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_7708630
_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 N7 O8 Tb1)(Tb0.425 2.35(H2 O)), 1.275(Cl), 7.8(H2 O)'
_chemical_formula_sum            'C34 H54.3 Cl1.27 N7 O18.15 Tb1.42'
_chemical_formula_weight         1122.24
_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
_audit_creation_date             2021-10-24
_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                 101.195(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.2162(18)
_cell_length_b                   26.8066(18)
_cell_length_c                   16.0827(12)
_cell_measurement_reflns_used    9933
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      22.72
_cell_measurement_theta_min      2.41
_cell_volume                     9395.7(12)
_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(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_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  0.0826
_diffrn_reflns_av_unetI/netI     0.0393
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            131933
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.327
_diffrn_reflns_theta_min         1.519
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.282
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6076
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1274 before and 0.0568 after correction.
The Ratio of minimum to maximum transmission is 0.8148.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.567
_exptl_crystal_description       plate
_exptl_crystal_F_000             4418
_exptl_crystal_preparation
'see associated publication for synthetic details'
_exptl_crystal_recrystallization_method
'diffusion of glyme vapours in aqueous solutions'
_exptl_crystal_size_max          0.7
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.284
_refine_diff_density_min         -1.363
_refine_diff_density_rms         0.137
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.138
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     844
_refine_ls_number_reflns         11693
_refine_ls_number_restraints     657
_refine_ls_restrained_S_all      1.112
_refine_ls_R_factor_all          0.0828
_refine_ls_R_factor_gt           0.0578
_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^)+(0.0512P)^2^+100.7297P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1436
_refine_ls_wR_factor_ref         0.1557
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8795
_reflns_number_total             11693
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt02893f2.cif
_cod_data_source_block           eb19022
_cod_database_code               7708630
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.804
_shelx_estimated_absorpt_t_min   0.298
_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, All Cl(H,H,H,H,H,H,H,H) groups
2. Shared sites
{O19S, Tb2}
3. Restrained distances
 O19S-H4SB
 2.3 with sigma of 0.02
 O3B-C9B
 1.2 with sigma of 0.02
 O8B-C28B
 1.15 with sigma of 0.02
 O8A-C31A
 1.15 with sigma of 0.02
 O14S-H14A = O14S-H14B
 0.84 with sigma of 0.01
 O13S-H13B = O13S-H13A
 0.84 with sigma of 0.01
 O1S-H1SA = O1S-H1SB
 0.84 with sigma of 0.01
 O4S-H4SB = O4S-H4SA
 0.84 with sigma of 0.01
 H14A-H14B
 1.34 with sigma of 0.02
 H13A-H13B
 1.34 with sigma of 0.02
 H1SB-H1SA
 1.34 with sigma of 0.02
 H4SB-H4SA
 1.34 with sigma of 0.02
 C3B-C4B \\sim C3A-C4A
 with sigma of 0.02
 N2B-C3B \\sim N2A-C3A
 with sigma of 0.02
4. Rigid bond restraints
 N6A, N6B, C23, C24, O7, O6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C33A \\sim C25A \\sim C26A \\sim C27A \\sim C28A \\sim C32A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C3A \\sim C4A \\sim N3A \\sim C8A \\sim C9A \\sim O3A \\sim C7A \\sim C6A \\sim
C5A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
O2S \\sim O3S \\sim Tb2: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
