Post-functionalization of triamino-phenazinium dyes to reach near-infrared emission
Munteanu, Tatiana; Longevial, Jean-François; Canard, Gabriel; Jacquemin, Denis; Pascal, Simon; Siri, Olivier; RSC Advances 14 (2024) 19257–19263; doi:10.1039/D4RA03245D

data_7248885
_publ_section_title
;
 Post-functionalization of triamino-phenazinium dyes to reach
 near-infrared emission
;
_journal_issue                   27
_journal_name_full               'RSC Advances'
_journal_page_first              19257
_journal_page_last               19263
_journal_paper_doi               10.1039/D4RA03245D
_journal_volume                  14
_journal_year                    2024
_chemical_formula_moiety         'F6 P, C42 H63 N8 O4'
_chemical_formula_sum            'C42 H63 F6 N8 O4 P'
_chemical_formula_weight         888.97
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-09-15
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-03-12 deposited with the CCDC.	2024-05-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.416(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.7061(5)
_cell_length_b                   35.5623(12)
_cell_length_c                   9.8813(3)
_cell_measurement_reflns_used    7465
_cell_measurement_temperature    180.00(10)
_cell_measurement_theta_max      69.8720
_cell_measurement_theta_min      3.7800
_cell_volume                     4620.0(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      180.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3045
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.978
_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    -84.00 -59.00   1.00    5.00    --    0.00-159.00-163.00   25
  2  \w    -57.00 -30.00   1.00    5.00    --    0.00 118.00  75.00   27
  3  \w   -142.00 -98.00   1.00   10.00    --  -54.86-159.00-163.00   44
  4  \w   -137.00-112.00   1.00   10.00    --  -54.86-118.00 -11.00   25
  5  \w    -67.00 -42.00   1.00   10.00    --  -54.86 118.00  75.00   25
  6  \w    110.00 150.00   1.00   10.00    --   54.86 159.00-132.00   40
  7  \w     42.00  67.00   1.00   20.00    --  109.71-118.00 -11.00   25
  8  \w    115.00 140.00   1.00   20.00    --  109.71 118.00  75.00   25
  9  \w     93.00 118.00   1.00   20.00    --  109.71 159.00-132.00   25
 10  \w     87.00 135.00   1.00   20.00    --  109.71-159.00-163.00   48
 11  \w     -7.00  21.00   1.00    5.00    --    0.00 -77.00-120.00   28
 12  \w     -2.00  40.00   1.00    5.00    --    0.00  77.00 -60.00   42
 13  \w     12.00  52.00   1.00    5.00    --    0.00 -99.00 150.00   40
 14  \w     59.00 100.00   1.00    5.00    --    0.00-178.00 -90.00   41
 15  \w   -115.00 -84.00   1.00   10.00    --  -54.86 -94.00  30.00   31
 16  \w   -155.00 -83.00   1.00   10.00    --  -54.86 -94.00 150.00   72
 17  \w    105.00 147.00   1.00   10.00    --   54.86 125.00 150.00   42
 18  \w    104.00 151.00   1.00   10.00    --   54.86  77.00 -30.00   47
 19  \w    108.00 157.00   1.00   10.00    --   54.86  77.00   0.00   49
 20  \w    104.00 150.00   1.00   10.00    --   54.86  77.00-120.00   46
 21  \w    100.00 138.00   1.00   10.00    --   54.86 125.00-180.00   38
 22  \w    103.00 132.00   1.00   10.00    --   54.86  77.00  60.00   29
 23  \w    103.00 150.00   1.00   20.00    --  109.71  77.00   0.00   47
 24  \w    115.00 176.00   1.00   20.00    --  109.71 111.00 120.00   61
 25  \w    110.00 143.00   1.00   20.00    --  109.71 178.00 150.00   33
 26  \w    103.00 139.00   1.00   20.00    --  109.71  77.00-150.00   36
 27  \w     58.00 109.00   1.00   20.00    --  109.71-111.00   0.00   51
 28  \w     98.00 155.00   1.00   20.00    --  109.71 -77.00 120.00   57
 29  \w    103.00 178.00   1.00   20.00    --  109.71  77.00  90.00   75
 30  \w      5.00  94.00   1.00   20.00    --  109.71 -77.00 120.00   89
 31  \w    146.00 173.00   1.00   20.00    --  109.71  77.00-150.00   27
 32  \w     77.00 128.00   1.00   20.00    --  109.71 178.00 -60.00   51
 33  \w    103.00 177.00   1.00   20.00    --  109.71  77.00 -60.00   74
 34  \w    107.00 132.00   1.00   20.00    --  109.71  77.00 150.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0506069000
_diffrn_orient_matrix_UB_12      -0.0355060000
