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_7707160
_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         'C33 H39 Er N3 O12, 3(Cl O4)'
_chemical_formula_sum            'C33 H39 Cl3 Er N3 O24'
_chemical_formula_weight         1135.28
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_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                 93.2566(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.67503(12)
_cell_length_b                   12.92128(15)
_cell_length_c                   26.7999(2)
_cell_measurement_reflns_used    35173
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      74.0900
_cell_measurement_theta_min      3.2760
_cell_volume                     4382.14(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.56a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.56a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.56a (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 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(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 0.991
_diffrn_measured_fraction_theta_max 0.978
_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    -65.00 -40.00   0.50    0.80    --  -28.00 -66.00-123.76   50
  2  \w    -93.00 -59.00   0.50    0.80    --  -52.43 -15.00 -60.00   68
  3  \w    -54.00 -24.00   0.50    0.80    --  -52.43 -15.00 -60.00   60
  4  \w     34.00  60.00   0.50    0.80    --   68.73-125.00 -90.00   52
  5  \w     68.00  94.00   0.50    0.80    --   68.73-125.00 -60.00   52
  6  \w     36.00  64.00   0.50    0.80    --   68.73-125.00 -60.00   56
  7  \w     64.00  94.00   0.50    0.80    --   68.73-125.00  30.00   60
  8  \w     49.00  94.00   0.50    0.80    --   69.88-125.00  60.00   90
  9  \w     37.00  83.00   0.50    0.80    --   69.88   0.00   0.00   92
 10  \w     37.00  95.00   0.50    0.80    --   69.88-125.00-120.00  116
 11  \w     36.00 101.00   0.50    0.80    --   69.88   0.00  90.00  130
 12  \w     46.00 103.00   0.50    0.80    --   75.25-130.00 121.25  114
 13  \w     72.00  97.00   0.50    0.80    --   75.25-118.00 -16.03   50
 14  \w     49.00  78.00   0.50    0.80    --   75.25-113.00 124.11   58
 15  \w     38.00  63.00   0.50    0.80    --   75.25-125.00  34.18   50
 16  \w     61.00  87.00   0.50    0.80    --   75.25-120.00 179.24   52
 17  \w     35.00  68.00   0.50    0.80    --   75.25-118.00 -16.03   66
 18  \w     71.00  96.00   0.50    0.80    --   75.25-115.00 -96.31   50
 19  \w     35.00  60.00   0.50    0.80    --   75.25 -53.00  94.38   50
 20  \w     54.00  87.00   0.50    0.80    --   75.25-108.00 -91.20   66
 21  \w     89.00 114.00   0.50    0.80    --   75.25  19.00 137.58   50
 22  \w     63.00  99.00   0.50    0.80    --   75.25  20.00   6.84   72
 23  \w     79.00 104.00   0.50    0.80    --   75.25  22.00  54.92   50
 24  \w     39.00  64.00   0.50    0.80    --   75.25-102.00 176.31   50
 25  \w     49.00  95.00   0.50    0.80    --   75.25-114.00 -51.89   92
 26  \w     44.00 111.00   0.50    0.80    --   75.25   6.00 117.30  134
 27  \w     50.00  75.00   0.50    0.80    --   75.25-110.00 145.57   50
 28  \w     36.00  62.00   0.50    0.80    --   75.25-122.00 147.46   52
 29  \w     81.00 109.00   0.50    0.80    --   75.25   6.00 -92.65   56
 30  \w     42.00  67.00   0.50    0.80    --   75.25 -98.00 -44.33   50
 31  \w     46.00  72.00   0.50    0.80    --   75.25-116.00  53.84   52
 32  \w     37.00  62.00   0.50    0.80    --   75.25 -60.00 143.17   50
 33  \w     45.00  70.00   0.50    0.80    --   75.25   6.00 -92.65   50
 34  \w     61.00 109.00   0.50    0.80    --   75.25  20.00-159.92   96
 35  \w     36.00  84.00   0.50    0.80    --   75.25-113.00 -41.96   96
 36  \w     69.00  96.00   0.50    0.80    --   75.25-116.00   9.51   54
 37  \w     90.00 120.00   0.50    0.80    --   75.25  34.00 172.36   60
 38  \w     73.00  99.00   0.50    0.80    --   75.25-122.00 147.46   52
 39  \w     72.00  97.00   0.50    0.80    --   75.25-118.00-151.11   50
 40  \w     66.00  91.00   0.50    0.80    --   75.25   0.00-121.14   50
 41  \w     61.00  96.00   0.50    0.80    --   75.25-115.00-134.33   70
 42  \w     39.00  67.00   0.50    0.80    --   75.25-115.00 -96.31   56
 43  \w     73.00  98.00   0.50    0.80    --   75.25-120.00-120.09   50
 44  \w     39.00  78.00   0.50    0.80    --   75.25-128.00  25.65   78
