Combined colourimetric and turn-on luminescence from a redox-switchable 2-aza-anthraquinone bridged dimetallic assembly.
Ibbott, Alexandra R.; Horton, Peter N.; Coles, Simon J.; Pope, Simon J. A.; Dalton transactions (Cambridge, England : 2003) 54 (2025) 15986–15990; doi:10.1039/d5dt02287h

data_7719700
_publ_section_title
;
 Combined colourimetric and turn-on luminescence from a redox-switchable
 2-aza-anthraquinone bridged dimetallic assembly.
;
_journal_issue                   43
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              15986
_journal_page_last               15990
_journal_paper_doi               10.1039/d5dt02287h
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety
'0.5(C H Cl3), C37 H21 N7 O2, 0.5[C6H14O], 0.5[CHCl3]'
_chemical_formula_sum            'C41 H29 Cl3 N7 O2.5'
_chemical_formula_weight         766.06
_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             2023-06-01
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-07-12 deposited with the CCDC.	2025-10-21 downloaded from the CCDC.
;
_cell_angle_alpha                85.6670(10)
_cell_angle_beta                 89.0710(10)
_cell_angle_gamma                88.3140(10)
_cell_formula_units_Z            4
_cell_length_a                   14.0892(3)
_cell_length_b                   14.5170(2)
_cell_length_c                   16.7295(3)
_cell_measurement_reflns_used    23561
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      75.4330
_cell_measurement_theta_min      7.7600
_cell_volume                     3410.14(11)
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (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      100(2)
_diffrn_detector                 'hybrid pixel array detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_dtime           0.000
_diffrn_detector_type            'Rigaku, HyPix 6000HE'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.952
_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    -68.00  11.00   0.50    6.00    --  -45.30  84.00 -57.00  158
  2  \w    -17.00  69.00   0.50    6.00    --   45.30 -84.00-177.00  172
  3  \w    -92.00 -23.00   0.50   30.00    --  -97.00  84.00 -57.00  138
  4  \w     37.00  84.00   0.50   30.00    --  109.75 -84.00-177.00   94
  5  \w     99.00 175.00   0.50   30.00    --  109.75  84.00 -57.00  152
  6  \w    -23.00  30.00   0.50    6.00    --  -45.30  38.00 -30.00  106
  7  \w    -62.00 -32.00   0.50    6.00    --  -45.30 -61.00  43.69   60
  8  \w    -62.00 -33.00   0.50    6.00    --  -45.30 -60.00  71.23   58
  9  \w   -119.00 -37.00   0.50    6.00    --  -45.30 -46.00 168.57  164
 10  \w    -62.00 -35.00   0.50    6.00    --  -45.30 -55.00 -94.57   54
 11  \w    -62.00 -34.00   0.50    6.00    --  -45.30 -58.00  -5.38   56
 12  \w    -30.00  15.00   0.50    6.00    --   45.30 -38.00-150.00   90
 13  \w    -30.00  15.00   0.50    6.00    --   45.30 -38.00 -60.00   90
 14  \w    -30.00  15.00   0.50    6.00    --   45.30 -38.00-180.00   90
 15  \w    -30.00  15.00   0.50    6.00    --   45.30 -38.00-120.00   90
 16  \w    -30.00  15.00   0.50    6.00    --   45.30 -38.00  90.00   90
 17  \w    -92.00 -23.00   0.50   30.00    --  -97.00  94.00 -38.72  138
 18  \w    -93.00 -25.00   0.50   30.00    --  -97.00 104.00 -51.18  136
