π-Extended diphosphonium-bridged ladder stilbenes: water-soluble fluorophores with up to eight annulated rings.
Senn, Sebastian; Mörsdorf, Jean-Marc; Bertrams, Maria-Sophie; Kerzig, Christoph; Ballmann, Joachim; Chemical science 16 (2025) 20517–20526; doi:10.1039/d5sc03752b

data_1575887
_publ_section_title
;
 &#x3c0;-Extended diphosphonium-bridged ladder stilbenes: water-soluble
 fluorophores with up to eight annulated rings.
;
_journal_issue                   43
_journal_name_full               'Chemical science'
_journal_page_first              20517
_journal_page_last               20526
_journal_paper_doi               10.1039/d5sc03752b
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C42 H44 P2, 2(C H4 O), 2(Cl)'
_chemical_formula_sum            'C44 H52 Cl2 O2 P2'
_chemical_formula_weight         745.69
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-07-20
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2025-03-14 deposited with the CCDC.	2025-09-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.6366(8)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.48118(8)
_cell_length_b                   13.37430(9)
_cell_length_c                   13.10304(12)
_cell_measurement_reflns_used    41172
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      70.9380
_cell_measurement_theta_min      4.7720
_cell_volume                     1963.27(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.989
_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    -21.00  69.00   1.00    1.00    --    0.00  57.00-150.00   90
  2  \w    -69.00  21.00   1.00    1.00    --    0.00 -57.00-150.00   90
  3  \w    -61.00  -6.00   1.00    1.00    --    0.00 132.00 -64.00   55
  4  \w    -70.00  30.00   1.00    1.00    --    0.00 -77.00  90.00  100
  5  \w    -46.00  -6.00   1.00    1.00    --   14.00 130.00 -12.44   40
  6  \w     -2.00  34.00   1.00    5.00    --   34.00  87.00-143.98   36
  7  \w     -2.00  25.00   1.00    5.00    --   38.00  95.00 100.34   27
  8  \w      5.00  32.00   1.00    5.00    --   42.00  90.00 116.09   27
  9  \w      6.00  33.00   1.00    5.00    --   42.00  88.00 -10.05   27
 10  \w     12.00  38.00   1.00    5.00    --   46.00  84.00 -17.96   26
 11  \w     13.00  45.00   1.00    5.00    --   46.00  82.00-106.67   32
 12  \w     12.00  38.00   1.00    5.00    --   46.00  84.00-175.52   26
 13  \w     13.00  40.00   1.00    5.00    --   46.00  83.00  19.30   27
 14  \w     18.00  45.00   1.00    5.00    --   50.00  81.00 131.84   27
 15  \w     19.00  45.00   1.00    5.00    --   50.00  78.00 -25.97   26
 16  \w     18.00  45.00   1.00    5.00    --   50.00  81.00  84.91   27
 17  \w     18.00  45.00   1.00    5.00    --   50.00  80.00 -67.88   27
 18  \w     18.00  45.00   1.00    5.00    --   50.00  81.00  59.14   27
 19  \w     24.00 125.00   1.00    5.00    --   54.49  77.00 120.00  101
 20  \w    -14.00  76.00   1.00    5.00    --   54.49 -57.00  90.00   90
 21  \w     23.00 110.00   1.00    5.00    --   54.49-125.00  60.00   87
 22  \w     24.00 125.00   1.00    5.00    --   54.49  77.00 150.00  101
 23  \w     24.00 125.00   1.00    5.00    --   54.49  77.00   0.00  101
 24  \w     24.00 125.00   1.00    5.00    --   54.49  77.00  30.00  101
 25  \w     24.00 125.00   1.00    5.00    --   54.49  77.00 -30.00  101
 26  \w     24.00 125.00   1.00    5.00    --   54.49  77.00  60.00  101
 27  \w     24.00 125.00   1.00    5.00    --   54.49  77.00-120.00  101
 28  \w      1.00  95.00   1.00    5.00    --   54.49 -99.00-120.00   94
 29  \w     28.00 128.00   1.00    5.00    --   58.00  77.00 -79.52  100
