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_1552305
_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         'C180 H289 B3 Cl4 Cu47 F12 O22 P2 V2'
_chemical_formula_sum            'C180 H289 B3 Cl4 Cu47 F12 O22 P2 V2'
_chemical_formula_weight         6357.9246
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-03-31
_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                90.482(2)
_cell_angle_beta                 101.813(2)
_cell_angle_gamma                116.372(2)
_cell_formula_units_Z            2
_cell_length_a                   19.9192(17)
_cell_length_b                   20.0207(17)
_cell_length_c                   32.564(3)
_cell_measurement_reflns_used    9280
_cell_measurement_temperature    173
_cell_measurement_theta_max      25.59
_cell_measurement_theta_min      2.50
_cell_volume                     11315.2(17)
_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 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0436
_diffrn_reflns_av_unetI/netI     0.0419
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            162295
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         0.643
_exptl_absorpt_coefficient_mu    4.507
_exptl_absorpt_correction_T_max  0.914
_exptl_absorpt_correction_T_min  0.730
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008)
;
_exptl_crystal_colour            'rose red'
_exptl_crystal_density_diffrn    1.855
_exptl_crystal_description       plate
_exptl_crystal_F_000             6278.5
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.02
_refine_diff_density_max         3.572
_refine_diff_density_min         -1.796
_refine_diff_density_rms         0.183
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.115
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2656
_refine_ls_number_reflns         39554
_refine_ls_number_restraints     258
_refine_ls_restrained_S_all      1.117
_refine_ls_R_factor_all          0.0934
_refine_ls_R_factor_gt           0.0681
_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^)+(0.0626P)^2^+197.8928P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1683
_refine_ls_wR_factor_ref         0.1920
_reflns_Friedel_coverage         0.000
_reflns_number_gt                30553
_reflns_number_total             39554
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc03455b2.cif
_cod_data_source_block           4
_cod_original_cell_volume        11315.1(17)
_cod_database_code               1552305
_shelx_shelxl_version_number     2017/1
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C9-C10 = C9-C11 = C9-C12 = C9B-C10B = C9B-C11B = C9B-C12 = C9B-C12B
 1.53 with sigma of 0.01
 C81-C82A = C81-C82B = C81-C83A = C81-C83B = C81-C84 = C81-C84
 1.53 with sigma of 0.01
 C15-C17A = C15-C17B = C33-C36 = C87A-C90A
 1.53 with sigma of 0.01
 C173-C174 = C175-C176
 1.53 with sigma of 0.01
 C177-C178 = C179-C180
 1.53 with sigma of 0.01
 C174-O20 = C175-O20
 1.4 with sigma of 0.01
 C178-O21 = C179-O21
 1.4 with sigma of 0.01
 Cl3-C172 = Cl4-C172
 1.75 with sigma of 0.01
3. Rigid bond restraints
 C8, C9, C81, C84, C93, C94A
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.01
 C123, C124
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.01
 C177, C178, C179, C180
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.01
 O21, C178, O21, C179
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C4) \\sim Ueq, Uanis(C82A) \\sim Ueq, Uanis(C82B) \\sim Ueq, Uanis(C83A)
\\sim Ueq, Uanis(C17A) \\sim Ueq, Uanis(C17B) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C24) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42)
\\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C90) \\sim Ueq,
Uanis(C94) \\sim Ueq, Uanis(C94A) \\sim Ueq, Uanis(C95) \\sim Ueq, Uanis(C90A)
\\sim Ueq, Uanis(C112) \\sim Ueq, Uanis(C123) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C65) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C76)
\\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C87A) \\sim Ueq,
Uanis(C88) \\sim Ueq, Uanis(C126) \\sim Ueq, Uanis(C130) \\sim Ueq, Uanis(C132)
\\sim Ueq, Uanis(C153) \\sim Ueq, Uanis(C154) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C177) \\sim Ueq, Uanis(C178) \\sim Ueq, Uanis(O21) \\sim Ueq, Uanis(C179)
