Ratiometric Turn-On Fluorophore Displacement Ensembles for Nitroaromatic Explosives Detection
Lee, Ji Yoon; Root, Harrison D.; Ali, Rashid; An, Won; Lynch, Vincent M.; Bähring, Steffen; Kim, In Su; Sessler, Jonathan L.; Park, Jung Su; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c08106

data_4135296
_publ_section_title
;
 Ratiometric Turn-On Fluorophore Displacement Ensembles for Nitroaromatic
 Explosives Detection
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c08106
_journal_year                    2020
_chemical_formula_moiety         'C60 H44 N4 S16, 2 (C28 H34 N2 O4)'
_chemical_formula_sum            'C116 H112 N8 O8 S16'
_chemical_formula_weight         2259.09
_space_group_crystal_system      tetragonal
_space_group_IT_number           88
_space_group_name_Hall           '-I 4ad'
_space_group_name_H-M_alt        'I 41/a :2'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-06-23
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.4388(3)
_cell_length_b                   20.4388(3)
_cell_length_c                   31.2788(5)
_cell_measurement_reflns_used    7586
_cell_measurement_temperature    223.15
_cell_measurement_theta_max      65.1280
_cell_measurement_theta_min      4.1590
_cell_volume                     13066.5(3)
_computing_cell_refinement       'Apex II release 2010, Bruker AXS, Inc.'
_computing_data_collection       'SAINT V8.40A, Bruker AXS, Inc.'
_computing_data_reduction        'Apex II release 2010, Bruker AXS, Inc.'
_computing_molecular_graphics    'XP SHELXTL/PC, Bruker AXS, Inc. 2009'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT n/a (Sheldrick, 2015)'
_diffrn_ambient_temperature      223.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \f   -130.83  71.17   1.00   30.00 -24.77-104.27  30.17    --   202
  2  \f    144.46 255.46   1.00   30.00  -9.52   7.92  59.16    --   111
  3  \f     72.83 298.83   1.00   30.00 -95.71-104.27 -30.17    --   226
  4  \w    -98.65  -7.65   1.00   30.00    --  -87.25  47.78-102.23   91
  5  \f     80.04 173.04   1.00   30.00 -87.02-104.27 -59.16    --    93
  6  \f   -339.96 -29.96   1.00   30.00 -72.02 -89.27 -59.16    --   310
  7  \f   -339.96 -39.96   1.00   30.00 -57.02 -74.27 -59.16    --   300
  8  \f     74.67 184.67   1.00   30.00  -0.52   7.92  30.17    --   110
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0385
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            32013
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.449
_diffrn_reflns_theta_min         2.582
_exptl_absorpt_coefficient_mu    2.873
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74328
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS, G. M. Sheldrick, 2009'
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.148
_exptl_crystal_description       block
_exptl_crystal_F_000             4736
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.273
_refine_diff_density_min         -0.263
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     569
_refine_ls_number_reflns         6014
_refine_ls_number_restraints     1646
_refine_ls_restrained_S_all      1.119
_refine_ls_R_factor_all          0.0661
_refine_ls_R_factor_gt           0.0453
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0865P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1249
_refine_ls_wR_factor_ref         0.1366
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4201
_reflns_number_total             6014
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c08106_si_002.cif
_cod_data_source_block           jungsu2
_cod_original_cell_volume        13066.5(4)
_cod_original_sg_symbol_H-M      'I 41/a'
_cod_database_code               4135296
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 S1-C5 = S1-C8 = S2-C6 = S2-C8 = S3-C9 = S3-C10 = S4-C9 = S4-C15
 1.74 with sigma of 0.02
 C1-C3 = C2-C3 = C3-C4
 1.5 with sigma of 0.02
 C4-C5 = C5-C6 = C6-C7 = C8-C9 = C10-C11 = C11-C12 = C12-C13 = C13-C14
 1.4 with sigma of 0.02
 C14-C15 = C10-C15
 1.4 with sigma of 0.02
 N1-C4 = N1-C7
 1.35 with sigma of 0.02
 C4-C6 = C5-C7 = C10-C12 = C11-C13 = C12-C14 = C13-C15 = C10-C14 = C11-C15
 2.4 with sigma of 0.02
 C10-C13 = C11-C14 = C12-C15
 2.8 with sigma of 0.02
 S3-C8 = S4-C8 = S2-C9 = S1-C9 = S1-C4 = S2-C7 = S3-C11 = S4-C14
 2.7 with sigma of 0.02
