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_4135295
_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(C38 H38 N2 O4)'
_chemical_formula_sum            'C136 H120 N8 O8 S16'
_chemical_formula_weight         2507.35
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-06-17
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_cell_angle_alpha                77.227(4)
_cell_angle_beta                 73.330(5)
_cell_angle_gamma                66.176(5)
_cell_formula_units_Z            2
_cell_length_a                   17.7127(9)
_cell_length_b                   20.8300(11)
_cell_length_c                   23.3893(12)
_cell_measurement_reflns_used    7690
_cell_measurement_temperature    223
_cell_measurement_theta_max      21.9590
_cell_measurement_theta_min      1.9980
_cell_volume                     7507.8(7)
_computing_cell_refinement       'SAINT V8.34A, Bruker AXS, Inc. 2013'
_computing_data_collection       'SAINT V8.34A, Bruker AXS, Inc. 2013'
_computing_data_reduction        'SAINT V8.34A, Bruker AXS, Inc. 2013'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 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
_diffrn_detector                 'Photon 100'
_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  \f   -350.17   9.83   1.20  100.00   7.14  -1.42 -30.17    --   300
  2  \w    -32.23  21.77   1.20  100.00    --   -1.42  83.74 -29.95   45
  3  \w    -82.00  23.60   1.20  100.00    --  -50.51  83.08-162.77   88
  4  \w    -32.23  21.77   1.20  100.00    --   -1.42  83.74  60.05   45
  5  \w    -79.76  13.84   1.20  100.00    --   -1.42 -59.68 110.24   78
;
_diffrn_measurement_device       'Bruker Photon 100'
_diffrn_measurement_device_type  'Bruker Kappa Stage'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0005084000
_diffrn_orient_matrix_UB_12      0.0342638000
_diffrn_orient_matrix_UB_13      -0.0131086000
_diffrn_orient_matrix_UB_21      0.0448449000
_diffrn_orient_matrix_UB_22      -0.0129464000
_diffrn_orient_matrix_UB_23      -0.0059969000
_diffrn_orient_matrix_UB_31      0.0019231000
_diffrn_orient_matrix_UB_32      -0.0080146000
_diffrn_orient_matrix_UB_33      -0.0284426000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0663
_diffrn_reflns_av_unetI/netI     0.1169
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            54557
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.344
_diffrn_reflns_theta_max         25.344
_diffrn_reflns_theta_min         1.992
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.282
_exptl_absorpt_correction_T_max  1.00
_exptl_absorpt_correction_T_min  0.838
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS, G. M. Sheldrick, 2008'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.109
_exptl_crystal_description       needle
_exptl_crystal_F_000             2624
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.602
_refine_diff_density_min         -0.341
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.907
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1655
_refine_ls_number_reflns         27406