 19  \w    -55.00 -23.00   0.50   30.00    --  -97.00  61.00 -60.00   64
 20  \w    -92.00 -25.00   0.50   30.00    --  -97.00  98.00 -64.77  134
 21  \w    -93.00 -25.00   0.50   30.00    --  -97.00  97.00 105.86  136
 22  \w    -92.00 -25.00   0.50   30.00    --  -97.00  99.00-128.68  134
 23  \w    -98.00 -27.00   0.50   30.00    --  -97.00 116.00  32.33  142
 24  \w    -97.00 -27.00   0.50   30.00    --  -97.00 114.00 103.10  140
 25  \w   -140.00 -90.00   0.50   30.00    --  -97.00 -15.00   0.00  100
 26  \w    -92.00 -25.00   0.50   30.00    --  -97.00  99.00   5.12  134
 27  \w    -93.00 -25.00   0.50   30.00    --  -97.00  97.00 150.59  136
 28  \w    -92.00 -25.00   0.50   30.00    --  -97.00  96.00 169.20  134
 29  \w   -170.00-106.00   0.50   30.00    --  -97.00 -77.00 150.00  128
 30  \w    -98.00 -27.00   0.50   30.00    --  -97.00 116.00-170.00  142
 31  \w    -92.00 -23.00   0.50   30.00    --  -97.00  95.00  21.24  138
 32  \w    -93.00 -25.00   0.50   30.00    --  -97.00  97.00  42.56  136
 33  \w   -167.00-107.00   0.50   30.00    --  -97.00 -84.00-177.00  120
 34  \w   -166.00-114.00   0.50   30.00    --  -97.00 -77.00 -60.00  104
 35  \w   -140.00-115.00   0.50   30.00    --  -97.00 -15.00  90.00   50
 36  \w    -92.00 -63.00   0.50   30.00    --  -97.00  95.00-144.97   58
 37  \w     37.00  91.00   0.50   30.00    --  109.75 -95.00   0.00  108
 38  \w     48.00  91.00   0.50   30.00    --  109.75 -95.00 120.00   86
 39  \w    105.00 162.00   0.50   30.00    --  109.75  30.00-150.00  114
 40  \w     49.00  91.00   0.50   30.00    --  109.75 -95.00  60.00   84
 41  \w    106.00 131.00   0.50   30.00    --  109.75  15.00 -60.00   50
 42  \w    105.00 131.00   0.50   30.00    --  109.75  15.00-180.00   52
 43  \w    104.00 130.00   0.50   30.00    --  109.75  15.00-150.00   52
 44  \w     37.00  62.00   0.50   30.00    --  109.75 -77.00   0.00   50
 45  \w    104.00 130.00   0.50   30.00    --  109.75  15.00-120.00   52
 46  \w    104.00 132.00   0.50   30.00    --  109.75  15.00   0.00   56
 47  \w     38.00  81.00   0.50   30.00    --  109.75 -95.00  30.00   86
 48  \w     38.00  70.00   0.50   30.00    --  109.75 -77.00 150.00   64
 49  \w     38.00  80.00   0.50   30.00    --  109.75 -95.00-150.00   84
 50  \w    106.00 131.00   0.50   30.00    --  109.75  15.00 120.00   50
 51  \w    105.00 131.00   0.50   30.00    --  109.75  15.00  30.00   52
 52  \w    104.00 129.00   0.50   30.00    --  109.75  15.00  90.00   50
 53  \w    104.00 132.00   0.50   30.00    --  109.75  15.00 -30.00   56
 54  \w     38.00  71.00   0.50   30.00    --  109.75 -77.00-120.00   66
 55  \w    106.00 132.00   0.50   30.00    --  109.75  15.00 150.00   52
 56  \w     37.00  93.00   0.50   30.00    --  109.75 -95.00 -90.00  112
 57  \w    107.00 162.00   0.50   30.00    --  109.75  30.00-120.00  110
 58  \w     37.00  86.00   0.50   30.00    --  109.75 -95.00  90.00   98
 59  \w     37.00  62.00   0.50   30.00    --  109.75 -77.00  90.00   50
 60  \w     37.00  62.00   0.50   30.00    --  109.75 -84.00-177.00   50
 61  \w    -62.00 -34.00   0.50    6.00    --  -45.30 -58.00 -50.75   56
 62  \w    -62.00 -33.00   0.50    6.00    --  -45.30 -59.00-120.46   58
 63  \w    -62.00 -34.00   0.50    6.00    --  -45.30 -58.00 104.21   56