 45  \w     51.00 100.00   0.50    0.80    --   75.25-124.00  14.20   98
;
_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      -0.0845062000
_diffrn_orient_matrix_UB_12      -0.0325113000
_diffrn_orient_matrix_UB_13      -0.0405240000
_diffrn_orient_matrix_UB_21      0.0260038000
_diffrn_orient_matrix_UB_22      -0.1147125000
_diffrn_orient_matrix_UB_23      0.0107142000
_diffrn_orient_matrix_UB_31      -0.0836372000
_diffrn_orient_matrix_UB_32      -0.0025427000
_diffrn_orient_matrix_UB_33      0.0394757000
_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  0.0290
_diffrn_reflns_av_unetI/netI     0.0209
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            57958
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.369
_diffrn_reflns_theta_min         3.303
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.045
_exptl_absorpt_correction_T_max  0.762
_exptl_absorpt_correction_T_min  0.526
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.56a (Rigaku Oxford Diffraction, 2020)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'pale pink'
_exptl_crystal_density_diffrn    1.721
_exptl_crystal_description       prism
_exptl_crystal_F_000             2276
_exptl_crystal_size_max          0.118
_exptl_crystal_size_mid          0.113
_exptl_crystal_size_min          0.048
_refine_diff_density_max         0.759
_refine_diff_density_min         -0.782
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     598
_refine_ls_number_reflns         8746
_refine_ls_number_restraints     87
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0380
_refine_ls_R_factor_gt           0.0333
_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^)+(0.0489P)^2^+4.3370P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0892
_refine_ls_wR_factor_ref         0.0921
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7711
_reflns_number_total             8746
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt01079d2.cif
_cod_data_source_block           2_Er(dpa-ester)3
_cod_depositor_comments
'Adding full bibliography for 7707159--7707161.cif.'
_cod_original_cell_volume        4382.14(8)
_cod_database_code               7707160
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C33 H39 Cl3 Er N3 O24'
_reflns_odcompleteness_completeness 97.44
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl3A-O21A = Cl3A-O22A = Cl3A-O23A = Cl3A-O24A
 1.5 with sigma of 0.02
 Cl3B-O21B = Cl3B-O22B = Cl3B-O23B = Cl3B-O24B
 1.5 with sigma of 0.02
 Cl3C-O21C = Cl3C-O22C = Cl3C-O23C = Cl3C-O24C
 1.5 with sigma of 0.02
 Cl3A-O21A \\sim Cl3A-O22A \\sim Cl3A-O23A \\sim Cl3A-O24A
 with sigma of 0.02
 O23A-O21A \\sim O22A-O24A \\sim O23A-O24A \\sim O22A-O21A \\sim O23A-O22A
\\sim O21A-O24A
 with sigma of 0.04
 Cl3B-O21B \\sim Cl3B-O22B \\sim Cl3B-O23B \\sim Cl3B-O24B
 with sigma of 0.02
 O23B-O21B \\sim O22B-O24B \\sim O23B-O24B \\sim O22B-O21B \\sim O23B-O22B
\\sim O21B-O24B
 with sigma of 0.04
 Cl3C-O21C \\sim Cl3C-O22C \\sim Cl3C-O23C \\sim Cl3C-O24C
 with sigma of 0.02
 O23C-O21C \\sim O22C-O24C \\sim O23C-O24C \\sim O22C-O21C \\sim O23C-O22C
\\sim O21C-O24C
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Cl3A \\sim O21A \\sim O22A \\sim O23A \\sim O24A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
Cl3B \\sim O21B \\sim O22B \\sim O23B \\sim O24B: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
Cl3C \\sim O21C \\sim O22C \\sim O23C \\sim O24C: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 Cl3A, O21A, O22A, O23A, O24A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl3B, O21B, O22B, O23B, O24B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl3C, O21C, O22C, O23C, O24C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: Cl3A(0.33333) O21A(0.33333) O22A(0.33333) O23A(0.33333)
 O24A(0.33333) Cl3B(0.33333) O21B(0.33333) O22B(0.33333) O23B(0.33333)
 O24B(0.33333) Cl3C(0.33333) O21C(0.33333) O22C(0.33333) O23C(0.33333)
 O24C(0.33333)
6.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C10(H10A,H10B), C13(H13A,H13B), C21(H21A,H21B), C24(H24A,H24B),
 C32(H32A,H32B)
6.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C16(H16), C17(H17), C18(H18), C27(H27), C28(H28),
 C29(H29)
6.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              74727
_shelx_hkl_checksum              21577
_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 1.218
_oxdiff_exptl_absorpt_empirical_full_min 0.822