A photoresponsive ionic hydrogen-bonded organic framework exhibiting pyridine protonation effects achieves room-temperature phosphorescence through polymer doping.
Wang, Jia-Yu; Zhou, Bin; Cao, Li-Hui; Chemical communications (Cambridge, England)  (2026) –; doi:10.1039/d6cc00877a

data_7135705
_publ_section_title
;
 A photoresponsive ionic hydrogen-bonded organic framework exhibiting
 pyridine protonation effects achieves room-temperature phosphorescence
 through polymer doping.
;
_journal_issue                   30
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              7804
_journal_page_last               7807
_journal_paper_doi               10.1039/d6cc00877a
_journal_volume                  62
_journal_year                    2026
_chemical_absolute_configuration ad
_chemical_formula_moiety         '9(C24 H15 O9 S3), 9(C15 H15 N4), 93(H2 O)'
_chemical_formula_sum            'C351 H456 N36 O174 S27'
_chemical_formula_weight         8829.11
_space_group_crystal_system      trigonal
_space_group_IT_number           145
_space_group_name_Hall           'P 32'
_space_group_name_H-M_alt        'P 32'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-09-16
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2025-09-16 deposited with the CCDC.	2026-03-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            1
_cell_length_a                   22.0448(9)
_cell_length_b                   22.0448(9)
_cell_length_c                   23.7361(13)
_cell_measurement_reflns_used    9833
_cell_measurement_temperature    193.15(10)
_cell_measurement_theta_max      26.689
_cell_measurement_theta_min      2.521
_cell_volume                     9989.7(8)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2016)'
_computing_data_collection       'Bruker D8 Venture diffractometer'
_computing_data_reduction        'SAINT V8.40B (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      193.15(10)
_diffrn_detector                 'Bruker PHOTON-II area detector'
_diffrn_detector_area_resol_mean 7.4
_diffrn_detector_type            'CMOS-PHOTONII area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0984
_diffrn_reflns_av_unetI/netI     0.1021
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            93865
_diffrn_reflns_point_group_measured_fraction_full 0.906
_diffrn_reflns_point_group_measured_fraction_max 0.892
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.548
_diffrn_reflns_theta_min         1.848
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           40.0
_diffrn_source_power             1.8
_diffrn_source_target            Mo
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    0.251
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5811
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1020 before and 0.0710 after correction.
The Ratio of minimum to maximum transmission is 0.7794.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.468
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             4638
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.830
_refine_diff_density_min         -0.578
_refine_diff_density_rms         0.121
_refine_ls_abs_structure_details
;
 Flack x determined using 5542 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.14(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1870
_refine_ls_number_reflns         27399
_refine_ls_number_restraints     310
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.1574
_refine_ls_R_factor_gt           0.1154
_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^)+(0.0756P)^2^+71.3807P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2695
_refine_ls_wR_factor_ref         0.2951
_reflns_Friedel_coverage         0.789
_reflns_Friedel_fraction_full    0.812
_reflns_Friedel_fraction_max     0.787
_reflns_number_gt                19265
_reflns_number_total             27399
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc00877a3.cif
_cod_data_source_block           250226lu_lgpz2401337_2-zcs
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 7135705.cif.