 64  \w    -62.00 -32.00   0.50    6.00    --  -45.30 -61.00 153.52   60
 65  \w    -62.00 -35.00   0.50    6.00    --  -45.30 -55.00-162.97   54
 66  \w    -62.00 -33.00   0.50    6.00    --  -45.30 -60.00  21.78   58
 67  \w    -62.00 -33.00   0.50    6.00    --  -45.30 -60.00-171.20   58
 68  \w   -122.00 -39.00   0.50    6.00    --  -45.30 -19.00 -30.00  166
 69  \w   -122.00 -39.00   0.50    6.00    --  -45.30 -19.00-150.00  166
 70  \w    -62.00 -35.00   0.50    6.00    --  -45.30 -55.00  87.76   54
 71  \w    -62.00 -33.00   0.50    6.00    --  -45.30 -59.00 142.44   58
 72  \w   -118.00 -35.00   0.50    6.00    --  -45.30 -53.00 -74.38  166
 73  \w    104.00 129.00   0.50   30.00    --  109.75  15.00  60.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_details 'Rigaku, UG2 \k goniometer'
_diffrn_measurement_device_type
'Rigaku 007HF diffractometer with HF Varimax confocal mirrors, an UG2 goniometer and HyPix 6000HE detector'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen loops'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0959641000
_diffrn_orient_matrix_UB_12      -0.0280572000
_diffrn_orient_matrix_UB_13      -0.0378320000
_diffrn_orient_matrix_UB_21      -0.0521916000
_diffrn_orient_matrix_UB_22      -0.0341992000
_diffrn_orient_matrix_UB_23      -0.0718732000
_diffrn_orient_matrix_UB_31      0.0059699000
_diffrn_orient_matrix_UB_32      0.0968434000
_diffrn_orient_matrix_UB_33      -0.0439693000
_diffrn_radiation_collimation    'HF Varimax focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_unetI/netI     0.0329
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            27741
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         77.151
_diffrn_reflns_theta_min         2.649
_diffrn_source                   'Rotating anode'
_diffrn_source_current           30.0
_diffrn_source_power             1.2
_diffrn_source_target            Cu
_diffrn_source_type              'Rigaku 007 HF'
_diffrn_source_voltage           40.0
_exptl_absorpt_coefficient_mu    2.862
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83265
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark blue'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.492
_exptl_crystal_description       block
_exptl_crystal_F_000             1580
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of diisopropyl ether and chloroform'
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.785
_refine_diff_density_min         -0.877
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1033
_refine_ls_number_reflns         27741
_refine_ls_number_restraints     403
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.1070
_refine_ls_R_factor_gt           0.0863
_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^)+(0.1504P)^2^+3.2637P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2440
_refine_ls_wR_factor_ref         0.2583
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21048
_reflns_number_total             27741
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 178.3110\% 
around [1.00 0.00 0.00] (reciprocal) or [1.00 -0.02 -0.01] (direct)
;
_cod_data_source_file            d5dt02287h2.cif
_cod_data_source_block           L1
_cod_depositor_comments
'Adding full bibliography for 7719700--7719701.cif.'
