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_1552303
_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         '(V10 O28) 6(H3O)'
_chemical_formula_sum            'H18 O34 V10'
_chemical_formula_weight         1071.5375
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_audit_creation_date             2019-04-02
_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                83.426(2)
_cell_angle_beta                 87.127(2)
_cell_angle_gamma                71.045(2)
_cell_formula_units_Z            2
_cell_length_a                   10.1593(8)
_cell_length_b                   10.2950(9)
_cell_length_c                   16.7352(13)
_cell_measurement_reflns_used    9862
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      27.91
_cell_measurement_theta_min      2.43
_cell_volume                     1644.4(2)
_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      296.46
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.996
_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  0.0237
_diffrn_reflns_av_unetI/netI     0.0154
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            52059
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.949
_diffrn_reflns_theta_min         2.120
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.837
_exptl_absorpt_correction_T_max  0.918
_exptl_absorpt_correction_T_min  0.815
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    2.164
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1172.0
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.963
_refine_diff_density_min         -1.104
_refine_diff_density_rms         0.303
_refine_ls_extinction_coef       0.0247(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.207
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     456
_refine_ls_number_reflns         7879
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.208
_refine_ls_R_factor_all          0.0394
_refine_ls_R_factor_gt           0.0346
_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^)+(0.0560P)^2^+1.7361P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1013
_refine_ls_wR_factor_ref         0.1049
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7027
_reflns_number_total             7879
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc03455b2.cif
_cod_data_source_block           hydronium
_cod_original_formula_sum        H18V10O34
_cod_database_code               1552303
_shelx_shelxl_version_number     2017/1
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All O(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(O37A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O37A) = Uanis(O37B)
3. Others
 Sof(O37B)=1-FVAR(1)
 Sof(O37A)=FVAR(1)
4.a Riding coordinates:
 O29(H29A,H29B,H29C), O30(H30A,H30B,H30C), O31(H31A,H31B,H31C), O32(H32A,H32B,
 H32C), O33(H33A,H33B,H33C), O34(H34A,H34B,H34C), O35(H35A,H35B,H35C), O36(H36A,
 H36B,H36C), O38(H38A,H38B,H38C), O39(H39A,H39B,H39C), O40(H40A,H40B,H40C),
 O37A(H37A,H37B,H37C)
;
_olex2_submission_special_instructions 'No special instructions were received'