Molecular light-upconversion: we have had a problem! When excited state absorption (ESA) overcomes energy transfer upconversion (ETU) in Cr(III)/Er(III) complexes.
Golesorkhi, Bahman; Taarit, Inès; Bolvin, Hélène; Nozary, Homayoun; Jiménez, Juan-Ramón; Besnard, Céline; Guénée, Laure; Fürstenberg, Alexandre; Piguet, Claude; Dalton transactions (Cambridge, England : 2003) 50 (2021) 7955–7968; doi:10.1039/d1dt01079d

data_7707159
_publ_section_title
;
 Molecular light-upconversion: we have had a problem! When excited state
 absorption (ESA) overcomes energy transfer upconversion (ETU) in
 Cr(III)/Er(III) complexes.
;
_journal_issue                   23
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              7955
_journal_page_last               7968
_journal_paper_doi               10.1039/d1dt01079d
_journal_volume                  50
_journal_year                    2021
_chemical_formula_moiety         'C21 H9 Er N3 O12, 2(C F3 O3 S), 5(C6 H16 N)'
_chemical_formula_sum            'C53 H89 Er F6 N8 O18 S2'
_chemical_formula_weight         1471.70
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-01-26
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2021-01-28 deposited with the CCDC.	2021-04-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.07717(9)
_cell_length_b                   23.7428(2)
_cell_length_c                   24.7043(2)
_cell_measurement_reflns_used    31087
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      70.5400
_cell_measurement_theta_min      2.5530
_cell_volume                     7083.86(10)
_computing_cell_refinement       'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(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 0.998
_diffrn_measured_fraction_theta_max 0.990
_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    -68.00 -13.00   0.50    5.00    --  -52.43 125.00 120.00  110
  2  \w    -74.00 -17.00   0.50    5.00    --  -52.43 125.00 -90.00  114
  3  \w    -46.00 -13.00   0.50    5.00    --  -52.43 125.00  90.00   66
  4  \w    -52.00 -24.00   0.50    5.00    --  -52.43 125.00-150.00   56
  5  \w    -91.00 -25.00   0.50    5.00    --  -52.43 -15.00  60.00  132
  6  \w    -48.00 -19.00   0.50    5.00    --  -52.43 125.00 150.00   58
  7  \w    -87.00 -31.00   0.50    5.00    --  -52.43 161.00 -66.00  112
  8  \w     45.00  91.00   0.50    5.00    --   68.69-125.00 -90.00   92
  9  \w     36.00  93.00   0.50    5.00    --   68.69-125.00 120.00  114
 10  \w     43.00  92.00   0.50    5.00    --   68.69  15.00 -90.00   98
 11  \w     61.00  86.00   0.50    5.00    --   68.69  15.00   0.00   50
 12  \w     61.00  94.00   0.50    5.00    --   68.69-125.00   0.00   66
 13  \w     56.00  96.00   0.50    5.00    --   68.69  15.00  90.00   80
 14  \w     35.00  60.00   0.50    5.00    --   68.69-125.00 150.00   50
 15  \w     36.00  86.00   0.50    5.00    --   68.69-125.00-150.00  100
 16  \w     42.00 111.00   0.50    5.00    --   68.69  15.00 150.00  138
 17  \w     79.00 106.00   0.50    5.00    --   68.69-161.00 -96.00   54
 18  \w     35.00  73.00   0.50    5.00    --   68.69-125.00  90.00   76
 19  \w     60.00  99.00   0.50    5.00    --   68.69  15.00 -60.00   78
 20  \w     38.00  65.00   0.50    5.00    --   68.69-125.00-180.00   54
 21  \w     82.00 107.00   0.50    5.00    --   68.69  15.00-180.00   50
 22  \w     60.00  92.00   0.50    5.00    --   68.69-125.00  60.00   64
;
_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      0.0770221000
_diffrn_orient_matrix_UB_12      -0.0508179000
_diffrn_orient_matrix_UB_13      -0.0091909000
_diffrn_orient_matrix_UB_21      -0.0031583000
_diffrn_orient_matrix_UB_22      -0.0131004000
_diffrn_orient_matrix_UB_23      0.0610609000
_diffrn_orient_matrix_UB_31      -0.1016124000
_diffrn_orient_matrix_UB_32      -0.0381418000
_diffrn_orient_matrix_UB_33      -0.0088323000
_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  0.0496
_diffrn_reflns_av_unetI/netI     0.0386
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            56119
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.207
_diffrn_reflns_theta_min         2.581
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.462
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78487
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.89a (Rigaku Oxford Diffraction, 2020)
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    1.380
_exptl_crystal_description       needle
_exptl_crystal_F_000             3044
_exptl_crystal_size_max          0.422
_exptl_crystal_size_mid          0.029
_exptl_crystal_size_min          0.025
_refine_diff_density_max         0.573
_refine_diff_density_min         -0.827
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
 The crystallization solution is a racemic. There seems to be some spontaneous 
 racemic resolution happening during
 crystallization. Another crystal was measured and contained 
 the other isomer but no further attempt to invertigate
 it was made.