_cod_original_formula_sum        'C41 H29 Cl3 N7 O2.50'
_cod_database_code               7719700
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C37 H21 N7 O2 CHCl3'
_chemical_oxdiff_usercomment     Al-phen
_shelx_estimated_absorpt_t_max   0.894
_shelx_estimated_absorpt_t_min   0.847
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6271(11)
 0.3729(11)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C206-C203
 -2.8 with sigma of 0.02
 C106-C104 \\sim C203-C201
 with sigma of 0.02
 O101-C104 \\sim O201-C201
 with sigma of 0.02
 O101-C101 \\sim O201-C204
 with sigma of 0.02
 C104-C105 \\sim C201-C202
 with sigma of 0.02
 C102-C101 \\sim C205-C204
 with sigma of 0.02
 C101-C103 \\sim C204-C206
 with sigma of 0.02
 C106-O101 \\sim C203-O201
 with sigma of 0.04
 C106-C105 \\sim C203-C202
 with sigma of 0.04
 O101-C102 \\sim O201-C205
 with sigma of 0.04
 O101-C105 \\sim O201-C202
 with sigma of 0.04
 O101-C103 \\sim O201-C206
 with sigma of 0.04
 C104-C101 \\sim C201-C204
 with sigma of 0.04
 C102-C103 \\sim C205-C206
 with sigma of 0.04
 Cl96-C94 \\sim Cl95-C94 \\sim Cl94-C94
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
O201 \\sim C205 \\sim C204 \\sim C206 \\sim C201 \\sim C203 \\sim C202 \\sim
Cl91 \\sim C91 \\sim Cl92 \\sim Cl93 \\sim O101 \\sim C106 \\sim C104 \\sim
C105 \\sim C101 \\sim C102 \\sim C103 \\sim Cl95 \\sim Cl94 \\sim C94 \\sim
Cl96: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
Uanis(C204) = Uanis(C205) = Uanis(O201) = Uanis(C206) = Uanis(C201) =
Uanis(C203) = Uanis(C202)
5. Rigid body (RIGU) restrains
 C201, C205, C204, O201, C206, C203, C202, Cl91, C91, Cl92, Cl93, Cl94, C94,
 Cl95, Cl96, C101, C106, C104, O101, C105, C102, C103
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
6. Others
 Sof(Cl94)=Sof(Cl95)=Sof(Cl96)=Sof(C94)=Sof(H94)=Sof(C205)=Sof(H20A)=Sof(H20B)=
 Sof(H20C)=Sof(C203)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C201)=Sof(H201)=
 Sof(O201)=Sof(C202)=Sof(H20G)=Sof(H20H)=Sof(H20I)=Sof(C204)=Sof(H204)=
 Sof(C206)=Sof(H20J)=Sof(H20K)=Sof(H20L)=1-FVAR(1)
 Sof(Cl91)=Sof(Cl92)=Sof(Cl93)=Sof(C91)=Sof(H91)=Sof(C106)=Sof(H10A)=Sof(H10B)=
 Sof(H10C)=Sof(O101)=Sof(C104)=Sof(H104)=Sof(C102)=Sof(H10D)=Sof(H10E)=
 Sof(H10F)=Sof(C101)=Sof(H101)=Sof(C105)=Sof(H10G)=Sof(H10H)=Sof(H10I)=
 Sof(C103)=Sof(H10J)=Sof(H10K)=Sof(H10L)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C81(H81), C91(H91), C104(H104), C101(H101), C94(H94), C201(H201), C204(H204)
7.b Me refined with riding coordinates:
 C205(H20A,H20B,H20C), C203(H20D,H20E,H20F), C202(H20G,H20H,H20I), C206(H20J,
 H20K,H20L)
7.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), C1(H1A), C2(H2A), C7(H7), C8(H8), C13(H13), C16(H16),
 C17(H17), C18(H18), C21(H21), C22(H22), C23(H23), C25(H25), C28(H28), C29(H29),
  C30(H30), C33(H33), C34(H34), C35(H35), C37(H37), N41(H41), N42(H42),
 C41(H41A), C42(H42A), C47(H47), C48(H48), C53(H53), C56(H56), C57(H57),
 C58(H58), C61(H61), C62(H62), C63(H63), C65(H65), C68(H68), C69(H69), C70(H70),
  C73(H73), C74(H74), C75(H75), C77(H77)
7.d Idealised Me refined as rotating group:
 C106(H10A,H10B,H10C), C102(H10D,H10E,H10F), C105(H10G,H10H,H10I), C103(H10J,
 H10K,H10L)
;
_shelx_res_checksum              8321
_shelx_hkl_checksum              9228
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in oil'
_olex2_submission_original_sample_id AI-phen
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.835
_oxdiff_exptl_absorpt_empirical_full_min 0.531
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2