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_7707161
_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         'C45 H69 Er N9 O6, 3(Cl O4)'
_chemical_formula_sum            'C45 H69 Cl3 Er N9 O18'
_chemical_formula_weight         1297.70
_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   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-01-07
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2021-01-28 deposited with the CCDC.	2021-04-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.5950(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.27946(12)
_cell_length_b                   12.89607(10)
_cell_length_c                   36.97997(19)
_cell_measurement_reflns_used    44174
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      74.6700
_cell_measurement_theta_min      2.3830
_cell_volume                     11097.59(12)
_computing_cell_refinement       'CrysAlisPro 1.171.41.49a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.41.49a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.41.49a (Rigaku OD, 2019)'
_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      150.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix-Arc
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.986
_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     76.00 107.00   0.50    1.00    --   75.13  30.00-150.00   62
  2  \w     86.00 114.00   0.50    1.00    --   81.25  72.00  72.82   56
  3  \w     97.00 123.00   0.50    1.00    --   81.25  64.00 124.36   52
  4  \w     93.00 126.00   0.50    1.00    --   81.25  55.00 154.23   66
  5  \w     96.00 122.00   0.50    1.00    --   77.04  30.00 120.00   52
  6  \w     83.00 108.00   0.50    1.00    --   81.25  23.00  17.47   50
  7  \w     78.00 103.00   0.50    1.00    --   77.04  30.00 -90.00   50
  8  \w     79.00 110.00   0.50    1.00    --   75.13  30.00 -90.00   62
  9  \w     94.00 130.00   0.50    1.00    --   81.25  20.00 -24.71   72
 10  \w     50.00  83.00   0.50    1.00    --   81.25  12.00 -58.42   66
 11  \w     52.00  89.00   0.50    1.00    --   81.25  20.00 -24.71   74
 12  \w     42.00  67.00   0.50    1.00    --   81.25   1.00  71.34   50
 13  \w     72.00 122.00   0.50    1.00    --   81.25   1.00  71.34  100
 14  \w    -35.00  -8.00   0.50    1.00    --  -57.24  30.00-150.00   54
 15  \w    -34.00  -8.00   0.50    1.00    --  -57.24  30.00-120.00   52
 16  \w    -35.00 -10.00   0.50    1.00    --  -57.24  30.00 -60.00   50
 17  \w    -67.00 -14.00   0.50    1.00    --  -57.24 124.00-101.00  106
 18  \w    -62.00 -36.00   0.50    1.00    --  -57.24 146.00  64.00   52
 19  \w     90.00 117.00   0.50    1.00    --   81.25  -1.00 -22.24   54
 20  \w     41.00  73.00   0.50    1.00    --   81.25  -1.00 -22.24   64
 21  \w     46.00  75.00   0.50    1.00    --   81.25 -77.00-155.75   58
 22  \w     44.00  69.00   0.50    1.00    --   81.25 -77.00 -52.84   50
 23  \w     43.00  69.00   0.50    1.00    --   81.25 -72.00 -39.16   52
 24  \w     48.00  74.00   0.50    1.00    --   81.25 -91.00 -89.52   52
 25  \w     75.00 113.00   0.50    1.00    --   81.25-129.00-165.27   76
 26  \w     45.00  71.00   0.50    1.00    --   81.25-129.00-165.27   52
 27  \w     84.00 111.00   0.50    1.00    --   81.25-124.00 -51.48   54
 28  \w     51.00  76.00   0.50    1.00    --   60.61-146.00  14.00   50
 29  \w     58.00  83.00   0.50    1.00    --   75.13-146.00  14.00   50
 30  \w     69.00 116.00   0.50    1.00    --   77.04-146.00  14.00   94
 31  \w     53.00 107.00   0.50    1.00    --   81.25-128.00  63.19  108
 32  \w     57.00  83.00   0.50    1.00    --   81.25-124.00 -51.48   52
 33  \w     36.00  72.00   0.50    1.00    --   77.04-124.00-179.00   72
 34  \w     69.00 105.00   0.50    1.00    --   75.13-124.00-179.00   72
 35  \w     52.00 105.00   0.50    1.00    --   81.25-115.00-146.01  106
