Why europium acylpyrazolonates are bad phosphors: lessons learned from the study of ionic and polymer complexes [MLnQ<sub>4</sub>], M = NEt<sub>4</sub><sup>+</sup>, Ag<sup/>.
Belousov, Yuriy A.; Polikovsky, Trofim A.; Metlin, Mikhail T.; Shikin, Daniil D.; Gontcharenko, Victoria E.; Lyssenko, Konstanin A.; Drozdov, Andrey A.; Korshunov, Vladislav M.; Taydakov, Ilya V.; Marchetti, Fabio; Pettinari, Claudio; Dalton transactions (Cambridge, England : 2003) 55 (2026) 3087–3100; doi:10.1039/d5dt02746b

data_7720241
_publ_section_title
;
 Why europium acylpyrazolonates are bad phosphors: lessons learned from
 the study of ionic and polymer complexes [MLnQ<sub>4</sub>], M =
 NEt<sub>4</sub><sup>+</sup>, Ag<sup/>.
;
_journal_issue                   7
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              3087
_journal_page_last               3100
_journal_paper_doi               10.1039/d5dt02746b
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C68 H52 Ag Gd N8 O8, 1.75(C2 H3 N)'
_chemical_formula_sum            'C71.5 H57.25 Ag Gd N9.75 O8'
_chemical_formula_weight         1446.14
_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             2024-07-24
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-07-29 deposited with the CCDC.	2026-01-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 113.0310(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.9878(3)
_cell_length_b                   29.1643(6)
_cell_length_c                   16.7245(3)
_cell_measurement_reflns_used    8590
_cell_measurement_temperature    110.00
_cell_measurement_theta_max      24.88
_cell_measurement_theta_min      2.48
_cell_volume                     6278.9(2)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      110.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker D8 Quest with Photon III Detector'
_diffrn_measurement_method       '\f and \w shutterless scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0866
_diffrn_reflns_av_unetI/netI     0.0756
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            53041
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.995
_diffrn_reflns_theta_min         1.496
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.425
_exptl_absorpt_correction_T_max  0.6478
_exptl_absorpt_correction_T_min  0.5660
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1513 before and 0.0685 after correction.
The Ratio of minimum to maximum transmission is 0.8737.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.530
_exptl_crystal_description       block
_exptl_crystal_F_000             2918
_exptl_crystal_size_max          0.099
_exptl_crystal_size_mid          0.098
_exptl_crystal_size_min          0.097
_refine_diff_density_max         1.391
_refine_diff_density_min         -0.751
_refine_diff_density_rms         0.118
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     795
_refine_ls_number_reflns         13696
_refine_ls_number_restraints     80
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0734
_refine_ls_R_factor_gt           0.0552
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0264P)^2^+17.6062P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1111
_refine_ls_wR_factor_ref         0.1223
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10643
_reflns_number_total             13696
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02746b2.cif