_refine_ls_number_restraints     3035
_refine_ls_restrained_S_all      0.921
_refine_ls_R_factor_all          0.1223
_refine_ls_R_factor_gt           0.0580
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0826P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1407
_refine_ls_wR_factor_ref         0.1603
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13597
_reflns_number_total             27406
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c08106_si_003.cif
_cod_data_source_block           mo_160722pjsno1
_cod_original_cell_volume        7507.8(8)
_cod_database_code               4135295
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C48H24N8O4S8
_shelx_estimated_absorpt_t_max   0.989
_shelx_estimated_absorpt_t_min   0.920
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.30
_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
 C123-C124 = C123-C127 = C124-C125 = C125-C126 = C127-C128 = C128-C129
 1.5 with sigma of 0.02
 C124-C127 = C124-C126 = C123-C125 = C123-C128 = C127-C129
 2.4 with sigma of 0.04
 C234-C235
 1.5 with sigma of 0.02
 C235-C236
 1.5 with sigma of 0.02
 C130-C234
 1.5 with sigma of 0.02
 C231-C232
 1.5 with sigma of 0.02
 C232-C233
 1.5 with sigma of 0.02
 C231-C130
 1.5 with sigma of 0.02
 C231-C233
 2.4 with sigma of 0.02
 C234-C236
 2.4 with sigma of 0.02
 C234-C231
 2.4 with sigma of 0.02
 C85-C86 = C86-C87 = C87-C88 = C85-C89 = C89-C90 = C90-C91
 1.5 with sigma of 0.02
 C92-C93 = C92-C96 = C93-C94 = C94-C95 = C96-C97 = C97-C98
 1.5 with sigma of 0.02
 C85-C87 = C85-C90 = C86-C88 = C89-C91 = C86-C89
 2.4 with sigma of 0.02
 C92-C94 = C92-C97 = C93-C96 = C93-C95 = C96-C98
 2.4 with sigma of 0.02
 C96A-C97A = C97A-C98A = C92-C96A
 1.5 with sigma of 0.02
 C92-C97A = C96A-C98A
 2.4 with sigma of 0.02
 C85-C86
 1.5 with sigma of 0.02
 C86-C87
 1.5 with sigma of 0.02
 C87-C88
 1.5 with sigma of 0.02
 C86-C89
 2.4 with sigma of 0.02
 C89-C91
 2.4 with sigma of 0.02
 C90-C85
 2.4 with sigma of 0.02
 C85-C87
 2.4 with sigma of 0.02
 C86-C88
 2.4 with sigma of 0.02
 C85-C89
 1.5 with sigma of 0.02
 C89-C90
 1.5 with sigma of 0.02
 C90-C91
 1.5 with sigma of 0.02
 C85-C89A
 1.5 with sigma of 0.02
 C89A-C90A
 1.5 with sigma of 0.02
 C90A-C91A
 1.5 with sigma of 0.02
 C89A-C91A
 2.4 with sigma of 0.02
 C85-C90A
 2.4 with sigma of 0.02
 C137-C85
 1.5 with sigma of 0.02
 C85-C138
 2.4 with sigma of 0.02
 C137-C139
 2.4 with sigma of 0.02
 C137-C138
 1.5 with sigma of 0.02
 C138-C139
 1.5 with sigma of 0.02
 C123-C124 = C123-C127
 1.5 with sigma of 0.01
 N5-C89 \\sim N5-C86 \\sim N6-C93 \\sim N6-C96
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C234 \\sim C134 \\sim C235 \\sim C135 \\sim C136 \\sim C236 \\sim C131 \\sim
C231 \\sim C132 \\sim C232 \\sim C133 \\sim C233: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
C96 \\sim C96A \\sim C97 \\sim C97A \\sim C98 \\sim C98A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C89 \\sim C90 \\sim C91 \\sim C90A \\sim C89A \\sim C91A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C86 \\sim C137 \\sim C87 \\sim C138 \\sim C139 \\sim C88: 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
