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_1551429
_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_formula_moiety         '2(C24 H36 Ag6 F9 N3 O6 S3), C2 H3 N'
_chemical_formula_sum            'C50 H75 Ag12 F18 N7 O12 S6'
_chemical_formula_weight         2794.97
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_cell_angle_alpha                91.3274(19)
_cell_angle_beta                 95.0852(19)
_cell_angle_gamma                94.9884(19)
_cell_formula_units_Z            2
_cell_length_a                   15.4518(4)
_cell_length_b                   15.8621(4)
_cell_length_c                   17.9312(4)
_cell_measurement_reflns_used    17607
_cell_measurement_temperature    279.99(10)
_cell_measurement_theta_max      26.3010
_cell_measurement_theta_min      2.7720
_cell_volume                     4358.91(19)
_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      air
_diffrn_ambient_temperature      279.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -17.00  89.00   0.50    2.00    --    2.80  38.00  30.00  212
  2  \w    -22.00  85.00   0.50    2.00    --    2.80  19.00 150.00  214
  3  \w    -33.00  30.00   0.50    2.00    --   -2.70 -82.00  30.00  126
  4  \w    -90.00  17.00   0.50    2.00    --   -2.70 -38.00 150.00  214
;
_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      -0.0058423000
_diffrn_orient_matrix_UB_12      0.0014302000
_diffrn_orient_matrix_UB_13      -0.0396197000
_diffrn_orient_matrix_UB_21      -0.0001104000
_diffrn_orient_matrix_UB_22      0.0446757000
_diffrn_orient_matrix_UB_23      0.0026459000
_diffrn_orient_matrix_UB_31      0.0459001000
_diffrn_orient_matrix_UB_32      0.0043359000
_diffrn_orient_matrix_UB_33      -0.0013910000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0217
_diffrn_reflns_av_unetI/netI     0.0226
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            59318
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.250
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         2.534
_diffrn_source                   MM007HF-DW
_diffrn_source_type              'Microfocus Rotating Anode X-ray Source'
_exptl_absorpt_coefficient_mu    2.863
_exptl_absorpt_correction_T_max  0.656
_exptl_absorpt_correction_T_min  0.577
_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    2.129
_exptl_crystal_description       block
_exptl_crystal_F_000             2684
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.218
_exptl_crystal_size_min          0.196
_refine_diff_density_max         1.264
_refine_diff_density_min         -0.691
_refine_diff_density_rms         0.080
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1172
_refine_ls_number_reflns         17770
_refine_ls_number_restraints     277
_refine_ls_restrained_S_all      1.101
_refine_ls_R_factor_all          0.0447
_refine_ls_R_factor_gt           0.0330
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0438P)^2^+5.1700P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0859
_refine_ls_wR_factor_ref         0.0925
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                14152
_reflns_number_total             17770
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2718-s6.cif
_cod_data_source_block           ag12-280k
_cod_original_cell_volume        4358.92(18)
_cod_database_code               1551429
_chemical_oxdiff_formula         'C50 H75 Ag12 F18 N7 O12 S6'
_chemical_oxdiff_usercomment     st
_shelx_estimated_absorpt_t_max   0.604
_shelx_estimated_absorpt_t_min   0.547
_reflns_odcompleteness_completeness 99.66
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N6-C47
 1.1 with sigma of 0.01
 N6-C48
 2.57 with sigma of 0.01
 N6-C48
 2.55 with sigma of 0.02
 C48-C47
 1.45 with sigma of 0.01
 C30-F7A \\sim C30-F7B \\sim C30-F7C \\sim C30-F8A \\sim C30-F8B \\sim C30-F8C
\\sim C30-F9A \\sim C30-F9B
 \\sim C30-F9C
 with sigma of 0.01
 C34-F13 \\sim C34-F13B \\sim C34-F14 \\sim C34-F14B \\sim C34-F15 \\sim
C34-F15B
 with sigma of 0.01
 F18B-F16B \\sim F18B-F17B \\sim F16B-F17B
 with sigma of 0.02
 C36-F16 \\sim C36-F17 \\sim C36-F18 \\sim C36B-F16B \\sim C36B-F17B \\sim
C36B-F18B
 with sigma of 0.01
 C35-O12 \\sim O12-C35B
 with sigma of 0.01
 S2B-C5 \\sim C5-S2
 with sigma of 0.01
3. Rigid bond restraints
 Ag10, S4
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C29, C30
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O5, C29
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C29, O6