;
_refine_ls_abs_structure_Flack   -0.007(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     922
_refine_ls_number_reflns         13503
_refine_ls_number_restraints     376
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0399
_refine_ls_R_factor_gt           0.0365
_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^)+(0.0609P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0932
_refine_ls_wR_factor_ref         0.0948
_reflns_Friedel_coverage         0.804
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.970
_reflns_number_gt                12452
_reflns_number_total             13503
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt01079d2.cif
_cod_data_source_block           1_Erdpa3_HNEt3
_cod_depositor_comments
'Adding full bibliography for 7707159--7707161.cif.'
_cod_original_cell_volume        7083.87(11)
_cod_database_code               7707159
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C53 H89  Er1 F6 N8 O18 S2'
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 1.007(9)
 -0.007(9)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 N6-C36B = N6-C38B = N6-C34B
 1.5 with sigma of 0.02
 C47A-C46A = C47B-C46B = C51B-C50B = C50A-C51A = C49B-C48B = C49A-C48A
 1.52 with sigma of 0.02
 C35B-C34B
 1.52 with sigma of 0.02
 N8B-C46B = N8A-C46A = N8A-C48A = N8B-C48B = N8A-C50A = N8B-C50B
 1.5 with sigma of 0.02
 C46A-C50A
 2.49 with sigma of 0.02
 C39B-C38B
 1.52 with sigma of 0.02
 C37B-C36B
 1.52 with sigma of 0.02
 C37A-C36A
 1.52 with sigma of 0.02
 C50B-C46B
 2.49 with sigma of 0.02
 N6-C36A
 1.5 with sigma of 0.02
 N8A-C51A
 2.51 with sigma of 0.04
 N8B-C49B
 2.51 with sigma of 0.04
 N8B-C47B
 2.51 with sigma of 0.04
 N6-C35B
 2.51 with sigma of 0.04
 N8B-C51B
 2.51 with sigma of 0.04
 N8A-C47A
 2.51 with sigma of 0.04
 N6-C39B
 2.51 with sigma of 0.04
 N6-C37B
 2.51 with sigma of 0.04
 C50A-C48A
 2.49 with sigma of 0.04
 C46B-C48B
 2.49 with sigma of 0.04
 C48A-C46A
 2.49 with sigma of 0.04
 N8A-C49A
 2.51 with sigma of 0.04
 C48B-C50B
 2.49 with sigma of 0.04
 S2A-O19A \\sim S2B-O19B \\sim S2A-O21A \\sim S2B-O21B \\sim S2B-O20B \\sim
S2A-O20A
 with sigma of 0.02
 S2A-C53A \\sim S2B-C53B
 with sigma of 0.02
 F6B-C53B \\sim F6A-C53A \\sim F5A-C53A \\sim F5B-C53B \\sim F4A-C53A \\sim
F4B-C53B
 with sigma of 0.02
 C53B-O19B \\sim C53B-O20B \\sim C53B-O21B \\sim C53A-O19A \\sim C53A-O20A
\\sim C53A-O21A
 with sigma of 0.04
 S2B-F4B \\sim S2B-F5B \\sim S2B-F6B \\sim S2A-F4A \\sim S2A-F5A \\sim S2A-F6A
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
N8A \\sim C46A \\sim C48A \\sim C50A \\sim C47A \\sim C51A \\sim C48B \\sim N8B
\\sim C46B \\sim C50B \\sim C47B \\sim C49B \\sim C51B \\sim C49A: within 1A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 1A
N6 \\sim C34A \\sim C34B \\sim C35A \\sim C35B \\sim C36A \\sim C36B \\sim C37A
\\sim C37B \\sim C38A \\sim C38B \\sim C39A \\sim C39B: within 1A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 1A
S2A \\sim F4A \\sim F5A \\sim F6A \\sim O19A \\sim O20A \\sim O21A \\sim C53A
\\sim S2B \\sim F4B \\sim F5B \\sim F6B \\sim O19B \\sim O20B \\sim O21B \\sim