Uanis(C137) = Uanis(C86)
4. 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
5. Others
 Sof(H13H)=Sof(C235)=Sof(H23A)=Sof(H23B)=Sof(C234)=Sof(H23C)=Sof(H23D)=
 Sof(C231)=Sof(H23E)=Sof(H23F)=Sof(C236)=Sof(H23G)=Sof(H23H)=Sof(H23I)=
 Sof(C233)=Sof(H23J)=Sof(H23K)=Sof(H23L)=Sof(C232)=Sof(H23M)=Sof(H23N)=1-FVAR(1)
 Sof(H130)=Sof(C131)=Sof(H13I)=Sof(H13J)=Sof(C132)=Sof(H13K)=Sof(H13L)=
 Sof(C133)=Sof(H13M)=Sof(H13N)=Sof(H13O)=Sof(C134)=Sof(H13P)=Sof(H13Q)=
 Sof(C135)=Sof(H13R)=Sof(H13S)=Sof(C136)=Sof(H13T)=Sof(H13U)=Sof(H13V)=FVAR(1)
 Sof(C91A)=Sof(H91D)=Sof(H91E)=Sof(H91F)=Sof(C90A)=Sof(H90C)=Sof(H90D)=
 Sof(C89A)=Sof(H89C)=Sof(H89D)=Sof(C137)=Sof(H13A)=Sof(H13B)=Sof(C138)=
 Sof(H13C)=Sof(H13D)=Sof(C139)=Sof(H13E)=Sof(H13F)=Sof(H13G)=1-FVAR(2)
 Sof(C86)=Sof(H86A)=Sof(H86B)=Sof(C87)=Sof(H87A)=Sof(H87B)=Sof(C88)=Sof(H88A)=
 Sof(H88B)=Sof(H88C)=Sof(C89)=Sof(H89A)=Sof(H89B)=Sof(C90)=Sof(H90A)=Sof(H90B)=
 Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(H91C)=FVAR(2)
 Fixed Sof: H85(0.5) H85A(0.5) H92(0.5) H92A(0.5) C96(0.5) H96A(0.5) H96B(0.5)
 C97(0.5) H97A(0.5) H97B(0.5) C98(0.5) H98A(0.5) H98B(0.5) H98C(0.5) C97A(0.5)
 H97C(0.5) H97D(0.5) C98A(0.5) H98D(0.5) H98E(0.5) H98F(0.5) C96A(0.5)
 H96C(0.5) H96D(0.5)
6.a Ternary CH refined with riding coordinates:
 C85(H85), C85(H85A), C92(H92), C92(H92A), C123(H123), C130(H130), C130(H13H)
6.b Secondary CH2 refined with riding coordinates:
 C86(H86A,H86B), C87(H87A,H87B), C89(H89A,H89B), C90(H90A,H90B), C93(H93A,
 H93B), C94(H94A,H94B), C96(H96A,H96B), C97(H97A,H97B), C124(H12A,H12B),
 C125(H12C,H12D), C127(H12H,H12I), C128(H12J,H12K), C131(H13I,H13J), C132(H13K,
 H13L), C134(H13P,H13Q), C135(H13R,H13S), C97A(H97C,H97D), C96A(H96C,H96D),
 C235(H23A,H23B), C234(H23C,H23D), C231(H23E,H23F), C232(H23M,H23N), C90A(H90C,
 H90D), C89A(H89C,H89D), C137(H13A,H13B), C138(H13C,H13D)
6.c Me refined with riding coordinates:
 C88(H88A,H88B,H88C), C91(H91A,H91B,H91C), C98(H98A,H98B,H98C), C133(H13M,H13N,
 H13O), C136(H13T,H13U,H13V), C98A(H98D,H98E,H98F), C236(H23G,H23H,H23I),
 C233(H23J,H23K,H23L), C91A(H91D,H91E,H91F), C139(H13E,H13F,H13G)
6.d Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), N3(H3), N4(H4), C24(H24), C25(H25), C26(H26), C27(H27),
 C34(H34), C35(H35), C36(H36), C37(H37), C44(H44), C45(H45), C46(H46), C47(H47),
  C54(H54), C55(H55), C56(H56), C57(H57), C63(H63), C64(H64), C67(H67),
 C68(H68), C73(H73), C74(H74), C77(H77), C78(H78), C101(H101), C102(H102),
 C105(H105), C106(H106), C111(H111), C112(H112), C115(H115), C116(H116)
6.e Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C39(H39A,H39B,H39C), C40(H40A,H40B,
 H40C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C59(H59A,H59B,H59C), C60(H60A,
 H60B,H60C), C95(H95A,H95B,H95C), C126(H12E,H12F,H12G), C129(H12L,H12M,H12N)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              44814
_shelx_hkl_checksum              17923
_shelx_fab_checksum              80726
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.053
_oxdiff_exptl_absorpt_empirical_full_min 0.456