_cod_data_source_block           q_CCDC3
_cod_original_formula_sum        'C71.50 H57.25 Ag Gd N9.75 O8'
_cod_database_code               7720241
_shelx_shelxl_version_number     2018/3
_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
2. Restrained distances
 C54A-C55A = C55-C54
 1.5 with sigma of 0.02
 N2SA-C3SA = N2S-C3S
 1.13 with sigma of 0.02
 C4SA-C3SA = C4S-C3S
 1.47 with sigma of 0.02
 N2SA-C4SA
 2.6 with sigma of 0.02
 N2S-C4S
 2.6 with sigma of 0.02
 O8A-C56A \\sim O7-C52 \\sim O7A-C52A \\sim O8-C56
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C24) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C27)
\\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq,
Uanis(C43) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C45) \\sim Ueq: with sigma of
0.004 and sigma for terminal atoms of 0.008
Uanis(Ag1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.006
Uanis(N2SA) = Uanis(N2S)
Uanis(C3S) = Uanis(C3SA) = Uanis(C4SA) = Uanis(C4S)
Uanis(N2SA) = Uanis(C3SA) = Uanis(C4SA) = Uanis(N2S) = Uanis(C3S) = Uanis(C4S)
Uanis(C57) = Uanis(C62) = Uanis(C61) = Uanis(C58) = Uanis(C59) = Uanis(C60) =
Uanis(C64A) = Uanis(C63A) = Uanis(C68A) = Uanis(C67A) = Uanis(C66A) =
Uanis(C65A)
Uanis(C54A) = Uanis(C54) = Uanis(C53A) = Uanis(C53)
Uanis(C52A) = Uanis(C56) = Uanis(C52) = Uanis(C56A)
Uanis(C63) = Uanis(C64) = Uanis(C65) = Uanis(C66) = Uanis(C67) = Uanis(C68) =
Uanis(C57A) = Uanis(C58A) = Uanis(C59A) = Uanis(C60A) = Uanis(C61A) =
Uanis(C62A)
Uanis(N8) = Uanis(N7) = Uanis(N7A) = Uanis(N8A)
Uanis(C55A) = Uanis(C55)
4. Others
 Fixed Sof: O8(0.7) O7(0.7) C54(0.7) N8(0.7) C56(0.7) C63(0.7) C64(0.7)
 H64(0.7) C65(0.7) H65(0.7) C66(0.7) H66(0.7) C67(0.7) H67(0.7) C68(0.7)
 H68(0.7) C52(0.7) C53(0.7) N7(0.7) C57(0.7) N2S(0.5) C62(0.7) H62(0.7)
 C61(0.7) H61(0.7) C55(0.7) H55A(0.7) H55B(0.7) H55C(0.7) C58(0.7) H58(0.7)
 C59(0.7) H59(0.7) C60(0.7) H60(0.7) N8A(0.3) C64A(0.3) H64A(0.3) C63A(0.3)
 C68A(0.3) H68A(0.3) C67A(0.3) H67A(0.3) C66A(0.3) H66A(0.3) C65A(0.3)
 H65A(0.3) C56A(0.3) C52A(0.3) N7A(0.3) C53A(0.3) O8A(0.3) O7A(0.3) C55A(0.3)
 H55D(0.3) H55E(0.3) H55F(0.3) C57A(0.3) C58A(0.3) H58A(0.3) C59A(0.3)
 H59A(0.3) C60A(0.3) H60A(0.3) C61A(0.3) H61A(0.3) C62A(0.3) H62A(0.3)
 C54A(0.3) C3S(0.5) C4S(0.5) H4SA(0.5) H4SB(0.5) H4SC(0.5) C3SA(0.25)
 N2SA(0.25) C4SA(0.25) H4SD(0.25) H4SE(0.25) H4SF(0.25)
5.a Aromatic/amide H refined with riding coordinates:
 C30(H30), C34(H34), C13(H13), C7(H7), C17(H17), C51(H51), C24(H24), C33(H33),
 C14(H14), C16(H16), C15(H15), C47(H47), C11(H11), C10(H10), C50(H50), C48(H48),
  C31(H31), C32(H32), C9(H9), C49(H49), C25(H25), C45(H45), C8(H8), C41(H41),
 C64(H64), C65(H65), C66(H66), C67(H67), C68(H68), C28(H28), C26(H26), C44(H44),
  C43(H43), C42(H42), C27(H27), C62(H62), C61(H61), C58(H58), C59(H59),
 C60(H60), C64A(H64A), C68A(H68A), C67A(H67A), C66A(H66A), C65A(H65A),
 C58A(H58A), C59A(H59A), C60A(H60A), C61A(H61A), C62A(H62A)
5.b Fitted hexagon refined as free rotating group:
 C63(C64,C65,C66,C67,C68), C64A(C63A,C68A,C67A,C66A,C65A), C57A(C58A,C59A,C60A,
 C61A,C62A)
5.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C21(H21A,H21B,H21C), C38(H38A,H38B,H38C), C2S(H2SA,H2SB,
 H2SC), C55(H55A,H55B,H55C), C55A(H55D,H55E,H55F), C4S(H4SA,H4SB,H4SC),
 C4SA(H4SD,H4SE,H4SF)
;
_shelx_res_checksum              41926
_olex2_submission_special_instructions 'No special instructions were received'