 30  \w     29.00 128.00   1.00    5.00    --   58.00  76.00  73.16   99
 31  \w     31.00 127.00   1.00    5.00    --   58.00  71.00 -16.32   96
 32  \w     31.00 127.00   1.00    5.00    --   58.00  71.00 120.62   96
 33  \w     29.00 128.00   1.00    5.00    --   58.00  76.00-163.21   99
 34  \w     29.00 128.00   1.00    5.00    --   58.00  75.00 179.78   99
 35  \w     33.00 132.00   1.00    5.00    --   62.00  75.00 -80.48   99
 36  \w     33.00 132.00   1.00    5.00    --   62.00  75.00   0.35   99
 37  \w     33.00 132.00   1.00    5.00    --   62.00  76.00-148.20   99
 38  \w     33.00 132.00   1.00    5.00    --   62.00  76.00 158.99   99
 39  \w     33.00 132.00   1.00    5.00    --   62.00  76.00  32.28   99
 40  \w     32.00 132.00   1.00    5.00    --   62.00  77.00-120.94  100
 41  \w     33.00 132.00   1.00    5.00    --   62.00  76.00 123.88   99
 42  \w     32.00 132.00   1.00    5.00    --   62.00  77.00 -69.00  100
 43  \w     37.00 136.00   1.00    5.00    --   66.00  75.00-136.88   99
 44  \w     37.00 136.00   1.00    5.00    --   66.00  76.00 115.16   99
 45  \w     38.00 136.00   1.00    5.00    --   66.00  74.00 -67.00   98
 46  \w     36.00 136.00   1.00    5.00    --   66.00  77.00 -86.43  100
 47  \w     44.00 139.00   1.00    5.00    --   70.00  70.00 -39.37   95
 48  \w     42.00 140.00   1.00    5.00    --   70.00  74.00 -13.01   98
 49  \w     42.00 139.00   1.00    5.00    --   70.00  73.00  29.87   97
 50  \w     45.00 138.00   1.00    5.00    --   70.00  69.00 175.79   93
 51  \w     41.00 140.00   1.00    5.00    --   70.00  75.00  -3.62   99
 52  \w     40.00 140.00   1.00    5.00    --   70.00  77.00  79.76  100
 53  \w     50.00 142.00   1.00    5.00    --   74.00  68.00  57.17   92
 54  \w     48.00 143.00   1.00    5.00    --   74.00  70.00 -29.11   95
 55  \w     49.00 142.00   1.00    5.00    --   74.00  69.00-117.08   93
 56  \w     45.00 144.00   1.00    5.00    --   74.00  76.00 -98.36   99
 57  \w     49.00 148.00   1.00    5.00    --   78.00  76.00  26.10   99
 58  \w     56.00 146.00   1.00    5.00    --   78.00  61.00 -21.76   90
 59  \w     50.00 148.00   1.00    5.00    --   78.00  74.00 137.96   98
 60  \w     49.00 148.00   1.00    5.00    --   78.00  75.00  -4.02   99
 61  \w     48.00 148.00   1.00    5.00    --   78.00  77.00-109.27  100
 62  \w     55.00 145.00   1.00    5.00    --   78.00  64.00  -9.18   90
 63  \w     50.00 147.00   1.00    5.00    --   78.00  73.00-133.51   97
 64  \w     56.00 146.00   1.00    5.00    --   78.00  61.00 -62.31   90
 65  \w     54.00 152.00   1.00   15.00    --   82.00  74.00  30.98   98
 66  \w     59.00 150.00   1.00   15.00    --   82.00  65.00 104.33   91
 67  \w     59.00 150.00   1.00   15.00    --   82.00  66.00 -55.64   91
 68  \w     63.00 153.00   1.00   15.00    --   86.00  64.00-138.10   90
 69  \w     59.00 155.00   1.00   15.00    --   86.00  72.00 -25.88   96
 70  \w     56.00 156.00   1.00   15.00    --   86.00  77.00 164.95  100
 71  \w     58.00 156.00   1.00   15.00    --   86.00  74.00-159.17   98
 72  \w     60.00 160.00   1.00   15.00    --   90.00  77.00  97.04  100
 73  \w     60.00 160.00   1.00   15.00    --   90.00  77.00 156.83  100
 74  \w     62.00 160.00   1.00   15.00    --   90.00  74.00 152.24   98
 75  \w     75.00 169.00   1.00   15.00    --   98.00  48.00  35.30   94
 76  \w     77.00 176.00   1.00   15.00    --  106.00  75.00 130.72   99
 77  \w     83.00 178.00   1.00   15.00    --  108.98  38.00 -30.00   95
 78  \w     86.00 176.00   1.00   15.00    --  108.98  64.00-150.00   90
 79  \w     51.00 131.00   1.00   15.00    --  108.98 -50.00  60.00   80
