Tuning the Self-Trapped Emission: Reversible Transformation to 0D Copper Clusters Permits Bright Red Emission in Potassium and Rubidium Copper Bromides
Li, Yanyan; Zhou, Zhicong; Sheong, Fu Kit; Xing, Zengshan; Lortz, Rolf; Wong, Kam Sing; Sung, Herman H. Y.; Williams, Ian D.; Halpert, Jonathan E.; ACS Energy Letters  (2021) 4383–4389; doi:10.1021/acsenergylett.1c01957

data_4519191
_publ_section_title
;
 Tuning the Self-Trapped Emission: Reversible Transformation to 0D Copper
 Clusters Permits Bright Red Emission in Potassium and Rubidium Copper
 Bromides
;
_journal_name_full               'ACS Energy Letters'
_journal_page_first              4383
_journal_page_last               4389
_journal_paper_doi               10.1021/acsenergylett.1c01957
_journal_year                    2021
_chemical_formula_moiety
'C18 H54 Br13 Cu8 K6 O11.999 S8.64, Br4 Cu4 (H2 O) (O H)'
_chemical_formula_sum            'C24 H75 Br17 Cu12 K6 O14 S12'
_chemical_formula_weight         3328.11
_space_group_crystal_system      cubic
_space_group_IT_number           221
_space_group_name_Hall           '-P 4 2 3'
_space_group_name_H-M_alt        'P m -3 m'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-02
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2021.06.23 svn.r9b09db45 for OlexSys, GUI svn.r6363)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   13.3012(3)
_cell_length_b                   13.3012(3)
_cell_length_c                   13.3012(3)
_cell_measurement_reflns_used    4397
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      72.1850
_cell_measurement_theta_min      3.3080
_cell_volume                     2353.27(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1788
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    104.00 177.00   1.00   12.00    --  104.18  77.00  90.00   73
  2  \w   -114.00 -13.00   1.00    5.00    --  -40.20 -57.00 -60.00  101
  3  \w   -116.00 -16.00   1.00    5.00    --  -40.20 -37.00-180.00  100
  4  \w    -17.00  74.00   1.00    5.00    --   40.20 -77.00  60.00   91
  5  \w     34.00 109.00   1.00   12.00    --  104.18-111.00 -60.00   75
  6  \w     33.00 132.00   1.00   12.00    --  104.18 -45.00  30.00   99
  7  \w     74.00 178.00   1.00   12.00    --  104.18  30.00  60.00  104
  8  \w    104.00 178.00   1.00   12.00    --  104.18 111.00 120.00   74
  9  \w     59.00 133.00   1.00   12.00    --  104.18 -77.00 120.00   74
 10  \w     26.00 115.00   1.00   12.00    --  104.18 -30.00 120.00   89
 11  \w     32.00 105.00   1.00   12.00    --  104.18 -94.00  60.00   73
;
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0771330000
_diffrn_orient_matrix_UB_12      -0.0297179000
_diffrn_orient_matrix_UB_13      0.0810202000
_diffrn_orient_matrix_UB_21      -0.0019295000
_diffrn_orient_matrix_UB_22      -0.1082996000
_diffrn_orient_matrix_UB_23      -0.0415270000
_diffrn_orient_matrix_UB_31      0.0862255000
_diffrn_orient_matrix_UB_32      -0.0289296000
_diffrn_orient_matrix_UB_33      0.0715398000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0509
_diffrn_reflns_av_unetI/netI     0.0121
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            13961
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.243
_diffrn_reflns_theta_min         3.323
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.80
_diffrn_source_power             0.040
_diffrn_source_target            Cu
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    16.519
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57355
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.69a (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    2.348
_exptl_crystal_description       block
_exptl_crystal_F_000             1580
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.993
_refine_diff_density_min         -1.254
_refine_diff_density_rms         0.163
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     55
_refine_ls_number_reflns         532
_refine_ls_number_restraints     37
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0703
_refine_ls_R_factor_gt           0.0652
_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^)+(0.1431P)^2^+7.6263P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2075
_refine_ls_wR_factor_ref         0.2160
_reflns_Friedel_coverage         0.000
_reflns_number_gt                468
_reflns_number_total             532
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nz1c01957_si_002.cif
_cod_data_source_block           yanyan2d_173k
_cod_original_cell_volume        2353.27(16)
_cod_database_code               4519191
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.558
_shelx_estimated_absorpt_t_min   0.558
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Shared sites
{Br3, O2}
3. Restrained distances
 S1-C1 = S1A-C2
 1.8 with sigma of 0.02
 S1-C1
 1.8 with sigma of 0.02
 S1A-O1A = S1-O1
 1.59 with sigma of 0.02
 S1-O1
 1.59 with sigma of 0.02
 S1-O1A \\sim S1-O1
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C2) \\sim Ueq, Uanis(S1A) \\sim Ueq, Uanis(O1A) \\sim Ueq: with sigma of
0.03 and sigma for terminal atoms of 0.05
Uanis(Br3) = Uanis(O2)
5. Rigid body (RIGU) restrains
 K1, S1, O1A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 K1, S1, O1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Fixed Sof: S1(0.12) S1A(0.06) O1(0.16667) O1A(0.0833) C1(0.25) H1C(0.25)
 H1A(0.25) H1B(0.25) C2(0.125) H2A(0.125) H2B(0.125) H2C(0.125) Br3(0.08333)
 Cu2(0.08333) O2(0.04167) H3(0.02083) H4(0.04167)
7.a Riding coordinates:
 C1(H1C,H1A,H1B), C2(H2A,H2B,H2C), O2(H3,H4)
;
_shelx_res_checksum              50904
_shelx_hkl_checksum              41230
_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 2.364
_oxdiff_exptl_absorpt_empirical_full_min 0.635