Usov P.M., Leong C.F., Chan B. et al. · Physical Chemistry Chemical Physics · 2018 · 25772-25779
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 assigned main and SI documents do not provide a complete synthesis recipe for the MOF; they cite a previous Chem. Sci. literature method.
Caveat: A prior synthesis paper is needed for precursor identities/amounts, solvent, temperature, time, workup, and activation.
p002 / journal page 25773 · Synthesis of [(Zn(DMF))2(TTFTC)(DPNI)]
No abrupt pressure-induced neutral-ionic phase transition is observed in the Raman spectra.
Caveat: Based on absence of abrupt Raman changes over the measured pressure range.
p006 / journal page 25777 · Pressure-dependent resonance Raman scattering spectroscopy · Fig. 4 · Linked to 1 structured result
Raman spectroscopy detects neutral TTFTC and DPNI species in the framework, supporting heterogeneous charge distribution despite calculated partial charge transfer.
Caveat: DPNI radical anion and TTFTC radical cation peaks may be too weak to observe unambiguously by Raman.
p004 / journal page 25775 · Results and discussion · Fig. 2 · Linked to 3 structured results
Pressure causes monotonic Raman blue shifts and contraction of the a and b axes plus compression of beta, consistent with bond shortening and disruption/decrease of donor-acceptor charge transfer.
Caveat: Raman shift magnitudes were estimated visually from Fig. 4c; unit-cell parameters are reported in Table 1.
p007 / journal page 25778 · Pressure-dependent PXRD discussion · Fig. 4; Table 1 · Linked to 9 structured results
In situ Raman SEC shows oxidation of DPNI radical anion to neutral DPNI and neutral TTFTC to TTFTC radical cation, generating a TTFTC.+-DPNI charge-transfer complex.
Caveat: SEC oxidation is not reversible on the longer SEC timescale.
p005 / journal page 25776 · In situ Raman spectroelectrochemistry · Fig. 3; Scheme 1 · Linked to 4 structured results
Band-structure calculations indicate that hole transport is the primary mechanism for charge migration in the MOF.
Caveat: Mechanism is computationally inferred from band dispersion rather than directly measured carrier type.
p005 / journal page 25776 · Results and discussion · Fig. S6 · Linked to 1 structured result
The pressed-pellet conductivity and band-structure calculations support semiconducting behaviour in [(Zn(DMF))2(TTFTC)(DPNI)].
Caveat: Conductivity was measured by a two-point pressed-pellet geometry, so contact and grain-boundary effects are not isolated.
p004 / journal page 25775 · Results and discussion · Fig. S5-S6 · Linked to 3 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| [(Zn(DMF))2(TTFTC)(DPNI)] | [(Zn(DMF))2(TTFTC)(DPNI)]Zn(II) centres with coordinated DMF · TTFTC = tetrathiafulvalene tetracarboxylate; DPNI = N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide | 3D · PristineDonor-acceptor MOF with mixed stacks of donor TTFTC and acceptor DPNI ligands down the crystallographic a-axis. | p002 / journal page 25773 · Introduction · Fig. 1 |
| DPNI | N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimideDPNI acceptor ligand | 0D · Model SystemMolecular acceptor ligand control for Raman, CV, EPR, and DFT vibrational assignments. | p002 / journal page 25773 · Introduction |
| H4TTFTC | tetrathiafulvalene tetracarboxylic acidH4TTFTC donor precursor to TTFTC | 0D · Model SystemMolecular donor ligand control for Raman, CV, EPR, and DFT vibrational assignments. | p004 / journal page 25775 · Results and discussion · Fig. 2 |
| (TTFTC)(DPNI) model complex | (TTFTC)(DPNI)none in discrete model · TTFTC and DPNI extracted from the MOF crystal structure | 0D · Model SystemDiscrete donor-acceptor computational model extracted from the MOF crystal structure. | p003 / journal page 25774 · Density functional theory (DFT) calculations |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| bulk powder [(Zn(DMF))2(TTFTC)(DPNI)]research_0661__mat__mat_ct_mof | Powder · Target Sample · Pristine Framework | solid MOF powder synthesised according to a previously reported methodsilicon crystal substrate for Raman spectroscopy | p002 / journal page 25773 · Experimental |
| solid-state [(Zn(DMF))2(TTFTC)(DPNI)] CV electroderesearch_0661__mat__mat_ct_mof | Electrode · Target Sample · Pristine Framework | surface-confined powder mechanically immobilised or drop-cast from CH2Cl2 suspensionglassy carbon disc electrode or graphite paper strip with Pt wire current collector | SI p002 · Cyclic Voltammetry · Fig. S8 |
| periodic [(Zn(DMF))2(TTFTC)(DPNI)] DFT modelresearch_0661__mat__mat_ct_mof | Model · Model System · Model | optimised periodic MOF model for band-structure calculations | p003 / journal page 25774 · Band structure calculations · Fig. S6 |
| pressed pellet [(Zn(DMF))2(TTFTC)(DPNI)]research_0661__mat__mat_ct_mof | Pellet · Target Sample · Pristine Framework | powder pressed at 0.25 tonnes and contacted between two FTO platesFTO plates with conductive silver epoxy contacts · 7.14 mm diameter pellet; approximately 40 mg | p003 / journal page 25774 · Two-point probe conductivity |
| [(Zn(DMF))2(TTFTC)(DPNI)] powder in DAC for variable-pressure PXRDresearch_0661__mat__mat_ct_mof | Powder · Target Sample · Pristine Framework | powder loaded for synchrotron variable-pressure PXRDstainless steel gasket in DAC with Fluorinert FC-70 and NaCl internal standard · 200 um diameter gasket hole | p003 / journal page 25774 · Variable-pressure powder X-ray diffraction · Fig. 4d; Table 1 |
| [(Zn(DMF))2(TTFTC)(DPNI)] powder on DS-150 screen-printed electroderesearch_0661__mat__mat_ct_mof | Electrode · Target Sample · Pristine Framework | powder mechanically immobilised on working electrode; 0.2 M LiClO4/ethylene glycol droplet addedDS-150 screen-printed electrode with glassy carbon working electrode, Pt counter strip, and Ag reference plate | p003 / journal page 25774 · In situ solid state Raman spectroelectrochemistry · Fig. S1-S2 |
| single crystal [(Zn(DMF))2(TTFTC)(DPNI)] in DACresearch_0661__mat__mat_ct_mof | Single Crystal · Target Sample · Pristine Framework | single crystal loaded for pressure-dependent Raman spectroscopy; ruby pressure standarddiamond anvil cell with Daphne 7474 pressure medium | p006 / journal page 25777 · Pressure-dependent resonance Raman scattering spectroscopy · Fig. 4a-c |
| solid DPNIresearch_0661__mat__mat_dpni | Powder · Model System · Model | solid DPNI reference/controlscreen-printed electrode for electrochemical Raman where specified | p003 / journal page 25774 · Results and discussion · Fig. 2 |
| H4TTFTC solutionresearch_0661__mat__mat_h4ttftc | Unknown · Model System · Model | 0.03 mM H4TTFTC solution for CV; solid H4TTFTC also used for Raman/EPRglassy carbon disc electrode for solution-state CV | SI p007 · Figure S8 caption · Fig. S8 |
| (TTFTC)(DPNI) discrete computational modelresearch_0661__mat__mat_ttftc_dpni_model | Model · Model System · Model | geometry extracted from MOF crystal structure without modification | p003 / journal page 25774 · Density functional theory (DFT) calculations |