 O1-C51 = O2-C52 = O3-C57 = O4-C58
 1.2 with sigma of 0.02
 C65-C66 = C66-C67 = C67-C68 = C65-C69 = C69-C70 = C70-C71
 1.5 with sigma of 0.02
 C72-C73 = C72-C76 = C73-C74 = C74-C75 = C76-C77 = C77-C78
 1.5 with sigma of 0.02
 N2-C65 = N3-C72
 1.45 with sigma of 0.02
 C65-C70 = C65-C67 = C66-C68 = C69-C71
 2.45 with sigma of 0.02
 C72-C74 = C72-C77 = C73-C75 = C76-C78 = C73-C76 = C66-C69
 2.45 with sigma of 0.02
 C52-C65 = C51-C65 = C72-C58 = C72-C57
 2.45 with sigma of 0.02
 O1-N2 = O1-C62 = O2-N2 = O2-C53 = O3-N3 = O3-C56 = O4-N3 = O4-C59
 2.35 with sigma of 0.02
 N2-C51 = N2-C52 = C52-C53 = C53-C63 = C63-C62 = C62-C61
 1.4 with sigma of 0.02
 C64-C63 = C60-C61 = C54-C55 = C55-C56 = C56-C57 = C59-C64
 1.4 with sigma of 0.02
 C58-C59 = C56-C57
 1.4 with sigma of 0.02
 C57-C55 = C57-C58 = C58-C60 = C58-C64 = C57-C64
 2.4 with sigma of 0.02
 C55-C64 = C55-C53 = C54-C56 = C54-C63 = C63-C61 = C63-C59
 2.4 with sigma of 0.02
 C60-C62 = C62-C53 = C63-C52 = C52-C51 = C51-C63
 2.4 with sigma of 0.02
 C58-C56 = C59-C57 = N3-C64 = C56-C53 = C64-C54 = C63-C55
 2.8 with sigma of 0.02
 C60-C63 = C64-C61 = C62-C52 = C63-N2 = C53-C51
 2.8 with sigma of 0.02
 S3-C9 \\sim S3A-C9A
 with sigma of 0.02
 S3-C10 \\sim S3A-C10A
 with sigma of 0.02
 S4-C9 \\sim S4A-C9A
 with sigma of 0.02
 S4-C15 \\sim S4A-C15A
 with sigma of 0.02
 C8-C9 \\sim C8-C9A
 with sigma of 0.02
 C10-C11 \\sim C10A-C11A
 with sigma of 0.02
 C10-C15 \\sim C10A-C15A
 with sigma of 0.02
 C11-C12 \\sim C11A-C12A
 with sigma of 0.02
 C12-C13 \\sim C12A-C13A
 with sigma of 0.02
 C13-C14 \\sim C13A-C14A
 with sigma of 0.02
 C14-C15 \\sim C14A-C15A
 with sigma of 0.02
 S3-S4 \\sim S3A-S4A
 with sigma of 0.04
 S3-C8 \\sim S3A-C8
 with sigma of 0.04
 S3-C11 \\sim S3A-C11A
 with sigma of 0.04
 S3-C15 \\sim S3A-C15A
 with sigma of 0.04
 S4-C8 \\sim S4A-C8
 with sigma of 0.04
 S4-C10 \\sim S4A-C10A
 with sigma of 0.04
 S4-C14 \\sim S4A-C14A
 with sigma of 0.04
 C9-C10 \\sim C9A-C10A
 with sigma of 0.04
 C9-C15 \\sim C9A-C15A
 with sigma of 0.04
 C10-C12 \\sim C10A-C12A
 with sigma of 0.04
 C10-C14 \\sim C10A-C14A
 with sigma of 0.04
 C11-C13 \\sim C11A-C13A
 with sigma of 0.04
 C11-C15 \\sim C11A-C15A
 with sigma of 0.04
 C12-C14 \\sim C12A-C14A
 with sigma of 0.04
 C13-C15 \\sim C13A-C15A
 with sigma of 0.04
3. Restrained planarity
 N2, N3, O1, O2, O3, O4, C51, C52, C53, C54, C55, C56, C57, C58, C59, C60, C61,
  C62, C63, C64
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.01 and sigma
for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C9A)=Sof(S3A)=Sof(C10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=
 Sof(H13A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(S4A)=1-FVAR(1)
 Sof(S3)=Sof(S4)=Sof(C9)=Sof(C10)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=Sof(C13)=
 Sof(H13)=Sof(C14)=Sof(H14)=Sof(C15)=FVAR(1)
 Fixed Sof: O1(0.5) O2(0.5) O3(0.5) O4(0.5) N2(0.5) N3(0.5) C51(0.5) C52(0.5)
 C53(0.5) C54(0.5) H54(0.5) C55(0.5) H55(0.5) C56(0.5) C57(0.5) C58(0.5)
 C59(0.5) C60(0.5) H60(0.5) C61(0.5) H61(0.5) C62(0.5) C63(0.5) C64(0.5)
 C65(0.5) H65(0.5) C66(0.5) H66A(0.5) H66B(0.5) C67(0.5) H67A(0.5) H67B(0.5)
 C68(0.5) H68A(0.5) H68B(0.5) H68C(0.5) C69(0.5) H69A(0.5) H69B(0.5) C70(0.5)
 H70A(0.5) H70B(0.5) C71(0.5) H71A(0.5) H71B(0.5) H71C(0.5) C72(0.5) H72(0.5)
 C73(0.5) H73A(0.5) H73B(0.5) C74(0.5) H74A(0.5) H74B(0.5) C75(0.5) H75A(0.5)
 H75B(0.5) H75C(0.5) C76(0.5) H76A(0.5) H76B(0.5) C77(0.5) H77A(0.5) H77B(0.5)
 C78(0.5) H78A(0.5) H78B(0.5) H78C(0.5)
7.a Ternary CH refined with riding coordinates:
 C65(H65), C72(H72)
7.b Secondary CH2 refined with riding coordinates:
 C66(H66A,H66B), C67(H67A,H67B), C69(H69A,H69B), C70(H70A,H70B), C73(H73A,
 H73B), C74(H74A,H74B), C76(H76A,H76B), C77(H77A,H77B)
7.c Me refined with riding coordinates:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C68(H68A,H68B,H68C), C71(H71A,H71B,H71C),
 C75(H75A,H75B,H75C), C78(H78A,H78B,H78C)
7.d Aromatic/amide H refined with riding coordinates:
 N1(H1), C11(H11), C12(H12), C13(H13), C14(H14), C54(H54), C55(H55), C60(H60),
 C61(H61), C11A(H11A), C12A(H12A), C13A(H13A), C14A(H14A)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              21776
_shelx_hkl_checksum              36751
_shelx_fab_checksum              69806
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;