Reduced quenching effect of pyridine ligands in highly luminescent Ln(III) complexes: the role of tertiary amide linkers
Kocsi, Daniel; Kovacs, Daniel; Wells, Jordann A. L.; Borbas, Eszter; Dalton Transactions  (2021) –; doi:10.1039/D1DT02893F

data_7708629
_publ_section_title
;
 Reduced quenching effect of pyridine ligands in highly luminescent
 Ln(III) complexes: the role of tertiary amide linkers
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT02893F
_journal_year                    2021
_chemical_formula_moiety
'(C34 H34 Gd1 N7 O8)(Gd0.375 1.775(H2O)), 11.025(H2 O), 1.125(Cl)'
_chemical_formula_sum            'C34 H59.6 Cl1.12 Gd1.38 N7 O20.8'
_chemical_formula_weight         1155.99
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-10-21
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2021-10-24 deposited with the CCDC.	2021-10-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.168(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.3377(6)
_cell_length_b                   26.9746(6)
_cell_length_c                   16.0949(4)
_cell_measurement_reflns_used    9121
_cell_measurement_temperature    170.0(10)
_cell_measurement_theta_max      25.35
_cell_measurement_theta_min      2.39
_cell_volume                     9514.3(4)
_computing_cell_refinement       'BRUKER APEX-III'
_computing_data_collection       'BRUKER APEX-III'
_computing_data_reduction        'BRUKER APEX-III'
_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 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      170.0(10)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0491
_diffrn_reflns_av_unetI/netI     0.0211
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            155499
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.483
_diffrn_reflns_theta_min         1.197
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.052
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6598
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker 2014/5) was used for absorption correction.
wR2(int) was o.1370 before and 0.0472 after correction.
The Ratio of minimum to maximum transmission is 0.8843.
The \I/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.585
_exptl_crystal_description       plate
_exptl_crystal_F_000             4527
_exptl_crystal_preparation
'See associated manuscript for synthetic details.'
_exptl_crystal_recrystallization_method
'Diffusion of glyme vapour into aqueous solution.'
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.455
_refine_diff_density_min         -0.923
_refine_diff_density_rms         0.101
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.137
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     851
_refine_ls_number_reflns         10892
_refine_ls_number_restraints     802
_refine_ls_restrained_S_all      1.110
_refine_ls_R_factor_all          0.0597
_refine_ls_R_factor_gt           0.0402
_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^)+(0.0480P)^2^+42.2115P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1001
_refine_ls_wR_factor_ref         0.1175
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8622
_reflns_number_total             10892
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt02893f2.cif
_cod_data_source_block           eb19021
_cod_original_formula_sum        'C34 H59.6 Cl1.12 Gd1.38 N7 O20.80'
_cod_database_code               7708629
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.684
