Tailoring Exciplex Formation in Metal-Induced Supramolecular Organization
Le-Hoang, Giau; Guénée, Laure; Piguet, Claude; Dalton Transactions  (2026) –; doi:10.1039/D6DT00490C

data_7720825
_publ_section_title
;
 Tailoring Exciplex Formation in Metal-Induced Supramolecular Organization
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D6DT00490C
_journal_year                    2026
_chemical_formula_moiety
'C82 H64 Eu F18 N5 O6, 0.5(C H2 Cl2), 1.5[C6H14]'
_chemical_formula_sum            'C91.5 H86 Cl Eu F18 N5 O6'
_chemical_formula_weight         1881.06
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-01-13
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2026-02-17 deposited with the CCDC.	2026-04-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.09750(11)
_cell_length_b                   14.10417(6)
_cell_length_c                   30.15350(18)
_cell_measurement_reflns_used    33308
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      75.2650
_cell_measurement_theta_min      2.9320
_cell_volume                     8547.27(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.981
_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   -102.00 -64.00   0.50    2.00    --  -57.24 -15.00  60.00   76
  2  \w    -50.00 -24.00   0.50    2.00    --  -57.24 -15.00 -30.00   52
  3  \w    -51.00 -25.00   0.50    2.00    --  -57.24 -15.00  60.00   52
  4  \w    -60.00 -32.00   0.50    2.00    --  -57.24 -15.00  90.00   56
  5  \w    -77.00 -25.00   0.50    2.00    --  -57.24 126.00 159.00  104
  6  \w   -100.00 -74.00   0.50    2.00    --  -57.24 -15.00  90.00   52
  7  \w    -96.00 -64.00   0.50    2.00    --  -57.24 -15.00 -30.00   64
  8  \w     22.00  53.00   0.50    2.00    --   60.25 -94.00   0.00   62
  9  \w     21.00  46.00   0.50    2.00    --   60.25 -94.00 -30.00   50
 10  \w     23.00  68.00   0.50    2.00    --   60.25 -94.00  90.00   90
 11  \w     47.00  98.00   0.50    2.00    --   74.77-125.00-180.00  102
 12  \w     54.00  86.00   0.50    2.00    --   79.86 -94.00-150.00   64
 13  \w     42.00  79.00   0.50    2.00    --   79.86 -94.00   0.00   74
 14  \w     49.00  87.00   0.50    2.00    --   79.86 -94.00-120.00   76
 15  \w     47.00 110.00   0.50    2.00    --   79.86  15.00  30.00  126
 16  \w     49.00 124.00   0.50    2.00    --   79.86  15.00  90.00  150
 17  \w     68.00 107.00   0.50    2.00    --   79.86  15.00 -30.00   78
 18  \w     40.00  73.00   0.50    2.00    --   79.86 -94.00 -90.00   66
 19  \w     42.00  75.00   0.50    2.00    --   79.86 -94.00 -30.00   66
 20  \w     81.00 109.00   0.50    2.00    --   83.50-122.00 134.06   56
 21  \w     48.00 112.00   0.50    2.00    --   83.50  19.00 -75.72  128
 22  \w     46.00  88.00   0.50    2.00    --   83.50-124.00 158.14   84
 23  \w     44.00  69.00   0.50    2.00    --   83.50-122.00 134.06   50
 24  \w     60.00  86.00   0.50    2.00    --   83.50-142.00-113.89   52
 25  \w     92.00 124.00   0.50    2.00    --   83.50-142.00-113.89   64
 26  \w     82.00 115.00   0.50    2.00    --   83.50-129.00-159.18   66
 27  \w     39.00  65.00   0.50    2.00    --   83.50-129.00-159.18   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0652827000
_diffrn_orient_matrix_UB_12      -0.0055054000
_diffrn_orient_matrix_UB_13      0.0266298000
_diffrn_orient_matrix_UB_21      0.0401122000
_diffrn_orient_matrix_UB_22      0.0047271000
_diffrn_orient_matrix_UB_23      -0.0434852000
_diffrn_orient_matrix_UB_31      0.0015676000
_diffrn_orient_matrix_UB_32      0.1090069000
_diffrn_orient_matrix_UB_33      0.0032118000
_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  0.0236
_diffrn_reflns_av_unetI/netI     0.0155
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            69809
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.967
_diffrn_reflns_theta_min         2.931
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.373
_exptl_absorpt_correction_T_max  0.609
_exptl_absorpt_correction_T_min  0.372
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.462
_exptl_crystal_description       prism
_exptl_crystal_F_000             3840
_exptl_crystal_size_max          0.225
_exptl_crystal_size_mid          0.147
_exptl_crystal_size_min          0.092
_refine_diff_density_max         1.494
_refine_diff_density_min         -0.668
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     521
_refine_ls_number_reflns         8753
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0677
_refine_ls_R_factor_gt           0.0636
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1105P)^2^+17.2334P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1829
_refine_ls_wR_factor_ref         0.1869
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7904
_reflns_number_total             8753
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00490c2.cif
_cod_data_source_block           L1Eu
_cod_original_formula_sum        'C91.50 H86 Cl Eu F18 N5 O6'
_cod_database_code               7720825
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C85.50 H72 N5 O6 F18 Cl1 Eu1 '
_shelx_estimated_absorpt_t_max   0.592
_shelx_estimated_absorpt_t_min   0.328
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C13B-C14B
 1.53 with sigma of 0.02
 C13B-C15B
 1.53 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uiso(C15B) = Uiso(C15A)
Uiso(C13B) = Uiso(C13A)
Uiso(C14B) = Uiso(C14A)
4. Others
 Sof(H12C)=Sof(H12D)=Sof(C13B)=Sof(H13B)=Sof(C14B)=Sof(H14D)=Sof(H14E)=
 Sof(H14F)=Sof(C15B)=Sof(H15D)=Sof(H15E)=Sof(H15F)=1-FVAR(1)
 Sof(H12A)=Sof(H12B)=Sof(C13A)=Sof(H13A)=Sof(C14A)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=Sof(C15A)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(1)
 Fixed Sof: Cl1(0.25) Cl2(0.25) C43(0.25) H43A(0.25) H43B(0.25)
5.a Riding coordinates:
 C14A(H14A,H14B,H14C), C14B(H14D,H14E,H14F)
5.b Ternary CH refined with riding coordinates:
 C13A(H13A), C13B(H13B)
5.c Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12C,H12D), C12(H12A,H12B), C16(H16A,H16B), C17(H17A,
 H17B), C18(H18A,H18B), C43(H43A,H43B)
5.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C6(H6), C8(H8), C9(H9), C21(H21), C22(H22), C24(H24),
 C25(H25), C26(H26), C28(H28), C29(H29), C31(H31), C32(H32), C37(H37), C42(H42)
5.e Idealised Me refined as rotating group:
 C15A(H15A,H15B,H15C), C15B(H15D,H15E,H15F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 288 electrons were 
found in a volume of 960\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1.5[C6H14] per formula unit 
which account for 300 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              26502
_shelx_hkl_checksum              23951
_shelx_fab_checksum              29496
_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 1.258
_oxdiff_exptl_absorpt_empirical_full_min 0.714