Aromatic Fluorine-Induced One-Pot Synthesis of Ring-Perfluorinated Trimethine Cyanine Dye and Its Remarkable Fluorescence Properties.
Funabiki, Kazumasa; Saito, Yuki; Kikuchi, Takashi; Yagi, Kazutaka; Kubota, Yasuhiro; Inuzuka, Toshiyasu; Miwa, Yohei; Yoshida, Michiyuki; Sakurada, Osamu; Kutsumizu, Shoichi; The Journal of organic chemistry 84 (2019) 4372–4380; doi:10.1021/acs.joc.9b00378

data_4034230
_publ_section_title
;
 Aromatic Fluorine-Induced One-Pot Synthesis of Ring-Perfluorinated
 Trimethine Cyanine Dye and Its Remarkable Fluorescence Properties.
;
_journal_issue                   7
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4372
_journal_page_last               4380
_journal_paper_doi               10.1021/acs.joc.9b00378
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C F3 O3 S, C33 H21 F12 N2'
_chemical_formula_sum            'C34 H21 F15 N2 O3 S'
_chemical_formula_weight         822.59
_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             2018-10-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                87.846(3)
_cell_angle_beta                 80.072(3)
_cell_angle_gamma                70.549(3)
_cell_formula_units_Z            2
_cell_length_a                   8.5044(2)
_cell_length_b                   9.2497(3)
_cell_length_c                   21.4736(10)
_cell_measurement_reflns_used    9565
_cell_measurement_temperature    93
_cell_measurement_theta_max      73.2350
_cell_measurement_theta_min      5.0280
_cell_volume                     1568.56(10)
_computing_cell_refinement       'CrysAlisPro 1.171.40.21a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.21a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.21a (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      93
_diffrn_detector                 'Rigaku HyPix-6000 area detector'
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HPC area detector'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.965
_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   -124.00 -76.00   0.50    5.00    --  -35.00 -77.00-180.00   96
  2  \w   -124.00  54.00   0.50    5.00    --  -35.00   0.00 150.00  356
  3  \w    -39.00  10.00   0.50    5.00    --  -35.00 -82.00 -30.00   98
  4  \w    -39.00  10.00   0.50    5.00    --  -35.00 -82.00 -60.00   98
  5  \w   -124.00 -76.00   0.50    5.00    --  -35.00 -77.00  30.00   96
  6  \w    -39.00  10.00   0.50    5.00    --  -35.00 -82.00  90.00   98
  7  \w   -124.00 -76.00   0.50    5.00    --  -35.00 -77.00 -30.00   96
  8  \w    -45.00  88.00   0.50    5.00    --   43.50 -38.00   0.00  266
  9  \w      3.00  48.00   0.50    5.00    --   43.50  77.00 120.00   90
 10  \w      3.00  48.00   0.50    5.00    --   43.50  77.00-120.00   90
 11  \w      3.00  48.00   0.50    5.00    --   43.50  77.00 -60.00   90
 12  \w     74.00 199.00   0.50   25.00    --  109.30  61.00  30.00  250
 13  \w     20.00 145.00   0.50   25.00    --  109.30 -61.00-120.00  250
 14  \w     54.00 199.00   0.50   25.00    --  109.30  30.00   0.00  290
 15  \w     54.00 199.00   0.50   25.00    --  109.30  30.00 120.00  290
 16  \w     20.00 155.00   0.50   25.00    --  109.30 -82.00 -90.00  270
 17  \w     20.00 155.00   0.50   25.00    --  109.30 -82.00-180.00  270
 18  \w     74.00 199.00   0.50   25.00    --  109.30  61.00-180.00  250
 19  \w     66.00 199.00   0.50   25.00    --  109.30  41.00 -64.67  266
 20  \w     74.00 199.00   0.50   25.00    --  109.30  61.00-180.00  250
 21  \w     74.00 199.00   0.50   25.00    --  109.30  61.00  30.00  250
 22  \w     20.00 155.00   0.50   25.00    --  109.30 -82.00 -60.00  270
 23  \w     20.00 155.00   0.50   25.00    --  109.30 -82.00  90.00  270
 24  \w     82.00 199.00   0.50   25.00    --  109.30  82.00   0.00  234
 25  \w     20.00 145.00   0.50   25.00    --  109.30 -61.00  90.00  250
 26  \w   -124.00 -76.00   0.50    5.00    --  -35.00 -77.00 120.00   96
