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_1551423
_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, 4.4(O2)'
_chemical_formula_sum            'C80 H104 Ag12 F12 N8 O16.8 S8'
_chemical_formula_weight         3225.43
_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                   17.2768(2)
_cell_length_b                   17.2768(2)
_cell_length_c                   20.4482(3)
_cell_measurement_reflns_used    6068
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      72.4190
_cell_measurement_theta_min      3.3410
_cell_volume                     6103.54(13)
_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      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.980
_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    -32.00  82.00   0.50    3.00    --   45.50 -57.00  90.00  228
  2  \w     64.00 104.00   0.50    9.00    --  100.10  45.00 120.00   80
  3  \w     76.00 178.00   0.50    9.00    --  100.10  61.00  30.00  204
  4  \w    147.00 186.00   0.50    9.00    --  100.10  45.00 120.00   78
  5  \w    111.00 184.00   0.50    9.00    --  100.10  61.00 -90.00  146
  6  \w     68.00  98.00   0.50    9.00    --  100.10  61.00 -90.00   60
;
_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      0.0024581000
_diffrn_orient_matrix_UB_12      -0.0044145000
_diffrn_orient_matrix_UB_13      0.0751437000
_diffrn_orient_matrix_UB_21      0.0890380000
_diffrn_orient_matrix_UB_22      -0.0028663000
_diffrn_orient_matrix_UB_23      -0.0021714000
_diffrn_orient_matrix_UB_31      0.0029870000
_diffrn_orient_matrix_UB_32      0.0891503000
_diffrn_orient_matrix_UB_33      0.0036789000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0351
_diffrn_reflns_av_unetI/netI     0.0412
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            7697
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        66.750
_diffrn_reflns_theta_max         72.613
_diffrn_reflns_theta_min         3.349
_diffrn_source                   MM007HF-DW
_diffrn_source_type              'Microfocus Rotating Anode X-ray Source'
_exptl_absorpt_coefficient_mu    16.970
_exptl_absorpt_correction_T_max  0.449
_exptl_absorpt_correction_T_min  0.095
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7b (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.755
_exptl_crystal_description       block
_exptl_crystal_F_000             3149
_exptl_crystal_size_max          0.182
_exptl_crystal_size_mid          0.131
_exptl_crystal_size_min          0.061
_refine_diff_density_max         0.862
_refine_diff_density_min         -0.765
_refine_diff_density_rms         0.160
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.02(3)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.210
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     184
_refine_ls_number_reflns         2904
_refine_ls_number_restraints     41
_refine_ls_restrained_S_all      1.217
_refine_ls_R_factor_all          0.0448
_refine_ls_R_factor_gt           0.0444
_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^)+(0.0427P)^2^+58.6709P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1177
_refine_ls_wR_factor_ref         0.1179
_reflns_Friedel_coverage         0.826
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                2867
_reflns_number_total             2904
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2718-s10.cif
_cod_data_source_block           ag12bpy_o2_100k
_cod_original_cell_volume        6103.54(17)
_cod_original_formula_sum        'C80 H104 Ag12 F12 N8 O16.80 S8'
_cod_database_code               1551423
_chemical_oxdiff_formula         'C80 H104 O8 N8 S8 Ag12 F12'
_chemical_oxdiff_usercomment     st
_reflns_odcompleteness_completeness 99.75
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.98(3) 0.02(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C3-C1 = C2-C1 = C5-C4 = C6-C4
 1.53 with sigma of 0.02
 F1-C8 \\sim F2-C8
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C6) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(F2) \\sim
Ueq, Uanis(F1) \\sim Ueq, Uanis(C8) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5. Others
 Fixed Sof: Ag3(0.25) H3A(0.5) H3B(0.5) H3C(0.5) H5A(0.5) H5B(0.5) H5C(0.5)
 O2(0.25) O3(0.25) O4(0.3) O5(0.3)
6.a Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C12(H12), C13(H13)
6.b 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 and t-butyl mercaptan anions were observed 
to be disordered, however, the related atoms were not split but rather 
had strong restraints applied. The geometry and ADPs of the trifluoroacetate 
were restrained using "SADI 0.01" and "ISOR 0.01", respectively. 
For the t-butyl mercaptan, ADP restraints "ISOR 0.01 0.02" were 
applied to C4, C5 and C6. The C-C distance was restrained by "DFIX 1.53 0.01". 
The determination of positions of molecular oxygen was done by comparing the 
difference Fourier maps of 100 K structure of evacuated Ag12bpy and Ag12bpy_O2
based on the same single crystal. The assigned oxygen molecules were
kept isotropic with fixed occupancies (0.25 and 0.3 for O2-O3 and
O4-O5, respectively). The structure is slightly twinned. 
So "TWIN" command was used with a refined BASF parameter of 0.018.
;
_shelx_res_checksum              36217
_shelx_hkl_checksum              89907