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_1552302
_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         'C84 H126 Cu15 N O3'
_chemical_formula_sum            'C84 H126 Cu15 N O3'
_chemical_formula_weight         2151.0942
_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'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-02-15
_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                 112.054(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   49.115(10)
_cell_length_b                   15.305(3)
_cell_length_c                   28.157(5)
_cell_measurement_reflns_used    9185
_cell_measurement_temperature    173
_cell_measurement_theta_max      20.077
_cell_measurement_theta_min      2.229
_cell_volume                     19617(7)
_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    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      173
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_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  0.1321
_diffrn_reflns_av_unetI/netI     0.1577
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       62
_diffrn_reflns_limit_h_min       -62
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            67408
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.999
_diffrn_reflns_theta_min         1.404
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.215
_exptl_absorpt_correction_T_max  0.825
_exptl_absorpt_correction_T_min  0.687
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.420
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             8336.0
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.206
_refine_diff_density_min         -1.344
_refine_diff_density_rms         0.173
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.000
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1012
_refine_ls_number_reflns         21344
_refine_ls_number_restraints     167
_refine_ls_restrained_S_all      0.998
_refine_ls_R_factor_all          0.1982
_refine_ls_R_factor_gt           0.0801
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1264P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2028
_refine_ls_wR_factor_ref         0.2704
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8840
_reflns_number_total             21344
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc03455b2.cif
_cod_data_source_block           1
_cod_database_code               1552302
_shelx_shelxl_version_number     2017/1
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C10A-C11A = C10A-C12A = C11A-C12A
 2.45 with sigma of 0.01
 C10B-C11B = C10B-C12B = C11B-C12B
 2.45 with sigma of 0.01
 C82A-C83A = C82A-C84A = C84A-C83A
 2.45 with sigma of 0.01
 C82B-C83B = C82B-C84B = C84B-C83B
 2.45 with sigma of 0.01
 C81-C82A = C81-C83A = C81-C84A
 1.52 with sigma of 0.01
 C81-C82B = C81-C83B = C81-C84B
 1.52 with sigma of 0.01
 C27-C30A \\sim C27-C30B
 with sigma of 0.02
 C27-C29A \\sim C27-C29B
 with sigma of 0.02
 C27-C28A \\sim C27-C28B
 with sigma of 0.02
 C9-C10A \\sim C9-C10B
 with sigma of 0.02
 C9-C11A \\sim C9-C11B
 with sigma of 0.02
 C9-C12A \\sim C9-C12B
 with sigma of 0.02
 C3-C6A \\sim C3-C6B
 with sigma of 0.02
 C3-C5A \\sim C3-C5B
 with sigma of 0.02
 C3-C4A \\sim C3-C4B
 with sigma of 0.02
3. Rigid bond restraints
 C15, C16
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C33, C35B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C4A) \\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C10A)
\\sim Ueq, Uanis(C11A) \\sim Ueq, Uanis(C12A) \\sim Ueq, Uanis(C34A) \\sim Ueq,
Uanis(C35A) \\sim Ueq, Uanis(C36A) \\sim Ueq, Uanis(C81) \\sim Ueq, Uanis(C82A)
\\sim Ueq, Uanis(C83A) \\sim Ueq: with sigma of 0.001 and sigma for terminal
atoms of 0.002
Uanis(C9) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18)
\\sim Ueq, Uanis(C28A) \\sim Ueq, Uanis(C29A) \\sim Ueq, Uanis(C30A) \\sim Ueq,
Uanis(C76A) \\sim Ueq, Uanis(C77A) \\sim Ueq, Uanis(C78A) \\sim Ueq,
Uanis(C84A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C78A) = Uanis(C78B)
Uanis(C77A) = Uanis(C77B)
Uanis(C76A) = Uanis(C76B)
Uanis(C29A) = Uanis(C29B)
Uanis(C28A) = Uanis(C28B)
Uanis(C30A) = Uanis(C30B)
Uanis(C36A) = Uanis(C36B)
Uanis(C35A) = Uanis(C35B)
Uanis(C34A) = Uanis(C34B)
Uanis(C82A) = Uanis(C82B)
Uanis(C83A) = Uanis(C83B)
Uanis(C84A) = Uanis(C84B)
Uanis(C10A) = Uanis(C10B)
Uanis(C11A) = Uanis(C11B)
Uanis(C12A) = Uanis(C12B)
Uanis(C4A) = Uanis(C4B)
Uanis(C5A) = Uanis(C5B)
Uanis(C6A) = Uanis(C6B)
5. Others
 Sof(C84B)=Sof(C83B)=Sof(C82B)=1-FVAR(1)
 Sof(C84A)=Sof(C83A)=Sof(C82A)=FVAR(1)
 Sof(C10B)=Sof(C11B)=Sof(C12B)=1-FVAR(2)
 Sof(C10A)=Sof(C11A)=Sof(C12A)=FVAR(2)
 Sof(C4B)=Sof(C5B)=Sof(C6B)=1-FVAR(3)
 Sof(C4A)=Sof(C5A)=Sof(C6A)=FVAR(3)
 Sof(C36B)=Sof(C35B)=Sof(C34B)=1-FVAR(4)
 Sof(C36A)=Sof(C35A)=Sof(C34A)=FVAR(4)
 Sof(C28A)=Sof(C29A)=Sof(C30A)=1-FVAR(5)
 Sof(C29B)=Sof(C28B)=Sof(C30B)=FVAR(5)
 Sof(C76B)=Sof(C78B)=Sof(C77B)=1-FVAR(6)
 Sof(C76A)=Sof(C78A)=Sof(C77A)=FVAR(6)
6.a Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C40(H40A,H40B,H40C), C41(H41A,
 H41B,H41C), C42(H42A,H42B,H42C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C),
 C48(H48A,H48B,H48C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,
 H54C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C64(H64A,
 H64B,H64C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C70(H70A,H70B,H70C),
 C71(H71A,H71B,H71C), C72(H72A,H72B,H72C)
;
_olex2_submission_special_instructions 'No special instructions were received'