Core-Dependent Properties of Copper Nanoclusters: Valence-Pure Nanoclusters as NIR TADF Emitters and Mixed-Valence Ones as Semiconductors
Zhang, Li-Min; Zhou, Guodong; Zhou, Guoqing; Lee, Hung Kay; Zhao, Ni; Prezhdo, Oleg V.; Mak, Thomas C. W.; Chemical Science  (2019) –; doi:10.1039/C9SC03455B

data_1552304
_publ_section_title
;
 Core-Dependent Properties of Copper Nanoclusters: Valence-Pure
 Nanoclusters as NIR TADF Emitters and Mixed-Valence Ones as
 Semiconductors
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC03455B
_journal_year                    2019
_chemical_formula_moiety         'C134 H204 S2 Cu28 O10'
_chemical_formula_sum            'C134 H204 Cu28 O10 S2'
_chemical_formula_weight         3818.4656
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-04-01
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-04-03 deposited with the CCDC.    2019-09-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.937(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   18.680(2)
_cell_length_b                   14.6314(17)
_cell_length_c                   31.316(4)
_cell_measurement_reflns_used    9513
_cell_measurement_temperature    173
_cell_measurement_theta_max      23.242
_cell_measurement_theta_min      2.257
_cell_volume                     8269.9(17)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      173
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1144
_diffrn_reflns_av_unetI/netI     0.1047
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            182816
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.253
_diffrn_reflns_theta_min         2.257
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.580
_exptl_absorpt_correction_T_max  0.867
_exptl_absorpt_correction_T_min  0.773
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.490
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3648.0
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.909
_refine_diff_density_min         -0.714
_refine_diff_density_rms         0.125
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     857
_refine_ls_number_reflns         20159
_refine_ls_number_restraints     112
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.1670
_refine_ls_R_factor_gt           0.0761
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1048P)^2^+5.7907P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1828
_refine_ls_wR_factor_ref         0.2144
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10426
_reflns_number_total             20159
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc03455b2.cif
_cod_data_source_block           2
_cod_original_formula_sum        'C134 H204 S2 Cu28 O10'
_cod_database_code               1552304
_shelx_shelxl_version_number     2017/1
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C39, C40B, C39, C41B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 O5, C67
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C10A) \\sim Ueq, Uanis(C11A) \\sim Ueq, Uanis(C12A) \\sim Ueq,
Uanis(C22A) \\sim Ueq, Uanis(C23A) \\sim Ueq, Uanis(C24A) \\sim Ueq,
Uanis(C40A) \\sim Ueq, Uanis(C41A) \\sim Ueq, Uanis(C42A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C34A) \\sim Ueq, Uanis(C35A) \\sim Ueq, Uanis(C36A) \\sim Ueq,
Uanis(C58A) \\sim Ueq, Uanis(C59A) \\sim Ueq, Uanis(C60A) \\sim Ueq,
Uanis(C65A) \\sim Ueq, Uanis(C66A) \\sim Ueq, Uanis(C67) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C60A) = Uanis(C60B)
Uanis(C59A) = Uanis(C59B)
Uanis(C58A) = Uanis(C58B)
Uanis(C36A) = Uanis(C36B)
Uanis(C35A) = Uanis(C35B)
Uanis(C34A) = Uanis(C34B)
Uanis(C66A) = Uanis(C66B)
Uanis(C65A) = Uanis(C65B)
Uanis(C10A) = Uanis(C10B)
Uanis(C11A) = Uanis(C11B)
Uanis(C12A) = Uanis(C12B)
Uanis(C40A) = Uanis(C40B)
Uanis(C41A) = Uanis(C41B)
Uanis(C42A) = Uanis(C42B)
Uanis(C22A) = Uanis(C22B)
Uanis(C23A) = Uanis(C23B)
Uanis(C24A) = Uanis(C24B)
4. Others
 Sof(C10B)=Sof(C12B)=Sof(C11B)=1-FVAR(1)
 Sof(C10A)=Sof(C11A)=Sof(C12A)=FVAR(1)
 Sof(C40B)=Sof(C42B)=Sof(C41B)=1-FVAR(2)
 Sof(C40A)=Sof(C42A)=Sof(C41A)=FVAR(2)
 Sof(C22B)=Sof(C23B)=Sof(C24B)=1-FVAR(3)
 Sof(C22A)=Sof(C23A)=Sof(C24A)=FVAR(3)
 Sof(C36B)=Sof(C35B)=Sof(C34B)=1-FVAR(4)
 Sof(C35A)=Sof(C34A)=Sof(C36A)=FVAR(4)
 Sof(C65B)=Sof(C66B)=1-FVAR(5)
 Sof(C65A)=Sof(C66A)=FVAR(5)
 Sof(C58B)=Sof(C59B)=Sof(C60B)=1-FVAR(6)
 Sof(C58A)=Sof(C59A)=Sof(C60A)=FVAR(6)
5.a Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C16(H16A,H16B,H16C),
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,
 H48B,H48C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C),
 C64(H64A,H64B,H64C)
;
_olex2_submission_special_instructions 'No special instructions were received'