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_1552307
_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         C165H231Cl4Cu48O22
_chemical_formula_sum            'C165 H231 Cl4 Cu48 O22'
_chemical_formula_weight         5758.6052
_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             2019-04-01
_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                 96.377(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   56.4611(18)
_cell_length_b                   19.3733(7)
_cell_length_c                   38.1762(13)
_cell_measurement_reflns_used    9912
_cell_measurement_temperature    173
_cell_measurement_theta_max      25.23
_cell_measurement_theta_min      2.38
_cell_volume                     41500(2)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0750
_diffrn_reflns_av_unetI/netI     0.0750
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_number            37955
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.350
_diffrn_reflns_theta_min         1.573
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.898
_exptl_absorpt_correction_T_max  0.822
_exptl_absorpt_correction_T_min  0.669
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1326 before and 0.0547 after correction.
The Ratio of minimum to maximum transmission is 0.7277.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            brown-black
_exptl_crystal_density_diffrn    1.833
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             22656.0
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.04
_refine_diff_density_max         3.274
_refine_diff_density_min         -1.504
_refine_diff_density_rms         0.172
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           fullcycle
_refine_ls_number_parameters     2235
_refine_ls_number_reflns         37955
_refine_ls_number_restraints     57
_refine_ls_restrained_S_all      1.342
_refine_ls_R_factor_all          0.1081
_refine_ls_R_factor_gt           0.0610
_refine_ls_shift/su_max          0.018
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1110P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1734
_refine_ls_wR_factor_ref         0.1936
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23795
_reflns_number_total             37955
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc03455b2.cif
_cod_data_source_block           3
_cod_original_formula_sum        C165H231Cl4Cu48O22
_cod_database_code               1552307
_shelx_shelxl_version_number     2017/1
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C143-C144 = C143-C145
 1.53 with sigma of 0.002
 C144-C145
 2.45 with sigma of 0.002
 C164-C165
 1.53 with sigma of 0.002
 C143-C144 \\sim C943-C944
 with sigma of 0.02
 C143-C145 \\sim C943-C945
 with sigma of 0.02
 C144-C145 \\sim C944-C945
 with sigma of 0.02
3. Rigid bond restraints
 C73, C74
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C164, C166
 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(C53) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(C118)
\\sim Ueq, Uanis(C139) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(C143) \\sim Ueq, Uanis(C144) \\sim Ueq, Uanis(C145) \\sim Ueq: with sigma
of 0.002 and sigma for terminal atoms of 0.001
Uanis(C143) = Uanis(C943)
Uanis(C144) = Uanis(C944)
Uanis(C145) = Uanis(C945)
Uiso(C140) = Uiso(C940)
5. Others
 Sof(Cu98)=1-FVAR(1)
 Sof(Cu48)=FVAR(1)
 Sof(Cu90)=1-FVAR(2)
 Sof(Cu40)=FVAR(2)
 Sof(C943)=Sof(C944)=Sof(C945)=1-FVAR(3)
 Sof(C143)=Sof(C144)=Sof(C145)=FVAR(3)
 Sof(C940)=1-FVAR(4)
 Sof(C140)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C3(H3), C8(H8), C13(H13), C18(H18), C23(H23), C28(H28), C33(H33), C38(H38),
 C43(H43), C48(H48), C53(H53), C58(H58), C63(H63), C68(H68), C73(H73), C78(H78),
  C83(H83), C88(H88), C93(H93), C98(H98), C103(H103), C108(H108), C113(H113),
 C123(H123), C128(H128), C133(H133), C149(H149), C154(H154), C159(H159),
 C164(H164), C118(H118)
6.b Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C39(H39A,H39B,H39C),
 C40(H40A,H40B,H40C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C49(H49A,H49B,
 H49C), C50(H50A,H50B,H50C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C59(H59A,
 H59B,H59C), C60(H60A,H60B,H60C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C),
 C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C74(H74A,H74B,H74C), C75(H75A,H75B,
 H75C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C), C84(H84A,H84B,H84C), C89(H89A,
 H89B,H89C), C90(H90A,H90B,H90C), C94(H94A,H94B,H94C), C95(H95A,H95B,H95C),
 C99(H99A,H99B,H99C), C100(H10D,H10E,H10F), C104(H10G,H10H,H10I), C105(H10J,
 H10K,H10L), C109(H10M,H10N,H10O), C110(H11A,H11B,H11C), C114(H11D,H11E,H11F),
 C115(H11G,H11H,H11I), C119(H11J,H11K,H11L), C120(H12A,H12B,H12C), C124(H12D,
 H12E,H12F), C125(H12G,H12H,H12I), C129(H12J,H12K,H12L), C130(H13A,H13B,H13C),
 C134(H13D,H13E,H13F), C135(H13G,H13H,H13I), C150(H15D,H15E,H15F), C151(H15G,
 H15H,H15I), C155(H15J,H15K,H15L), C156(H15M,H15N,H15O), C160(H16A,H16B,H16C),
 C161(H16D,H16E,H16F), C166(H16G,H16H,H16I), C85(H85A,H85B,H85C)
;
_olex2_submission_special_instructions 'No special instructions were received'