1551433
_chemical_oxdiff_formula         'C80 H104 O8 N8 S8 Ag12'
_chemical_oxdiff_usercomment     st
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O1-C7 \\sim C7-O2
 with sigma of 0.01
 F1B-F2B_$1 \\sim F2B_$1-F2B \\sim F1B-F2B
 with sigma of 0.01
 C8-F1 \\sim C8-F2_$1 \\sim C8-F1B \\sim C8-F2B_$1
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(O1) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8) \\sim
Ueq, Uanis(F2B) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F1B) \\sim Ueq, Uanis(F1)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(O1) = Uanis(O2)
4. Others
 Fixed Sof: Ag3(0.25) H3A(0.5) H3B(0.5) H3C(0.5) H6A(0.5) H6B(0.5) H6C(0.5)
 O1(0.5) O2(0.5) F1(0.35) F1B(0.15) F2(0.7) F2B(0.3)
5.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B)
5.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C12(H12), C13(H13)
5.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C)
Comments: The trifluoroacetate, the t-butyl mercaptan anions were 
disordered. For the trifluoroacetate, the acetate group was split 
over two equal parts with "PART -1" to suppress the symmetry. 
For the trifluoro group, two unequal parts were assigned 
with fixed occupancies (0.7:0.3) according to the difference 
electron maps. Restraints such as "SADI 0.01" and 
"ISOR 0.01 0.02" were applied for the geometry and ADPs, 
respectively, to make the anion chemically and 
crystallographically reasonable. In addition, "EADP" was 
used to constrain O1 and O2 because their equivalent positions 
were very close to each other. For the t-butyl mercaptan, 
the ADPs of C4, C5 and C6 were strictly restrained to be 
approximately isotropic by "ISOR 0.005 0.01".
;
_shelx_res_checksum              58726
_shelx_hkl_checksum              29995