_diffrn_orient_matrix_UB_13      -0.0436725000
_diffrn_orient_matrix_UB_21      -0.1044766000
_diffrn_orient_matrix_UB_22      -0.0239708000
_diffrn_orient_matrix_UB_23      0.0381626000
_diffrn_orient_matrix_UB_31      -0.1138138000
_diffrn_orient_matrix_UB_32      0.0062667000
_diffrn_orient_matrix_UB_33      -0.1018851000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0744
_diffrn_reflns_av_unetI/netI     0.0563
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       42
_diffrn_reflns_limit_k_min       -43
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            20778
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.962
_diffrn_reflns_theta_min         3.362
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.150
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83817
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.100a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.278
_exptl_crystal_description       prism
_exptl_crystal_F_000             1888
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.613
_refine_diff_density_min         -0.605
_refine_diff_density_rms         0.103
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.124
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     627
_refine_ls_number_reflns         8558
_refine_ls_number_restraints     102
_refine_ls_restrained_S_all      1.126
_refine_ls_R_factor_all          0.1501
_refine_ls_R_factor_gt           0.1313
_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^)+45.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2814
_refine_ls_wR_factor_ref         0.2901
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6602
_reflns_number_total             8558
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ra03245d2.cif
_cod_data_source_block           tm399
_cod_database_code               7248885
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'c42 h63 f6 n8 o4 p1'
_shelx_estimated_absorpt_t_max   0.955
_shelx_estimated_absorpt_t_min   0.820
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C44-C45
 1.48 with sigma of 0.002
 C38-C39
 1.48 with sigma of 0.002
 C40-C41
 1.48 with sigma of 0.002
 C38-C43
 1.48 with sigma of 0.002
 C43-C44
 1.48 with sigma of 0.002
 C39-C40
 1.48 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
C44 \\sim C45: within 1.7A with sigma of 0.0001 and sigma for terminal atoms of
0.0002 within 1.7A
C40 \\sim C41: within 1.7A with sigma of 0.0001 and sigma for terminal atoms of
0.0002 within 1.7A
C41 \\sim C42: within 1.7A with sigma of 0.0001 and sigma for terminal atoms of
0.0002 within 1.7A
C45 \\sim C46: within 1.7A with sigma of 0.0001 and sigma for terminal atoms of
0.0002 within 1.7A
C43 \\sim C44: within 1.7A with sigma of 0.0001 and sigma for terminal atoms of
0.0002 within 1.7A
C39 \\sim C40: within 1.7A with sigma of 0.0001 and sigma for terminal atoms of
0.0002 within 1.7A
4. Rigid body (RIGU) restrains
 P1, F1, F2, F3, F4, F5, F6, F7, F8
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Fixed Sof: F1(0.75) F2(0.75) F3(0.75) F4(0.75) F5(0.25) F6(0.25) F7(0.25)
 F8(0.25) H38A(0.5) H38B(0.5) H38C(0.5) H38D(0.5) C39(0.5) H39A(0.5) H39B(0.5)
 C40(0.5) H40A(0.5) H40B(0.5) C41(0.5) H41A(0.5) H41B(0.5) C42(0.5) H42A(0.5)
 H42B(0.5) H42C(0.5) C43(0.5) H43A(0.5) H43B(0.5) C44(0.5) H44A(0.5) H44B(0.5)
 C45(0.5) H45A(0.5) H45B(0.5) C46(0.5) H46A(0.5) H46B(0.5) H46C(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C27(H27A,H27B), C28(H28A,
 H28B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B),
 C33(H33A,H33B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B),
  C38(H38C,H38D), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C43(H43A,
 H43B), C44(H44A,H44B), C45(H45A,H45B)
6.b Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), N5(H5), N8(H8), C3(H3), C6(H6), C8(H8A), C9(H9), C12(H12),
 C19(H19), C22(H22)
6.c Idealised Me refined with riding coordinates:
 C42(H42A,H42B,H42C), C46(H46A,H46B,H46C)
6.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C26(H26A,H26B,
 H26C), C34(H34A,H34B,H34C)
;
_shelx_res_checksum              98291
_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 2.140
_oxdiff_exptl_absorpt_empirical_full_min 0.728