N6A \\sim C33A \\sim C25A \\sim C26A \\sim C27A \\sim C28A \\sim C32A \\sim N7A
\\sim C31A \\sim C30A \\sim C29A \\sim C34A \\sim O8A: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C26B \\sim C25B \\sim C32B \\sim N7B \\sim C27B \\sim C31B \\sim C30B \\sim
C29B \\sim C28B \\sim C33B \\sim C34B \\sim O8B: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C11A \\sim C10A \\sim N2A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C11B \\sim C10B \\sim N2B: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
N6A \\sim N6B \\sim C23 \\sim C24 \\sim O7 \\sim O6: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C8B \\sim N3B \\sim C4B \\sim C5B \\sim C6B \\sim C7B: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(O19S) = Uanis(Tb2)
Uanis(C3B) = Uanis(C3A)
Uanis(N6A) = Uanis(N6B)
Uanis(C10B) = Uanis(C11B)
6. Rigid body (RIGU) restrains
 O2S, O3S, Tb2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C33A, C25A, C26A, C27A, C28A, C32A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C3A, C4A, N3A, C8A, C9A, O3A, C7A, C6A, C5A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N6A, C33A, C25A, C26A, C27A, C28A, C32A, N7A, C31A, C30A, C29A, C34A, O8A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26B, C25B, C32B, N7B, C27B, C31B, C30B, C29B, C28B, C33B, C34B, O8B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11A, C10A, N2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11B, C10B, N2B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C8B, N3B, C4B, C5B, C6B, C7B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Fixed Sof: Tb2(0.425) N6A(0.5) N2A(0.5) O2A(0.5) H23C(0.5) H23D(0.5)
 H23A(0.5) H23B(0.5) N3A(0.5) C8A(0.5) C7A(0.5) H7A(0.5) C6A(0.5) H6A(0.5)
 C5A(0.5) H5A(0.5) C4A(0.5) O1S(0.85) C9A(0.5) H2AA(0.5) H2AB(0.5) H2BC(0.5)
 H2BD(0.5) C11A(0.5) H11A(0.5) H11B(0.5) O3A(0.5) C10A(0.5) H10A(0.5) H10B(0.5)
 C3A(0.5) H3AA(0.5) H3AB(0.5) C33A(0.5) H33A(0.5) C25A(0.5) C26A(0.5) H26A(0.5)
 C27A(0.5) H27A(0.5) C28A(0.5) C32A(0.5) N7A(0.5) H7AA(0.5) C31A(0.5) C30A(0.5)
 H30A(0.5) C29A(0.5) C34A(0.5) H34A(0.5) H34B(0.5) H34C(0.5) O8A(0.5) O2S(0.5)
 O3S(0.5) C26B(0.5) H26B(0.5) C25B(0.5) C32B(0.5) H32B(0.5) N7B(0.5) H7B(0.5)
 C27B(0.5) C31B(0.5) C30B(0.5) C29B(0.5) H29B(0.5) C28B(0.5) C33B(0.5)
 H33B(0.5) C34B(0.5) H34D(0.5) H34E(0.5) H34F(0.5) N6B(0.5) O8B(0.5) C6B(0.5)
 H6B(0.5) C4B(0.5) O2B(0.5) N3B(0.5) C5B(0.5) H5B(0.5) C9B(0.5) O3B(0.5)
 C8B(0.5) C7B(0.5) H7BA(0.5) C10B(0.5) H10C(0.5) H10D(0.5) N2B(0.5) C11B(0.5)
 H11C(0.5) H11D(0.5) Cl2(0.5) Cl3(0.275) O7S(0.7) O8S(0.6) O14S(0.6) Cl1(0.35)
 C3B(0.5) H3BA(0.5) H3BB(0.5) O19S(0.075) O11S(0.375) O12S(0.6) O13S(0.4)
 O10S(0.5) O18S(0.6) O16S(0.6) O9S(0.3) O17S(0.25) O15S(0.4) O6S(0.3) Cl4(0.15)
 H14A(0.6) H14B(0.6) H13A(0.4) H13B(0.4) H1SA(0.85) H1SB(0.85)
8.a Secondary CH2 refined with riding coordinates:
 C23(H23C,H23D), C23(H23A,H23B), C12(H12A,H12B), C21(H21A,H21B), C20(H20A,
 H20B), C1(H1A,H1B), C2(H2AA,H2AB), C2(H2BC,H2BD), C11A(H11A,H11B), C19(H19A,
 H19B), C10A(H10A,H10B), C3A(H3AA,H3AB), C10B(H10C,H10D), C11B(H11C,H11D),
 C3B(H3BA,H3BB)
8.b Aromatic/amide H refined with riding coordinates:
 C7A(H7A), C6A(H6A), C5A(H5A), C16(H16), C14(H14), C15(H15), C33A(H33A),
 C26A(H26A), C27A(H27A), N7A(H7AA), C30A(H30A), C26B(H26B), C32B(H32B),
 N7B(H7B), C29B(H29B), C33B(H33B), C6B(H6B), C5B(H5B), C7B(H7BA)
8.c Fitted hexagon refined as free rotating group:
 N3A(C8A,C7A,C6A,C5A,C4A), N7B(C27B,C31B,C30B,C29B,C28B)
8.d Naphthalene refined as free rotating group:
 C33A(C25A,C26A,C27A,C28A,C32A,N7A,C31A,C30A,C29A)
8.e Idealised Me refined as rotating group:
 C34A(H34A,H34B,H34C), C34B(H34D,H34E,H34F)
;
_shelx_res_checksum              23005
_olex2_exptl_crystal_mounting_method
'crystal mounting loop/high molecular weight fomblin oil.'
_olex2_submission_special_instructions 'No special instructions were received'