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_1551426
_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 O6 S8, 1.2(C2 H3 N)'
_chemical_formula_sum            'C82.4 H107.6 Ag12 F12 N9.2 O6 S8'
_chemical_formula_weight         3101.89
_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                   17.38140(10)
_cell_length_b                   17.38140(10)
_cell_length_c                   20.0977(3)
_cell_measurement_reflns_used    12073
_cell_measurement_temperature    210.00(10)
_cell_measurement_theta_max      27.8460
_cell_measurement_theta_min      3.6700
_cell_volume                     6071.78(10)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41k (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41k (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41k (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      210.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.936
_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    -23.00  23.40   0.80    7.50    --  -15.18 -99.00-150.00   58
  2  \w    -24.00  17.60   0.80    7.50    --  -15.18 -99.00  60.00   52
  3  \w     10.00  86.00   0.80    7.50    --   18.07  37.00  60.00   95
  4  \w     50.00  89.20   0.80    7.50    --   18.07 178.00-150.00   49
  5  \w     35.00  90.20   0.80    7.50    --   18.07-178.00 -60.00   69
  6  \w     -1.00  85.40   0.80    7.50    --   18.07  19.00 150.00  108
  7  \w     23.00  64.60   0.80    7.50    --   18.07  57.00-180.00   52
  8  \w     36.00  63.20   0.80    7.50    --   18.07 178.00   0.00   34
  9  \w    -21.00  35.00   0.80    7.50    --   18.07 -57.00 -60.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0151335000
_diffrn_orient_matrix_UB_12      0.0087153000
_diffrn_orient_matrix_UB_13      0.0310512000
_diffrn_orient_matrix_UB_21      -0.0381652000
_diffrn_orient_matrix_UB_22      0.0063412000
_diffrn_orient_matrix_UB_23      0.0116767000
_diffrn_orient_matrix_UB_31      -0.0027703000
_diffrn_orient_matrix_UB_32      -0.0397336000
_diffrn_orient_matrix_UB_33      0.0086792000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0420
_diffrn_reflns_av_unetI/netI     0.0224
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.936
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            29297
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.936
_diffrn_reflns_theta_full        25.250
_diffrn_reflns_theta_max         27.100
_diffrn_reflns_theta_min         3.315
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.088
_exptl_absorpt_correction_T_max  0.764
_exptl_absorpt_correction_T_min  0.600
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41k (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    1.697
_exptl_crystal_description       block
_exptl_crystal_F_000             3029
_exptl_crystal_size_max          0.318
_exptl_crystal_size_mid          0.209
_exptl_crystal_size_min          0.153
_refine_diff_density_max         1.477
_refine_diff_density_min         -0.621
_refine_diff_density_rms         0.104
_refine_ls_abs_structure_details
;
 Flack x determined using 1273 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.047(17)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     200
_refine_ls_number_reflns         3293
_refine_ls_number_restraints     62
_refine_ls_restrained_S_all      1.113
_refine_ls_R_factor_all          0.0398
_refine_ls_R_factor_gt           0.0338
_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^)+(0.0563P)^2^+12.0974P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0927
_refine_ls_wR_factor_ref         0.0966
_reflns_Friedel_coverage         0.825
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.935
_reflns_number_gt                2992
_reflns_number_total             3293
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2718-s13.cif
_cod_data_source_block           ag12bpy_acetonitrile
_cod_original_cell_volume        6071.78(11)
_cod_original_formula_sum        'C82.40 H107.60 Ag12 F12 N9.20 O6 S8'
_cod_database_code               1551426
_chemical_oxdiff_formula         C80H104O8N8S8Ag12
_reflns_odcompleteness_completeness 99.56
_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
 C14-N2
 1.15 with sigma of 0.02
 C14-C15
 1.4 with sigma of 0.02
 O1-O2
 2.2 with sigma of 0.01
 C6-C4 = C5-C4
 1.53 with sigma of 0.01
 C7-C8
 1.54 with sigma of 0.01
 F1-C8 \\sim F2B-C8 \\sim F2-C8 \\sim F1B-C8
 with sigma of 0.01
 O2-C7 \\sim C7-O1
 with sigma of 0.01
3. Restrained planarity
 O2, O1, C7, C8
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C7) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F1B) \\sim Ueq, Uanis(F2) \\sim
Ueq, Uanis(F2B) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(O2) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C5) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(O1) = Uanis(O2)
5. Others
 Fixed Sof: Ag2(0.65) Ag2B(0.35) 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(0.25) F1(0.275) F1B(0.225) F2(0.55) F2B(0.45)
 N2(0.15) C14(0.15) C15(0.15) H15A(0.15) H15B(0.15) H15C(0.15)
6.a Riding coordinates:
 C15(H15A,H15B,H15C)
6.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C12(H12), C13(H13)
6.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C)
Comments: Several groups, including one of the silver ions, 
trifluoroacetate, one t-butyl mercaptan anion and guest acetonitrile 
molecules, were observed to be disordered. Among them, 
the t-butyl mercaptan anion was not split, but the ADP of C5 
was refined with "ISOR 0.003 0.006". The C-C bond lengths 
in one of the anions were restrained using "DFIX 1.53 0.01". 
For the trifluoroacetate, the fluorine and oxygen atoms 
were split over two equal parts. The geometry was restrained 
using the "SADI" or "DFIX" commands, whereas their thermal 
parameters were restrained using "ISOR 0.01 0.02". In addition, 
the C-CO2 group was restrained in the same plane with
"FLAT". A large electron peak was detected close to Ag2. 
The disordered model obtained by splitting the Ag2 over two 
sites with fixed occupancy ratio of 0.65:0.35 was applied, 
resulting in a better result. The guest acetonitrile was seriously 
disordered due to the high lattice symmetry and the small size 
of the molecule compared with the cavity. Thus, only the 
main part was assigned, as can be observed from the 
difference Fourier map. &#x00A1;&#x00B0;DFIX&#x00A1;&#x00B1; restrained the C-N triple 
bond length to be 1.15 angstroms, and &#x00A1;&#x00B0;DFIX 1.4&#x00A1;&#x00B1; 
restrained the C-C length, with only the isotropic thermal 
parameters being refined for the three atoms.
;
_shelx_res_checksum              17746
_shelx_hkl_checksum              73898