 36  \w     62.00  87.00   0.50    1.00    --   60.61-124.00-179.00   50
 37  \w     85.00 110.00   0.50    1.00    --   81.25-121.00-101.03   50
 38  \w     40.00  68.00   0.50    1.00    --   81.25-121.00-101.03   56
 39  \w     55.00  94.00   0.50    1.00    --   81.25-113.00 -43.04   78
 40  \w     44.00  83.00   0.50    1.00    --   75.13 -94.00   0.00   78
 41  \w     49.00  91.00   0.50    1.00    --   81.25-123.00 141.89   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix-Arc'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0156625000
_diffrn_orient_matrix_UB_12      -0.0921507000
_diffrn_orient_matrix_UB_13      -0.0243487000
_diffrn_orient_matrix_UB_21      -0.0117359000
_diffrn_orient_matrix_UB_22      -0.0754830000
_diffrn_orient_matrix_UB_23      0.0311842000
_diffrn_orient_matrix_UB_31      -0.0632967000
_diffrn_orient_matrix_UB_32      -0.0087062000
_diffrn_orient_matrix_UB_33      -0.0130117000
_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  0.0248
_diffrn_reflns_av_unetI/netI     0.0163
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            60481
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.803
_diffrn_reflns_theta_min         2.391
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.797
_exptl_absorpt_correction_T_max  0.773
_exptl_absorpt_correction_T_min  0.644
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.49a (Rigaku Oxford Diffraction, 2019)
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            pink
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.553
_exptl_crystal_description       prism
_exptl_crystal_F_000             5320
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.07
_refine_diff_density_max         1.529
_refine_diff_density_min         -0.600
_refine_diff_density_rms         0.069
_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     721
_refine_ls_number_reflns         11246
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0333
_refine_ls_R_factor_gt           0.0317
_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^)+(0.0352P)^2^+34.2207P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0790
_refine_ls_wR_factor_ref         0.0800
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10652
_reflns_number_total             11246
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt01079d2.cif
_cod_data_source_block           3_Er(dpa-amide)3
_cod_depositor_comments
'Adding full bibliography for 7707159--7707161.cif.'
_cod_original_cell_volume        11097.58(12)
_cod_database_code               7707161
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C45 H69 Cl3 Er N9 O18'
_shelx_estimated_absorpt_t_max   0.730
_shelx_estimated_absorpt_t_min   0.553
_reflns_odcompleteness_completeness 98.75
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C45B) = Uanis(C45A)
3. Others
 Sof(H44C)=Sof(H44D)=Sof(C45B)=Sof(H45D)=Sof(H45E)=Sof(H45F)=1-FVAR(1)
 Sof(H44A)=Sof(H44B)=Sof(C45A)=Sof(H45A)=Sof(H45B)=Sof(H45C)=FVAR(1)
 Sof(O17B)=Sof(O18B)=1-FVAR(2)
 Sof(O17A)=Sof(O18A)=FVAR(2)
4.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C9(H9A,H9B), C12(H12A,H12B), C14(H14A,H14B), C22(H22A,H22B),
 C24(H24A,H24B), C27(H27A,H27B), C29(H29A,H29B), C37(H37A,H37B), C39(H39A,H39B),
  C42(H42A,H42B), C44(H44A,H44B), C44(H44C,H44D)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C17(H17), C18(H18), C19(H19), C32(H32), C33(H33),
 C34(H34)
4.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C13(H13A,H13B,H13C), C15(H15A,H15B,
 H15C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C28(H28A,H28B,H28C), C30(H30A,
 H30B,H30C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C43(H43A,H43B,H43C),
 C45A(H45A,H45B,H45C), C45B(H45D,H45E,H45F)
;
_shelx_res_checksum              83626
_shelx_hkl_checksum              5859
_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 1.111
_oxdiff_exptl_absorpt_empirical_full_min 0.887