;
_cod_original_cell_volume        9989.7(10)
_cod_database_code               7135705
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.952
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Uiso/Uaniso restraints and constraints
O31 \\sim O31A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
N9 \\sim N12 \\sim C89 \\sim C90 \\sim C91 \\sim C92 \\sim C93 \\sim N12A \\sim
C89A \\sim C90A \\sim C91A \\sim C92A \\sim C93A: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
O34 \\sim O34A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
O52 \\sim O52A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
O51 \\sim O51A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
O58 \\sim O58A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(O31) \\sim Ueq, Uanis(O31A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O34) \\sim Ueq, Uanis(O34A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O52) \\sim Ueq, Uanis(O52A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O51) \\sim Ueq, Uanis(O51A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O58) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O56) \\sim Ueq, Uanis(O32) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
3. Same fragment restrains
{N9, N12A, C89A, C90A, C91A, C92A, C93A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{N9, N12, C89, C90, C91, C92, C93}
4. Others
 Sof(O31A)=Sof(H31c)=Sof(H31d)=1-FVAR(1)
 Sof(O31)=Sof(H31a)=Sof(H31b)=FVAR(1)
 Sof(O34A)=Sof(H34c)=Sof(H34d)=1-FVAR(2)
 Sof(O34)=Sof(H34a)=Sof(H34b)=FVAR(2)
 Sof(O52A)=Sof(H52c)=Sof(H52d)=1-FVAR(3)
 Sof(O52)=Sof(H52a)=Sof(H52b)=FVAR(3)
 Sof(O51A)=Sof(H51c)=Sof(H51d)=1-FVAR(4)
 Sof(O51)=Sof(H51a)=Sof(H51b)=FVAR(4)
 Sof(O58A)=Sof(H58c)=Sof(H58d)=1-FVAR(5)
 Sof(O58)=Sof(H58a)=Sof(H58b)=FVAR(5)
 Sof(N12A)=Sof(H12A)=Sof(C89A)=Sof(C90A)=Sof(H90A)=Sof(C91A)=Sof(H91A)=
 Sof(C92A)=Sof(H92A)=Sof(C93A)=Sof(H93A)=1-FVAR(6)
 Sof(N12)=Sof(H12)=Sof(C89)=Sof(C90)=Sof(H90)=Sof(C91)=Sof(H91)=Sof(C92)=
 Sof(H92)=Sof(C93)=Sof(H93)=FVAR(6)
5.a Riding coordinates:
 O28(H28a,H28b), O29(H29a,H29b), O30(H30a,H30b), O32(H32a,H32b), O33(H33a,
 H33b), O35(H35a,H35b), O36(H36a,H36b), O37(H37a,H37b), O38(H38a,H38b),
 O39(H39a,H39b), O40(H40a,H40b), O41(H41a,H41b), O42(H42a,H42b), O43(H43a,H43b),
  O44(H44a,H44b), O45(H45a,H45b), O46(H46a,H46b), O47(H47a,H47b), O48(H48a,
 H48b), O49(H49a,H49b), O50(H50a,H50b), O53(H53a,H53b), O54(H54a,H54b),
 O55(H55a,H55b), O56(H56a,H56b), O57(H57a,H57b), O31(H31a,H31b), O34(H34a,H34b),
  O51(H51a,H51b), O52(H52a,H52b), O58(H58a,H58b), O31A(H31c,H31d), O34A(H34c,
 H34d), O51A(H51c,H51d), O52A(H52c,H52d), O58A(H58c,H58d)
5.b Aromatic/amide H refined with riding coordinates:
 C17(H17), C19(H19), C21(H21), C23(H23), C24(H24), C26(H26), C27(H27),
 C29(H29), C30(H30), C32(H32), C33(H33), C35(H35), C36(H36), C38(H38), C39(H39),
  C56(H56), C58(H58), C60(H60), C62(H62), C63(H63), C65(H65), C66(H66),
 C68(H68), C69(H69), C71(H71), C72(H72), C74(H74), C75(H75), C77(H77), C78(H78),
  C95(H95), C97(H97), C99(H99), C101(H101), C102(H102), C104(H104), C105(H105),
 C107(H107), C108(H108), C110(H110), C111(H111), C113(H113), C114(H114),
 C116(H116), C117(H117), N2(H2), N3(H3), N4(H4), C2(H2a), C3(H3a), C4(H4a),
 C5(H5), C7(H7), C8(H8), C9(H9), C10(H10a), C12(H12b), C13(H13), C14(H14),
 C15(H15), N6(H6), N7(H7a), N8(H8a), C41(H41), C42(H42), C43(H43), C44(H44),
 C46(H46), C47(H47), C48(H48), C49(H49), C51(H51), C52(H52), C53(H53), C54(H54),
  N12(H12), C90(H90), C91(H91), C92(H92), C93(H93), N10(H10), N11(H11),
 C80(H80), C81(H81), C82(H82), C83(H83), C85(H85), C86(H86), C87(H87), C88(H88),
  N12A(H12A), C90A(H90A), C91A(H91A), C92A(H92A), C93A(H93A)
;
_shelx_res_checksum              33372
_shelx_hkl_checksum              72838
_olex2_submission_special_instructions 'No special instructions were received'