 80  \w     89.00 176.00   1.00   15.00    --  108.98  64.00 -30.00   87
 81  \w     88.00 113.00   1.00   15.00    --  108.98  64.00  60.00   25
 82  \w     86.00 113.00   1.00   15.00    --  108.98  64.00-180.00   27
 83  \w     37.00  93.00   1.00   15.00    --  108.98 -92.00 -30.00   56
 84  \w    144.00 170.00   1.00   15.00    --  108.98 111.00 -30.00   26
 85  \w     37.00  80.00   1.00   15.00    --  108.98 -92.00 -90.00   43
 86  \w     87.00 114.00   1.00   15.00    --  108.98  64.00 -60.00   27
 87  \w     37.00 109.00   1.00   15.00    --  108.98 -92.00  90.00   72
 88  \w     86.00 112.00   1.00   15.00    --  108.98  64.00  90.00   26
 89  \w     80.00 105.00   1.00   15.00    --  108.98  77.00 159.62   25
 90  \w     80.00 107.00   1.00   15.00    --  108.98  77.00 150.00   27
 91  \w     87.00 170.00   1.00   15.00    --  108.98  64.00  30.00   83
 92  \w     87.00 113.00   1.00   15.00    --  108.98  64.00 -90.00   26
 93  \w     79.00 105.00   1.00   15.00    --  108.98  77.00-120.00   26
 94  \w     87.00 175.00   1.00   15.00    --  108.98  64.00 120.00   88
 95  \w     88.00 177.00   1.00   15.00    --  108.98  45.00 -77.05   89
 96  \w    110.00 177.00   1.00   15.00    --  108.98  77.00  60.00   67
 97  \w     80.00 105.00   1.00   15.00    --  108.98  77.00  60.00   25
 98  \w    116.00 178.00   1.00   15.00    --  108.98  77.00   0.00   62
 99  \w     88.00 175.00   1.00   15.00    --  108.98  64.00 150.00   87
100  \w     85.00 110.00   1.00   15.00    --  108.98  38.00  90.00   25
101  \w     79.00 105.00   1.00   15.00    --  108.98  77.00 120.00   26
102  \w     82.00 109.00   1.00   15.00    --  108.98  77.00   0.00   27
103  \w     79.00 106.00   1.00   15.00    --  108.98  77.00-150.00   27
104  \w    127.00 153.00   1.00   15.00    --  108.98  77.00 -60.00   26
105  \w     83.00 110.00   1.00   15.00    --  108.98  77.00 -60.00   27
106  \w     79.00 105.00   1.00   15.00    --  108.98  77.00 -30.00   26
107  \w     96.00 123.00   1.00   15.00    --  108.98  50.00  60.00   27
108  \w     83.00 115.00   1.00   15.00    --  108.98  38.00  30.00   32
109  \w     79.00 106.00   1.00   15.00    --  108.98  77.00 -90.00   27
110  \w     59.00 103.00   1.00   15.00    --  108.98 -92.00-180.00   44
111  \w     79.00 177.00   1.00   15.00    --  108.98  77.00-180.00   98
112  \w     79.00 105.00   1.00   15.00    --  108.98  77.00  30.00   26
113  \w     49.00 113.00   1.00   15.00    --  108.98-111.00  60.00   64
114  \w     86.00 175.00   1.00   15.00    --  108.98  64.00-120.00   89
115  \w    124.00 158.00   1.00   15.00    --  108.98  77.00  90.00   34
116  \w     83.00 121.00   1.00   15.00    --  108.98  77.00  90.00   38
117  \w     62.00  87.00   1.00   15.00    --  108.98-111.00 -90.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1202206000
_diffrn_orient_matrix_UB_12      -0.0180583000
_diffrn_orient_matrix_UB_13      0.0770427000
_diffrn_orient_matrix_UB_21      -0.0204235000
_diffrn_orient_matrix_UB_22      -0.1137453000
_diffrn_orient_matrix_UB_23      -0.0102235000
_diffrn_orient_matrix_UB_31      0.0636548000
_diffrn_orient_matrix_UB_32      -0.0024005000
_diffrn_orient_matrix_UB_33      -0.0919960000
_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  0.0532
_diffrn_reflns_av_unetI/netI     0.0154
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            75260
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.144
_diffrn_reflns_theta_min         4.785
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.530
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.444
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.51a (Rigaku Oxford Diffraction, 2022)