 27  \w    -39.00  88.00   0.50    5.00    --   43.50 -82.00-150.00  254
 28  \w      3.00  48.00   0.50    5.00    --   43.50  77.00-150.00   90
 29  \w      3.00  48.00   0.50    5.00    --   43.50  77.00   0.00   90
 30  \w      3.00  48.00   0.50    5.00    --   43.50  77.00  60.00   90
 31  \w      3.00  48.00   0.50    5.00    --   43.50  77.00  90.00   90
 32  \w      3.00  48.00   0.50    5.00    --   43.50  77.00 150.00   90
 33  \w     76.00 132.00   0.50    5.00    --   43.50  77.00-150.00  112
 34  \w    -39.00  88.00   0.50    5.00    --   43.50 -82.00 -90.00  254
 35  \w     69.00 199.00   0.50   25.00    --  109.30  45.00-180.00  260
 36  \w     69.00 199.00   0.50   25.00    --  109.30  45.00 -90.00  260
 37  \w     54.00 199.00   0.50   25.00    --  109.30  30.00  60.00  290
 38  \w     69.00 199.00   0.50   25.00    --  109.30  45.00 150.00  260
 39  \w     69.00 132.00   0.50   25.00    --  109.30  45.00 120.00  126
 40  \w     69.00 199.00   0.50   25.00    --  109.30  45.00-120.00  260
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB PRO'
_diffrn_measurement_method       '\\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0119728000
_diffrn_orient_matrix_UB_12      0.0118286000
_diffrn_orient_matrix_UB_13      0.0702892000
_diffrn_orient_matrix_UB_21      -0.0453319000
_diffrn_orient_matrix_UB_22      -0.1475365000
_diffrn_orient_matrix_UB_23      0.0129757000
_diffrn_orient_matrix_UB_31      0.1892180000
_diffrn_orient_matrix_UB_32      -0.0964721000
_diffrn_orient_matrix_UB_33      -0.0140747000
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.078
_diffrn_reflns_av_unetI/netI     0.0207
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            13053
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.844
_diffrn_reflns_theta_min         4.181
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              micromax007
_exptl_absorpt_coefficient_mu    2.138
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80854
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.21a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.742
_exptl_crystal_description       plate
_exptl_crystal_F_000             828
_exptl_crystal_size_max          0.088
_exptl_crystal_size_mid          0.073
_exptl_crystal_size_min          0.025
_refine_diff_density_max         0.880
_refine_diff_density_min         -0.562
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     503
_refine_ls_number_reflns         13053
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0790
_refine_ls_R_factor_gt           0.0616
_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^)+(0.1044P)^2^+0.5489P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1795
_refine_ls_wR_factor_ref         0.1914
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9767
_reflns_number_total             13053
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9780\% 
 around [0.58 -0.75 0.30] (reciprocal) or [0.71 -0.71 -0.00] (direct)
;
_cod_data_source_file            jo9b00378_si_002.cif
_cod_data_source_block           2a
_cod_original_cell_volume        1568.57(10)
_cod_database_code               4034230
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C34H21F15O3N2S
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.834
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6633(12)
 0.3367(12)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C13(H13), C15(H15), C14(H14)
3.b Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C33(H33A,H33B,H33C), C30(H30A,H30B,H30C), C32(H32A,H32B,
 H32C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C)
;
_shelx_res_checksum              5372
_shelx_hkl_checksum              90932
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 2.535
_oxdiff_exptl_absorpt_empirical_full_min 0.555
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2