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_7720237
_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 N8 O8 Sm, 1.75(C2 H3 N)'
_chemical_formula_sum            'C71.5 H57.25 Ag N9.75 O8 Sm'
_chemical_formula_weight         1439.24
_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                 113.1330(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.0221(5)
_cell_length_b                   29.1667(11)
_cell_length_c                   16.7398(6)
_cell_measurement_reflns_used    4603
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      23.56
_cell_measurement_theta_min      2.48
_cell_volume                     6295.7(4)
_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      100.00
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.0908
_diffrn_reflns_av_unetI/netI     0.0807
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            41620
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.758
_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    1.301
_exptl_absorpt_correction_T_max  0.6478
_exptl_absorpt_correction_T_min  0.5630
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1526 before and 0.0683 after correction.
The Ratio of minimum to maximum transmission is 0.8691.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.518
_exptl_crystal_description       block
_exptl_crystal_F_000             2910
_exptl_crystal_size_max          0.105
_exptl_crystal_size_mid          0.104
_exptl_crystal_size_min          0.103
_refine_diff_density_max         1.295
_refine_diff_density_min         -0.710
_refine_diff_density_rms         0.118
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     813
_refine_ls_number_reflns         11078
_refine_ls_number_restraints     89
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0764
_refine_ls_R_factor_gt           0.0553
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0321P)^2^+18.9272P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1145
_refine_ls_wR_factor_ref         0.1266
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8455
_reflns_number_total             11078
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02746b2.cif
_cod_data_source_block           q_CCDC1
_cod_original_formula_sum        'C71.50 H57.25 Ag N9.75 O8 Sm'
_cod_database_code               7720237
_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
 C55A-C54A = C54-C55
 1.51 with sigma of 0.02
 N2S-C3S
 1.14 with sigma of 0.02
 C3S-N2S
 1.137 with sigma of 0.01
 C3S-C4S
 1.456 with sigma of 0.01
 C4S-N2S
 2.593 with sigma of 0.02
 N2SA-C3SA = N2S-C3S
 1.15 with sigma of 0.002
 C4S-C3S = C4SA-C3SA
 1.45 with sigma of 0.002
 N2SA-C4SA
 2.6 with sigma of 0.002
 N2S-C4S
 2.6 with sigma of 0.002
 N2S-C4S
 2.59 with sigma of 0.04
 N7A-C54A \\sim N7-C54
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N2S \\sim C3S \\sim C4S: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(C26) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C24)
\\sim Ueq, Uanis(C25) \\sim Ueq: with sigma of 0.003 and sigma for terminal
atoms of 0.006
Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C44)
\\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(C54) = Uanis(C54A)
Uanis(N7A) = Uanis(N8) = Uanis(N7) = Uanis(N8A)
Uanis(C55) = Uanis(C55A)
Uanis(C53) = Uanis(C53A)
Uanis(C52A) = Uanis(C56) = Uanis(C52) = Uanis(C56A)
Uanis(O7A) = Uanis(O8) = Uanis(O7) = Uanis(O8A)
Uanis(C63A) = Uanis(C57) = Uanis(C63) = Uanis(C57A)
Uanis(C62A) = Uanis(C68) = Uanis(C58A) = Uanis(C64) = Uanis(C68A) = Uanis(C62)
= Uanis(C64A) = Uanis(C58)
Uanis(C67) = Uanis(C66) = Uanis(C65) = Uanis(C61A) = Uanis(C60A) = Uanis(C59A)
= Uanis(C61) = Uanis(C60) = Uanis(C59) = Uanis(C65A) = Uanis(C66A) = Uanis(C67A)
Uanis(C3SA) = Uanis(C3S)
Uanis(C4SA) = Uanis(C4S)
Uanis(N2S) = Uanis(N2SA)
4. Rigid body (RIGU) restrains
 N2S, C3S, C4S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: O8(0.7) O7(0.7) C54A(0.3) N8(0.7) C64(0.7) H64(0.7) N7(0.7)
 C56(0.7) C52(0.7) C57(0.7) C63(0.7) C53(0.7) C67(0.7) H67(0.7) C66(0.7)
 H66(0.7) C65(0.7) H65(0.7) C68(0.7) H68(0.7) C62(0.7) H62(0.7) C61(0.7)
 H61(0.7) C55(0.7) H55A(0.7) H55B(0.7) H55C(0.7) C60(0.7) H60(0.7) C59(0.7)
 H59(0.7) C58(0.7) H58(0.7) N8A(0.3) C56A(0.3) C53A(0.3) N7A(0.3) O8A(0.3)
 C52A(0.3) C55A(0.3) H55D(0.3) H55E(0.3) H55F(0.3) O7A(0.3) C57A(0.3) C62A(0.3)
 H62A(0.3) C61A(0.3) H61A(0.3) C60A(0.3) H60A(0.3) C59A(0.3) H59A(0.3)
 C58A(0.3) H58A(0.3) C63A(0.3) C64A(0.3) H64A(0.3) C65A(0.3) H65A(0.3)
 C66A(0.3) H66A(0.3) C67A(0.3) H67A(0.3) C68A(0.3) H68A(0.3) C54(0.7) N2S(0.5)
 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)
6.a Aromatic/amide H refined with riding coordinates:
 C7(H7), C30(H30), C34(H34), C51(H51), C13(H13), C24(H24), C14(H14), C48(H48),
 C47(H47), C33(H33), C50(H50), C17(H17), C15(H15), C16(H16), C49(H49), C10(H10),
  C31(H31), C8(H8), C11(H11), C45(H45), C64(H64), C28(H28), C32(H32), C9(H9),
 C41(H41), C25(H25), C26(H26), C44(H44), C43(H43), C67(H67), C27(H27), C66(H66),
  C65(H65), C42(H42), C68(H68), C62(H62), C61(H61), C60(H60), C59(H59),
 C58(H58), C62A(H62A), C61A(H61A), C60A(H60A), C59A(H59A), C58A(H58A),
 C64A(H64A), C65A(H65A), C66A(H66A), C67A(H67A), C68A(H68A)
6.b Fitted hexagon refined as free rotating group:
 C57A(C62A,C61A,C60A,C59A,C58A), C63A(C64A,C65A,C66A,C67A,C68A)
6.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              91032
_olex2_submission_special_instructions 'No special instructions were received'