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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.261
_exptl_crystal_description       irregular
_exptl_crystal_F_000             792
_exptl_crystal_size_max          0.254
_exptl_crystal_size_mid          0.207
_exptl_crystal_size_min          0.097
_refine_diff_density_max         0.429
_refine_diff_density_min         -0.237
_refine_diff_density_rms         0.046
_refine_ls_extinction_coef       0.0020(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.149
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     466
_refine_ls_number_reflns         3759
_refine_ls_number_restraints     611
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0534
_refine_ls_R_factor_gt           0.0516
_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^)+(0.0488P)^2^+1.4889P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1355
_refine_ls_wR_factor_ref         0.1367
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3602
_reflns_number_total             3759
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03752b3.cif
_cod_data_source_block           cmpd_4cAnth_ba_ss7
_cod_depositor_comments
'Adding full bibliography for 1575881--1575890.cif.'
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               1575887
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C44H52Cl2O2P2
_chemical_oxdiff_usercomment     'ss199, irregular, red'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O1-C22 \\sim O51-C72
 with sigma of 0.02
 C67-C66 \\sim C66-C68
 with sigma of 0.02
 C70-C69 \\sim C69-C71
 with sigma of 0.02
 C18-C16 \\sim C16-C17
 with sigma of 0.02
 C20-C19 \\sim C19-C21
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C51 \\sim C52 \\sim C53 \\sim C54
\\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62
\\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70
\\sim C71: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
O1 \\sim O51 \\sim C22 \\sim C72: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
4. Others
 Sof(Cl51)=Sof(P51)=Sof(C51)=Sof(C52)=Sof(C53)=Sof(H53)=Sof(C54)=Sof(C55)=
 Sof(H55)=Sof(C56)=Sof(C57)=Sof(H57)=Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=
 Sof(C60)=Sof(H60)=Sof(C61)=Sof(C62)=Sof(H62)=Sof(C63)=Sof(C64)=Sof(H64)=
 Sof(C65)=Sof(C66)=Sof(H66)=Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(H67C)=Sof(C68)=
 Sof(H68A)=Sof(H68B)=Sof(H68C)=Sof(C69)=Sof(H69)=Sof(C70)=Sof(H70A)=Sof(H70B)=
 Sof(H70C)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=1-FVAR(1)
 Sof(Cl1)=Sof(P1)=Sof(C1)=Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(C5)=Sof(H5)=
 Sof(C6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=
 Sof(C11)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(C16)=
 Sof(H16)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18)=Sof(H18A)=Sof(H18B)=
 Sof(H18C)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21)=
 Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(1)
 Sof(O51)=Sof(H51)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=1-FVAR(2)
 Sof(O1)=Sof(H1)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C16(H16), C19(H19), C66(H66), C69(H69)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10), C12(H12), C14(H14),
 C53(H53), C55(H55), C57(H57), C58(H58), C59(H59), C60(H60), C62(H62), C64(H64)
5.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C70(H70A,H70B,H70C), C71(H71A,
 H71B,H71C), C22(H22A,H22B,H22C), C72(H72A,H72B,H72C)
5.d Idealised tetrahedral OH refined as rotating group:
 O1(H1), O51(H51)
;
_shelx_res_checksum              12284
_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
;