C53B: within 1A with sigma of 0.04 and sigma for terminal atoms of 0.08 within
1A
Uanis(N8A) = Uanis(N8B)
Uanis(O21A) = Uanis(O21B)
Uanis(S2A) = Uanis(S2B)
5. Rigid body (RIGU) restrains
 N8A, C46A, C48A, C50A, C47A, C49A, C51A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S2B, F4B, F5B, F6B, O19B, O20B, O21B, C53B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 S2A, F4A, F5A, F6A, O19A, O20A, O21A, C53A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C38A, N6, C34A, C36A, C35A, C37A, C39A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H6A)=Sof(C34A)=Sof(H34A)=Sof(H34B)=Sof(C35A)=Sof(H35A)=Sof(H35B)=
 Sof(H35C)=Sof(C36A)=Sof(H36A)=Sof(H36B)=Sof(C37A)=Sof(H37A)=Sof(H37B)=
 Sof(H37C)=Sof(C38A)=Sof(H38A)=Sof(H38B)=Sof(C39A)=Sof(H39A)=Sof(H39B)=
 Sof(H39C)=1-FVAR(1)
 Sof(H6B)=Sof(C34B)=Sof(H34C)=Sof(H34D)=Sof(C35B)=Sof(H35D)=Sof(H35E)=
 Sof(H35F)=Sof(C36B)=Sof(H36C)=Sof(H36D)=Sof(C37B)=Sof(H37D)=Sof(H37E)=
 Sof(H37F)=Sof(C38B)=Sof(H38C)=Sof(H38D)=Sof(C39B)=Sof(H39D)=Sof(H39E)=
 Sof(H39F)=FVAR(1)
 Sof(S2A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(O19A)=Sof(O20A)=Sof(O21A)=Sof(C53A)=1-
 FVAR(2)
 Sof(S2B)=Sof(F4B)=Sof(F5B)=Sof(F6B)=Sof(O19B)=Sof(O20B)=Sof(O21B)=Sof(C53B)=
 FVAR(2)
 Sof(N8B)=Sof(H8B)=Sof(C46B)=Sof(H46C)=Sof(H46D)=Sof(C47B)=Sof(H47D)=Sof(H47E)=
 Sof(H47F)=Sof(C48B)=Sof(H48C)=Sof(H48D)=Sof(C49B)=Sof(H49D)=Sof(H49E)=
 Sof(H49F)=Sof(C50B)=Sof(H50C)=Sof(H50D)=Sof(C51B)=Sof(H51D)=Sof(H51E)=
 Sof(H51F)=1-FVAR(3)
 Sof(N8A)=Sof(H8A)=Sof(C46A)=Sof(H46A)=Sof(H46B)=Sof(C47A)=Sof(H47A)=Sof(H47B)=
 Sof(H47C)=Sof(C48A)=Sof(H48A)=Sof(H48B)=Sof(C49A)=Sof(H49A)=Sof(H49B)=
 Sof(H49C)=Sof(C50A)=Sof(H50A)=Sof(H50B)=Sof(C51A)=Sof(H51A)=Sof(H51B)=
 Sof(H51C)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 N4(H4A), N5(H5A), N6(H6A), N6(H6B), N7(H7), N8A(H8A), N8B(H8B)
7.b Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C24(H24A,H24B), C26(H26A,H26B), C28(H28A,H28B), C30(H30A,
 H30B), C32(H32A,H32B), C34A(H34A,H34B), C34B(H34C,H34D), C36A(H36A,H36B),
 C36B(H36C,H36D), C38A(H38A,H38B), C38B(H38C,H38D), C40(H40A,H40B), C43(H43A,
 H43B), C44(H44A,H44B), C46A(H46A,H46B), C48A(H48A,H48B), C50A(H50A,H50B),
 C46B(H46C,H46D), C48B(H48C,H48D), C50B(H50C,H50D)
7.c Me refined with riding coordinates:
 C35B(H35D,H35E,H35F), C37B(H37D,H37E,H37F), C39B(H39D,H39E,H39F), C51A(H51A,
 H51B,H51C), C47B(H47D,H47E,H47F), C49B(H49D,H49E,H49F), C51B(H51D,H51E,H51F)
7.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C10(H10), C11(H11), C12(H12), C17(H17), C18(H18),
 C19(H19)
7.e Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C29(H29A,H29B,
 H29C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C35A(H35A,H35B,H35C),
 C37A(H37A,H37B,H37C), C39A(H39A,H39B,H39C), C41(H41A,H41B,H41C), C42(H42A,H42B,
 H42C), C45(H45A,H45B,H45C), C47A(H47A,H47B,H47C), C49A(H49A,H49B,H49C)
;
_shelx_res_checksum              88946
_shelx_hkl_checksum              12950
_shelx_fab_checksum              96889
_platon_squeeze_void_probe_radius 1.20
_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 1.452
_oxdiff_exptl_absorpt_empirical_full_min 0.438