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_1551440
_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                   17.2348(3)
_cell_length_b                   17.2348(3)
_cell_length_c                   20.8923(9)
_cell_measurement_reflns_used    6006
_cell_measurement_temperature    100.3(5)
_cell_measurement_theta_max      27.7650
_cell_measurement_theta_min      3.6730
_cell_volume                     6205.8(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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      100.3(5)
_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 0.995
_diffrn_measurement_details
;
  1 omega  -22.00   23.60   0.8000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.1755  -99.0000  -90.0000 57

  2 omega  -25.00    2.20   0.8000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.1755  -99.0000  150.0000 34

  3 omega   58.00   89.20   0.8000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661 -178.0000  150.0000 39

  4 omega  -40.00   68.00   0.8000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661    0.0000   90.0000 135

  5 omega   -7.00   45.00   0.8000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661  -99.0000   30.0000 65

  6 omega   48.00   75.20   0.8000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661  178.0000  -90.0000 34
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0321114000
_diffrn_orient_matrix_UB_12      0.0173282000
_diffrn_orient_matrix_UB_13      0.0156800000
_diffrn_orient_matrix_UB_21      -0.0237347000
_diffrn_orient_matrix_UB_22      -0.0082266000
_diffrn_orient_matrix_UB_23      -0.0268911000
_diffrn_orient_matrix_UB_31      -0.0099672000
_diffrn_orient_matrix_UB_32      -0.0364151000
_diffrn_orient_matrix_UB_33      0.0135429000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0512
_diffrn_reflns_av_unetI/netI     0.0387
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            17698
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        25.250
_diffrn_reflns_theta_max         26.384
_diffrn_reflns_theta_min         3.343
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.049
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85237
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    1.764
_exptl_crystal_description       block
_exptl_crystal_F_000             3240
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.18
_refine_diff_density_max         1.335
_refine_diff_density_min         -0.756
_refine_diff_density_rms         0.122
_refine_ls_abs_structure_details
;
 Flack x determined using 1064 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.01(3)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     201
_refine_ls_number_reflns         3295
_refine_ls_number_restraints     121
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0725
_refine_ls_R_factor_gt           0.0559
_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^)+(0.0539P)^2^+56.7557P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1293
_refine_ls_wR_factor_ref         0.1387
_reflns_Friedel_coverage         0.807
_reflns_Friedel_fraction_full    0.974
_reflns_Friedel_fraction_max     0.976
_reflns_number_gt                2730
_reflns_number_total             3295
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2718-s23.cif
_cod_data_source_block           ag12bpy_o-xylene
_cod_database_code               1551440
_chemical_oxdiff_formula         C1H1O1N1S1Ag1
_reflns_odcompleteness_completeness 99.59
_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
 C4-C5 = C4-C6 = C4-C7
 1.54 with sigma of 0.01
 C8-C9
 1.54 with sigma of 0.02
 C22-C15 = C21-C16
 1.5 with sigma of 0.02
 C9-F1 \\sim C9-F1B \\sim C9-F2 \\sim C9-F2B
 with sigma of 0.01
 C5-C6 \\sim C6-C7 \\sim C5-C7
 with sigma of 0.01
 O1-C8 \\sim C8-O2
 with sigma of 0.01
 C20-C22 \\sim C22-C16 \\sim C15-C21 \\sim C21-C17
 with sigma of 0.01
3. Restrained planarity
 C15, C16, C17, C20, C21, C22
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C8 \\sim O1 \\sim O2: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02
C4 \\sim C6 \\sim C7: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02
Uanis(F2) \\sim Ueq, Uanis(F2B) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F1B)
\\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C9) \\sim Ueq,
Uanis(O1) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(Ag3B)
\\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms
of 0.02
Uanis(F2) = Uanis(F2B)
Uanis(O1) = Uanis(O2)
Uanis(C6) = Uanis(C7)
Uiso(C19) = Uiso(C16) = Uiso(C15) = Uiso(C17) = Uiso(C22) = Uiso(C20) =
Uiso(C21) = Uiso(C18)
5. Others
 Fixed Sof: Ag3(0.215) Ag3B(0.035) H3A(0.5) H3B(0.5) H3C(0.5) H5A(0.5)
 H5B(0.5) H5C(0.5) C6(0.5) H6A(0.5) H6B(0.5) H6C(0.5) C7(0.5) H7A(0.5) H7B(0.5)
 H7C(0.5) O1(0.5) O2(0.5) F1(0.25) F1B(0.25) F2(0.5) F2B(0.5) C15(0.25)
 C16(0.25) C17(0.25) H17(0.25) C18(0.25) H18(0.25) C19(0.25) H19(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)
6.a Riding coordinates:
 C7(H7A,H7B,H7C), 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), C17(H17), C18(H18), C19(H19), 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)
Comments: Several groups in this structure involving silver atoms, 
trifluoroacetate, t-butyl mercaptan anions, and lattice o-xylene 
molecules were disordered. They were treated with different 
strategies according to the electron density distribution. For the 
cluster framework, relatively large residual densities were observed 
around the central Ag-Ag part. The related Ag was split over two 
sites with fixed occupancies of 0.43:0.07 and restrained ADP for 
the minor part with "ISOR 0.01 0.02", which gave rise to 
better refinement results. With this model, the entire central 
Ag-Ag was disordered over four parts. For the trifluoroacetate, 
two equal parts were assigned to model the disorder. The C-F 
and C-O distances were restrained to be the same with "SADI 0.01", 
respectively. The C-C bond length was restrained to be 1.54 
angstrom with "DFIX 1.54". Anisotropic displacement parameters 
were restrained with "ISOR 0.01 0.02" for all atoms in the 
trifluoroacetate apart from C8. F2 and F2B, as well as O1 and O2, 
were constrained to have the same ADPs, because their equivalent 
positions were very close to each other. For the two t-butyl 
mercaptan anions, only half of the anions were shown in the 
asymmetric unit. In the anion with S2, the three terminal carbon 
atoms with 0.5 occupancy were assigned, whereas in the 
anion with S1, only one full and one half terminal carbon atoms 
were assigned. The C-C distances in the t-butyl group were 
restrained using "DFIX 1.54 0.01", and the ADPs of the carbon 
atoms were also restrained using "ISOR 0.01 0.02" or 
"SIMU 0.01 0.02". Due to the close equivalent positions, the ADPs 
of C6 and C7 were constrained to also be the same. The lattice o-xylene 
molecules were heavily disordered because of the high lattice symmetry, 
the geometry of the guest, and the relatively large volume of the pore 
compared with the guest. More than one site for the o-xylene was 
observed from the difference Fourier map; however, only the main part 
was assigned with strong geometry restraints using "DFIX", 
"SADI 0.01" and "FLAT". All the atoms in this model were constrained 
to have the same isotropic displacement parameters. 
;
_shelx_res_checksum              24449
_shelx_hkl_checksum              60774