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_1551425
_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(C H Cl3)'
_chemical_formula_sum            'C84 H108 Ag12 Cl12 F12 N8 O8 S8'
_chemical_formula_weight         3562.10
_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                   17.1887(3)
_cell_length_b                   17.1887(3)
_cell_length_c                   20.4219(19)
_cell_measurement_reflns_used    1745
_cell_measurement_temperature    100.00(5)
_cell_measurement_theta_max      27.1300
_cell_measurement_theta_min      3.7260
_cell_volume                     6033.7(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_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_temperature      100.00(5)
_diffrn_detector_area_resol_mean 16.2312
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.878
_diffrn_measurement_details
;
  1 omega  -52.00   40.00   1.0000   75.0000
omega____ theta____ kappa____ phi______ frames
    -       19.6323  -19.0000   90.0000 92

  2 omega   60.00   86.00   1.0000   75.0000
omega____ theta____ kappa____ phi______ frames
    -       19.6323  178.0000   60.0000 26
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0271675000
_diffrn_orient_matrix_UB_12      0.0114015000
_diffrn_orient_matrix_UB_13      -0.0243779000
_diffrn_orient_matrix_UB_21      -0.0171095000
_diffrn_orient_matrix_UB_22      -0.0375087000
_diffrn_orient_matrix_UB_23      0.0010956000
_diffrn_orient_matrix_UB_31      -0.0259524000
_diffrn_orient_matrix_UB_32      0.0128426000
_diffrn_orient_matrix_UB_33      0.0247087000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0465
_diffrn_reflns_av_unetI/netI     0.0765
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.878
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            7208
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.831
_diffrn_reflns_theta_full        25.250
_diffrn_reflns_theta_max         29.162
_diffrn_reflns_theta_min         2.831
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.373
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.96296
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
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    1.961
_exptl_crystal_description       block
_exptl_crystal_F_000             3472
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.940
_refine_diff_density_min         -0.738
_refine_diff_density_rms         0.137
_refine_ls_abs_structure_details
;
 Flack x determined using 948 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.05(4)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     233
_refine_ls_number_reflns         3542
_refine_ls_number_restraints     101
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0827
_refine_ls_R_factor_gt           0.0526
_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^)+(0.0528P)^2^+13.2670P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1107
_refine_ls_wR_factor_ref         0.1251
_reflns_Friedel_coverage         0.735
_reflns_Friedel_fraction_full    0.967
_reflns_Friedel_fraction_max     0.774
_reflns_number_gt                2659
_reflns_number_total             3542
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2718-s12.cif
_cod_data_source_block           ag12bpy_chloroform
_cod_database_code               1551425
_chemical_oxdiff_formula         C1H1O1N1S1Ag1
_shelx_estimated_absorpt_t_max   0.833
_shelx_estimated_absorpt_t_min   0.717
_reflns_odcompleteness_completeness 99.72
_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
 C2-C1 = C3-C1
 1.53 with sigma of 0.01
 C8-F3
 1.35 with sigma of 0.02
 O1-C7 = C7-O2
 1.21 with sigma of 0.01
 C7-C8
 1.54 with sigma of 0.01
 O1-C8 = C8-O2
 2.4 with sigma of 0.01
 C14-Cl1 \\sim C14-Cl2 \\sim C14-Cl3
 with sigma of 0.02
 F1-F2 \\sim F2-F3 \\sim F1-F3
 with sigma of 0.02
 F1-C8 \\sim F3-C8 \\sim F2-C8
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(O1) \\sim Ueq, Uanis(O2) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C6) \\sim
Ueq, Uanis(C5) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C14)
\\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F3) \\sim Ueq,
Uanis(Cl1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl2) = Uanis(Cl3)
4. Others
 Fixed Sof: Ag2(0.5) Ag2B(0.5) 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) C7(0.5) C8(0.5) F1(0.5) F2(0.5) F3(0.5)
 Cl1(0.5) Cl2(0.5) Cl3(0.5) C14(0.5) H14(0.5)
5.a Ternary CH refined with riding coordinates:
 C14(H14)
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 silver atom (Ag2) was found to be disordered over 
two sites with the same occupancy of 0.5. The trifluoroacetate 
anion was also disordered; however, only the two majorities 
related by symmetry were assigned for clarity, and their 
occupancies were each set to 0.5. The geometry was constrained 
with similar C-F bonds and C-O bonds using "SADI 0.01" 
and "SADI", respectively. The "PART -1" command was 
applied to suppress the symmetry according to the chemistry. 
The same disorder was also exhibited by chloroform. It 
was treated the same manner as the trifluoroacetate. 
The geometry of the groups involved in the disorder 
was restrained using "DFIX" or "SADI" based on the 
chemistry, and their ADPs were restrained with strict 
"ISOR" commands and constrained with "EADP" for 
the atoms very close to each other.
;
_shelx_res_checksum              33146
_shelx_hkl_checksum              3906