\\sim Ueq, Uanis(C180) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C40A) = Uanis(C40)
Uanis(Cu47) = Uanis(CU97)
Uanis(C35) = Uanis(C35A)
Uanis(C36) = Uanis(C36A)
Uanis(C53A) = Uanis(C53B)
Uanis(C83A) = Uanis(C83B)
Uanis(C94) = Uanis(C94A)
Uanis(C17A) = Uanis(C17B)
Uanis(C76) = Uanis(C76B)
Uanis(C9) = Uanis(C9B)
Uanis(C10) = Uanis(C10B)
Uanis(C41) = Uanis(C41A)
Uanis(C11) = Uanis(C11B)
Uanis(C12) = Uanis(C12B)
Uanis(C106) = Uanis(C206)
Uanis(C107) = Uanis(C207)
Uanis(C108) = Uanis(C208)
5. Others
 Sof(CU97)=Sof(Cu2A)=Sof(Cu4A)=1-FVAR(1)
 Sof(Cu47)=Sof(Cu2)=Sof(Cu4)=FVAR(1)
 Sof(C8B)=Sof(C9B)=Sof(C10B)=Sof(H10V)=Sof(H9A)=Sof(H9B)=Sof(C11B)=Sof(H11S)=
 Sof(H11T)=Sof(H11U)=Sof(C12B)=Sof(H12Q)=Sof(H12D)=Sof(H12R)=Sof(C76B)=1-FVAR(2)
 Sof(C8)=Sof(C9)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=
 Sof(H11B)=Sof(H11C)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C76)=Sof(H76A)=
 Sof(H76B)=Sof(H76C)=FVAR(2)
 Sof(C82B)=Sof(H82D)=Sof(H82E)=Sof(H82F)=Sof(C83B)=Sof(H83D)=Sof(H83E)=
 Sof(H83F)=1-FVAR(3)
 Sof(C82A)=Sof(H82A)=Sof(H82B)=Sof(H82C)=Sof(C83A)=Sof(H83A)=Sof(H83B)=
 Sof(H83C)=FVAR(3)
 Sof(C17B)=1-FVAR(4)
 Sof(C17A)=FVAR(4)
 Sof(C53B)=Sof(H53D)=Sof(H53E)=Sof(H53F)=1-FVAR(5)
 Sof(C53A)=Sof(H53A)=Sof(H53B)=Sof(H53C)=FVAR(5)
 Sof(C87A)=Sof(C90A)=1-FVAR(6)
 Sof(C87)=Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(H90C)=FVAR(6)
 Sof(C94A)=1-FVAR(7)
 Sof(C94)=Sof(H94A)=Sof(H94B)=Sof(H94C)=FVAR(7)
 Sof(C40A)=Sof(H40F)=Sof(H40G)=Sof(H40H)=Sof(C41A)=Sof(H41D)=Sof(H41E)=
 Sof(H41F)=Sof(C35A)=Sof(H35E)=Sof(H35F)=Sof(H35G)=Sof(C206)=Sof(H20A)=
 Sof(H20B)=Sof(H20C)=Sof(C207)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C208)=
 Sof(H20G)=Sof(H20H)=Sof(H20I)=Sof(C36A)=Sof(H36C)=Sof(H35H)=Sof(H36D)=1-FVAR(8)
 Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C106)=Sof(H10D)=Sof(H10E)=Sof(H10F)=
 Sof(C107)=Sof(H10G)=Sof(H10H)=Sof(H10I)=Sof(C108)=Sof(H10J)=Sof(H10K)=
 Sof(H10L)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H35D)=FVAR(8)
 Fixed Sof: C179(0.5) C180(0.5) C172(0.5) C272(0.5) C280(0.5) C279(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C171(H17D,H17E)
6.b Me refined with riding coordinates:
 C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C40A(H40F,H40G,H40H), C41A(H41D,
 H41E,H41F), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C35(H35A,H35B,H35C), C106(H10D,H10E,H10F), C107(H10G,H10H,H10I), C108(H10J,
 H10K,H10L), C36(H36A,H36B,H35D), C42(H42,H40D,H40E), C76(H76A,H76B,H76C),
 C78(H78A,H78B,H78C), C95(H95A,H95B,H95C), C96(H96A,H96B,H96C), C35A(H35E,H35F,
 H35G), C206(H20A,H20B,H20C), C207(H20D,H20E,H20F), C208(H20G,H20H,H20I),
 C36A(H36C,H35H,H36D), C53A(H53A,H53B,H53C), C82A(H82A,H82B,H82C), C83A(H83A,
 H83B,H83C), C10B(H10V,H9A,H9B), C11B(H11S,H11T,H11U), C12B(H12Q,H12D,H12R),
 C53B(H53D,H53E,H53F), C82B(H82D,H82E,H82F), C83B(H83D,H83E,H83F)
6.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C16(H16A,H16B,H16C),
 C18(H18A,H18B,H18C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), 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),
 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), C77(H77A,H77B,H77C),
 C84(H84A,H84B,H84C), C88(H88A,H88B,H88C), C89(H89A,H89B,H89C), C90(H90A,H90B,
 H90C), C94(H94A,H94B,H94C), C100(H10M,H10N,H10O), C101(H10P,H10Q,H10R),
 C102(H10S,H10T,H10U), C112(H11D,H11E,H11F), C113(H11G,H11H,H11I), C114(H11J,
 H11K,H11L), C118(H11M,H11N,H11O), C119(H11P,H11Q,H11R), C120(H12E,H12F,H12G),
 C124(H12H,H12I,H12J), C125(H12K,H12L,H12M), C126(H12N,H12O,H12P), C130(H13A,
 H13B,H13C), C131(H13D,H13E,H13F), C132(H13G,H13H,H13I), C136(H13J,H13K,H13L),
 C137(H13M,H13N,H13O), C138(H13P,H13Q,H13R), C142(H14A,H14B,H14C), C143(H14D,
 H14E,H14F), C144(H14G,H14H,H14I), C148(H14J,H14K,H14L), C149(H14M,H14N,H14O),
 C150(H15A,H15B,H15C), C154(H15D,H15E,H15F), C155(H15G,H15H,H15I), C156(H15J,
 H15K,H15L), C160(H16D,H16E,H16F), C161(H16G,H16H,H16I), C162(H16J,H16K,H16L),
 C164(H16M,H16N,H16O), C165(H16P,H16Q,H16R), C166(H16S,H16T,H16U), C168(H16V,
 H16W,H16X), C169(H16Y,H,HA), C170(H17A,H17B,H17C)
;
_olex2_submission_special_instructions 'No special instructions were received'