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
Uanis(F3) \\sim Ueq, Uanis(O11) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C52)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C30) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(F13)
\\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(C35B) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C36B) \\sim Ueq, Uanis(C36)
\\sim Ueq, Uanis(F16B) \\sim Ueq, Uanis(F18) \\sim Ueq, Uanis(F18B) \\sim Ueq,
Uanis(F16) \\sim Ueq, Uanis(F17B) \\sim Ueq, Uanis(C18B) \\sim Ueq, Uanis(C20B)
\\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C17B) \\sim Ueq, Uanis(C18) \\sim Ueq,
Uanis(C20) \\sim Ueq, Uanis(O5) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(F13B)
\\sim Ueq, Uanis(F15B) \\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F15) \\sim Ueq,
Uanis(F14B) \\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(C29)
\\sim Ueq, Uanis(F5) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(F17) = Uanis(F17B)
Uanis(C36) = Uanis(C36B)
Uanis(F16) = Uanis(F16B)
5. Others
 Fixed Sof: Ag3(0.5) Ag3B(0.5) Ag5B(0.5) Ag5(0.5) S1(0.5) S1B(0.5) S2(0.5)
 S2B(0.5) F7A(0.33333) F8A(0.33333) F9A(0.33333) F7B(0.33333) F8B(0.33333)
 F9B(0.33333) F7C(0.33333) F8C(0.33333) F9C(0.33333) Ag7(0.5) Ag7B(0.5)
 Ag8(0.5) Ag8B(0.5) Ag9(0.5) Ag9B(0.5) Ag11(0.5) Ag12(0.5) Ag13(0.5) Ag14(0.5)
 C17(0.5) C17B(0.5) C18(0.5) H18A(0.5) H18B(0.5) H18C(0.5) C18B(0.5) H18D(0.5)
 H18E(0.5) H18F(0.5) C19(0.5) H19A(0.5) H19B(0.5) H19C(0.5) C19B(0.5) H19D(0.5)
 H19E(0.5) H19F(0.5) C20(0.5) H20A(0.5) H20B(0.5) H20C(0.5) C20B(0.5) H20D(0.5)
 H20E(0.5) H20F(0.5) F13(0.5) F14(0.5) F15(0.5) F13B(0.5) F14B(0.5) F15B(0.5)
 O11(0.5) O11B(0.5) C35(0.5) C35B(0.5) C36(0.5) C36B(0.5) F16(0.5) F17(0.5)
 F18(0.5) F16B(0.5) F17B(0.5) F18B(0.5) N6(0.5) C47(0.5) C48(0.5) H48A(0.5)
 H48B(0.5) H48C(0.5) N7(0.5) C49(0.5) C50(0.5) H50A(0.5) H50B(0.5) H50C(0.5)
 Fixed Uiso: N6(0.14) C47(0.14) C48(0.18)
6.a Riding coordinates:
 C48(H48A,H48B,H48C)
6.b Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C7(H7A,
 H7B,H7C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,
 H12B,H12C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C42(H42A,H42B,H42C),
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,
 H18C), C18B(H18D,H18E,H18F), C19(H19A,H19B,H19C), C19B(H19D,H19E,H19F),
 C20(H20A,H20B,H20C), C20B(H20D,H20E,H20F), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C), C50(H50A,
 H50B,H50C), C52(H52A,H52B,H52C)
Comments: The two cluster halves involved disorder. The related Ag and S atoms 
were split over two sites with fixed occupancy of 0.5. All trifluoroacetate
anions were also found to exhibit disorder. Among them, three anions were 
treated without splitting but with relatively "hard" atomic displacement 
parameter (ADP) restraints, such as "ISOR 0.005 0.01" or "ISOR 0.01 0.02".
In another two anions, some atoms were split over two or three sites 
according to the observed electron distribution. The geometry and ADP 
were also strictly restrained with the "DFIX", "SADI, "ISOR" or "DELU" 
commands. The entire remaining anion was split over two sites. 
The C-F bonds, the adjacent F-F distances, and the C-O distances
were restrained to have similar lengths using the "SADI 0.01" or
"SADI" commands. The ADPs were restrained with "ISOR 0.005 0.01" 
or "ISOR 0.01 0.02". The very close carbon pairs and fluorine 
pairs were also constrained to have the same ADPs by "EADP". The 
disorder of the t-butyl mercaptan anions was reflected in the bad 
anisotropic thermal parameters. These anions were restrained with 
hard "ISOR" commands if necessary. Only one t-butyl group was split 
into two parts with 0.5 occupancy due to rotation along the C-S bond. 
The ADPs therein were strongly restrained with "ISOR 0.005 0.01". S1 
and S2 were also split due to the Hirshfeld rigid body test warning. 
For the acetonitrile molecules, two were fixed to have 0.5 occupancy 
because of symmetry requirements. "PART -1" was applied to suppress 
the symmetry for consistency with chemically reasonable modelling. 
One of these two MeCN molecules was badly disordered, whose geometry 
was strictly restrained and the thermal vibration parameters were kept 
isotropic with fixed values. The anisotropic displacement parameters 
for the other MeCN molecules were also restrained.
;
_shelx_res_checksum              32018
_shelx_hkl_checksum              82007