_shelx_estimated_absorpt_t_min   0.372
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups, All O(H,H,H,H,H,H,H,H) groups
2. Shared sites
{O26S, Gd2}
3. Restrained distances
 O7S-H7SA = O7S-H7SB
 0.84 with sigma of 0.02
 O12S-H12C = O12S-H12D
 0.84 with sigma of 0.02
 C33-H33 = O14S-H14A = O14S-H14B
 0.84 with sigma of 0.02
 O8S-H8SB = O8S-H8SA
 0.84 with sigma of 0.02
 O2S-H2SB = O2S-H2SA
 0.84 with sigma of 0.02
 H7SB-H7SA
 1.34 with sigma of 0.02
 H12C-H12D
 1.34 with sigma of 0.02
 H14A-H14B
 1.34 with sigma of 0.02
 H8SB-H8SA
 1.34 with sigma of 0.02
 H2SA-H2SB
 1.34 with sigma of 0.02
 N7A-C32 \\sim N7B-C32
 with sigma of 0.02
 N7A-C31A \\sim N7B-C31B
 with sigma of 0.02
 O8A-C31A \\sim O8B-C31B
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
N7A \\sim C31A \\sim C30A \\sim C29A \\sim C28 \\sim C32 \\sim O8A \\sim C34A
\\sim O8B \\sim C30B \\sim C31B \\sim N7B \\sim C29B \\sim C34B: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C4A \\sim N4A \\sim C8A \\sim C7A \\sim C6A \\sim C5A \\sim C3A \\sim C6B \\sim
C4B \\sim C7B \\sim C5B \\sim C3B \\sim O2A \\sim C9A \\sim O3A \\sim O2B \\sim
O3B \\sim C9B \\sim N4B \\sim C8B: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
O15S \\sim O9: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
Uanis(O26S) = Uanis(Gd2)
5. Rigid body (RIGU) restrains
 O2A, C9A, O3A, C4A, N4A, C8A, C7A, C6A, C5A, C3A, O2B, O3B, C9B, C6B, N4B,
 C4B, C7B, C5B, C3B, C8B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N7A, C31A, C30A, C29A, C28, C32, O8A, C34A, O8B, C30B, C31B, N7B, C29B, C34B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O15S, O9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(O9)=1-FVAR(1)
 Sof(O15S)=FVAR(1)
 Fixed Sof: Gd2(0.375) O2A(0.5) C9A(0.5) N7A(0.5) H7A(0.5) C31A(0.5) C30A(0.5)
 H30A(0.5) C29A(0.5) O3A(0.5) C4A(0.5) N4A(0.5) C8A(0.5) C7A(0.5) H7AA(0.5)
 C6A(0.5) H6A(0.5) C5A(0.5) H5A(0.5) C3A(0.5) H3AA(0.5) H3AB(0.5) O8A(0.5)
 C34A(0.5) H34A(0.5) H34B(0.5) H34C(0.5) O3S(0.4) O2S(0.6) O4S(0.5) O8S(0.65)
 Cl1(0.375) O11S(0.65) O9S(0.35) O12S(0.45) O7S(0.6) O25S(0.625) O5S(0.375)
 O6S(0.4) O8B(0.5) C30B(0.5) H30B(0.5) C31B(0.5) N7B(0.5) H7B(0.5) C29B(0.5)
 C34B(0.5) H34D(0.5) H34E(0.5) H34F(0.5) O2B(0.5) O3B(0.5) C9B(0.5) C6B(0.5)
 H6B(0.5) N4B(0.5) C4B(0.5) C7B(0.5) H7BA(0.5) C5B(0.5) H5B(0.5) C3B(0.5)
 H3BA(0.5) H3BB(0.5) C8B(0.5) O24S(0.65) O10S(0.45) Cl2(0.75) O14S(0.4)
 O18S(0.4) O17S(0.45) O23S(0.35) O16S(0.55) O19S(0.6) O21S(0.5) O13S(0.3)
 O20S(0.3) O22S(0.125) O26S(0.125) H7SA(0.6) H7SB(0.6) H12C(0.45) H12D(0.45)
 H14A(0.4) H14B(0.4) H8SA(0.65) H8SB(0.65) H2SA(0.6) H2SB(0.6)
7.a Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C12(H12A,H12B), C23(H23A,H23B), C20(H20A,H20B), C1(H1A,H1B),
 C10(H10A,H10B), C11(H11A,H11B), C19(H19A,H19B), C2(H2A,H2B), C3A(H3AA,H3AB),
 C3B(H3BA,H3BB)
7.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C33(H33), C16(H16), N7A(H7A), C30A(H30A), C15(H15), C7A(H7AA),
 C6A(H6A), C5A(H5A), C27(H27), C26(H26), C30B(H30B), N7B(H7B), C6B(H6B),
 C7B(H7BA), C5B(H5B)
7.c Fitted hexagon refined as free rotating group:
 N7A(C31A,C30A,C29A,C28,C32), C4A(N4A,C8A,C7A,C6A,C5A)
7.d Idealised Me refined as rotating group:
 C34A(H34A,H34B,H34C), C34B(H34D,H34E,H34F)
;
_shelx_res_checksum              5779
_olex2_exptl_crystal_mounting_method 'Glass capillary/fomblin oil (high MW)'
_olex2_submission_original_sample_id EB19021
_olex2_submission_special_instructions 'No special instructions were received'