Yang L., Dinca M. · Angewandte Chemie - International Edition · 2021 · 23784-23789
Open a family to keep every result attached to its sample, method and conditions.
Paraphrased for this database from the authors’ stated interpretations — never quoted verbatim — and kept separate from reported measurements.
The trinickel HOTP complexes are molecular models of the smallest building blocks of conductive 2D metal-organic frameworks such as Ni-HOTP.
Caveat: The paper does not synthesize or measure an extended conductive MOF in this work.
p001 / article p.23784 · Abstract
No first-hand electrical transport, thermoelectric or porosity data are reported; conductive-MOF relevance is by molecular modelling and analogy to Ni-HOTP frameworks.
p001-p006 · Full article · Linked to 1 structured result
Complex 2 is assigned as a Robin-Day class III mixed-valence compound with full delocalisation among the three semiquinonate sub-units.
Caveat: Based on mixed-valence interpretation of redox potential separation for the molecular complex.
SI p008 / printed p.7 · Electrochemical Characterizations and Electrolysis · Figure S3 · Linked to 2 structured results
The three complexes form a ligand-centred redox ladder with HOTP formal charges -4, -3 and -2 in complexes 1, 2 and 3, respectively, with no formal Ni oxidation-state changes.
Caveat: Assignment integrates electrochemistry, spectroscopy and structural comparison rather than direct Ni oxidation-state measurement alone.
p002 / article p.23785 · Results and Discussion · Figure 2; Scheme 1 · Linked to 7 structured results
Oxidation from complex 1 to 3 increases HOTP quinoidal character, shown by blue-shifted near-IR absorption and C-O stretching bands.
p002 / article p.23785 · Results and Discussion · Figures S6-S7 · Linked to 6 structured results
Spin coupling strength decreases as HOTP becomes more oxidised, likely due to decreased spin density on the bridging ligand.
Caveat: Magnetic models depend on fitted Hamiltonians and assumed coupling schemes.
p005 / article p.23788 · Conclusion · Figures 3-4 · Linked to 7 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| crude [(Me3TPANi)3(HOTP)](BF4)n mixture | [(Me3TPANi)3(HOTP)](BF4)nTrinickel HOTP cations · HOTP bridge and Me3TPA capping ligands | 0D · Model SystemCrude molecular mixture composed mostly of complex 1 with a minor fraction of complex 2, based on CV and UV-visible spectra. | SI p008 / printed p.8 · Electrochemical Characterizations and Electrolysis · Figure S5 |
| complex 1, [(Me3TPANi)3(HOTP)](BF4)2 | [(Me3TPANi)3(HOTP)](BF4)2; analytical formula C81H78N12O6Ni3B2F8 with lattice solventThree Ni2+ centres capped by Me3TPA and bridged by one HOTP unit · 2,3,6,7,10,11-hexaoxytriphenylene (HOTP4-) plus Me3TPA capping ligands | 0D · Model SystemMolecular trinickel HOTP model complex; HOTP formal charge -4 with singlet diradical character and S = 3 spin ground state. | p001 / article p.23784 · Abstract; Introduction · Scheme 1 |
| complex 2, [(Me3TPANi)3(HOTP)](BF4)3 | C81H78B3F12N12Ni3O6Three Ni2+ centres capped by Me3TPA and bridged by one HOTP unit · HOTP3- semiquinonate bridge plus Me3TPA capping ligands | 0D · Model SystemSingle-crystal structure in P21/n; molecular [Ni3HOTP]3+ units separated by Me3TPA and BF4- anions; HOTP3- monoradical, Robin-Day class III mixed-valence. | p002 / article p.23785 · Results and Discussion · Figure 1 |
| complex 3, [(Me3TPANi)3(HOTP)](BF4)4 | [(Me3TPANi)3(HOTP)](BF4)4; analytical formula C81H78N12O6Ni3B4F16 with lattice solventThree Ni2+ centres capped by Me3TPA and bridged by one HOTP unit · HOTP2- closed-shell bridge plus Me3TPA capping ligands | 0D · Model SystemMolecular trinickel HOTP model complex; HOTP formal charge -2 with closed-shell configuration and weak antiferromagnetic interactions. | p001 / article p.23784 · Abstract · Scheme 1 |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| complex 1 dark green ribbon-shaped crystalsresearch_0290__mat__mat_ni3hotp_1 | Single Crystal · Model System · Model | Electrolysed and recrystallised twice from dichloromethane/hexane; also used as crushed microcrystalline powder in eicosane for magnetometry and as frozen DCM glass for EPR. | SI p004 / printed p.3 · Synthesis of 1 · Scheme S1b |
| complex 2 dark blue needle-shaped crystalsresearch_0290__mat__mat_ni3hotp_2 | Single Crystal · Model System · Model | Oxidised from complex 1 with ferrocenium tetrafluoroborate and recrystallised twice from dichloromethane/hexane.0.25 x 0.02 x 0.02 mm3 for XRD crystal | SI p005 / printed p.4 · Synthesis of 2 |
| complex 3 dark violet needle-shaped crystalsresearch_0290__mat__mat_ni3hotp_3 | Single Crystal · Model System · Model | Oxidised from complex 1 with silver tetrafluoroborate and recrystallised twice from dichloromethane/hexane. | SI p005 / printed p.4 · Synthesis of 3 |
| crude [(Me3TPANi)3(HOTP)](BF4)n mixtureresearch_0290__mat__mat_crude_ni3hotp_mixture | Unknown · Model System · Model | Black-navy solid from air synthesis; recrystallised to a mixture of dark blue plate-shaped and dark green ribbon-shaped crystals. | SI p004 / printed p.3 · Synthesis of the crude mixture · Scheme S1a |