Neumann T., Liu J., Wachter T. et al. · ACS Nano · 2016 · 7085-7093
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 KMC calculations assume perfectly loaded MOFs, while the exact experimental guest loading density is unknown.
Caveat: ToF-SIMS supports homogeneous TCNQ distribution but does not quantify absolute loading density.
7091 · Results and Discussion · Linked to 2 structured results
Use of oriented SURMOF films on SAM-modified Au and Hg-drop junctions was intended to reduce artefacts from defects, MOF-electrode interfaces and orientation differences.
Caveat: This is an experimental-design claim; remaining discrepancy with prior F4-TCNQ literature is unresolved.
7089 · Results and Discussion · Linked to 2 structured results
Alternative DCM loading and an alternative COOH-terminated SAM template gave qualitatively similar electrical effects for homogeneous loaded samples, but the SI reports no systematic quantitative dataset.
Caveat: Some DCM-loaded samples were incomplete/inhomogeneous; no F4-TCNQ loading was performed with the alternative SAM template.
S11 · 2.5-2.6 · Linked to 2 structured results
TCNQ and F4-TCNQ loading leaves the HKUST-1 SURMOF framework orientation/crystallinity and characteristic framework IR bands largely intact.
Caveat: XRD evidence is qualitative for loaded samples; relative intensity changes are attributed tentatively to form-factor changes.
7089 · Results and Discussion · Figure 4 · Linked to 5 structured results
In the preferred calculated configuration, TCNQ/F4-TCNQ guest molecules bind through nitrile nitrogens to Cu sites, creating additional hopping sites and enabling superexchange paths.
Caveat: Binding geometry is computationally optimised on fixed HKUST-1 subsets and supported by spectroscopic shifts rather than direct crystallographic location of guests.
7087 · Results and Discussion · Figure 2 · Linked to 5 structured results
The proposed superexchange mechanism accounts for the conductivity enhancement only for electron transport; hole-transport simulations do not show a comparable superexchange-enhanced mobility.
Caveat: Carrier type is inferred from model consistency; authors state the Seebeck coefficient in the hopping transport model remains to be determined.
7088 · Results and Discussion · Figure 3d,e · Linked to 2 structured results
The large conductivity increase in TCNQ- and F4-TCNQ-loaded HKUST-1 SURMOFs is explained by electron hopping via molecular superexchange through virtual MOF states, not by simple direct hopping or band transport.
Caveat: Exact guest loading density is unknown; authors note hybrid mechanisms may also be possible.
7091 · Conclusions · Linked to 4 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| CMMT self-assembled monolayer on Au/Si | CMMT SAM/Au/Si9-carboxy-10-(mercaptomethyl)triptycene thiol | unknown · UnknownCOOH-terminated SAM template for HKUST-1 SURMOF growth on Au/Si. | S2 · 1.2 Preparation of the SAMs template · Figure S1 |
| F4-TCNQ/HKUST-1 model systemBrowse family: HKUST-1 / Cu₃(BTC)₂ | F4-TCNQ plus HKUST-1 fragment modelCu-containing MOF sites in model fragment · BTC-derived saturated linker fragments plus F4-TCNQ | unknown · Model SystemDFT/KMC model with F4-TCNQ guest and four MOF-sites used for electronic coupling and superexchange calculations. | S13 · 3.2 Marcus theory of hopping · Figure S10 |
| F4-TCNQ-loaded HKUST-1 SURMOFBrowse family: HKUST-1 / Cu₃(BTC)₂ | F4-TCNQ@HKUST-1 / F4-TCNQ-loaded Cu-BTC SURMOFCu paddle-wheel / Cu2+ sites bridged by F4-TCNQ nitrile groups · BTC framework linker plus 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane guest | 3D · CompositeGuest-loaded HKUST-1 SURMOF; XRD indicates framework crystallinity retained and IRRAS/Raman indicate F4-TCNQ interaction with Cu2+ sites. | 7089 · Results and Discussion · Figure 4b,d |
| HKUST-1 SURMOFBrowse family: HKUST-1 / Cu₃(BTC)₂ | Cu-BTC framework; HKUST-1 conventionally Cu3(BTC)2Cu paddle-wheel / Cu2+ sites · 1,3,5-benzenetricarboxylate (BTC) | 3D · PristineSurface-anchored HKUST-1 film with crystalline [111] orientation perpendicular to the substrate; XRD shows characteristic (111), (222) and (333) peaks. | 7089 · Results and Discussion · Figure 4 |
| TCNQ/HKUST-1 model systemBrowse family: HKUST-1 / Cu₃(BTC)₂ | TCNQ plus HKUST-1 fragment modelCu-containing MOF sites in model fragment · BTC-derived saturated linker fragments plus TCNQ | unknown · Model SystemDFT/KMC model with TCNQ guest and four MOF-sites used for electronic coupling and superexchange calculations. | S13 · 3.2 Marcus theory of hopping · Figure S10 |
| TCNQ-loaded HKUST-1 SURMOFBrowse family: HKUST-1 / Cu₃(BTC)₂ | TCNQ@HKUST-1 / TCNQ-loaded Cu-BTC SURMOFCu paddle-wheel / Cu2+ sites bridged by TCNQ nitrile groups · BTC framework linker plus 7,7,8,8-tetracyanoquinodimethane guest | 3D · CompositeGuest-loaded HKUST-1 SURMOF; XRD indicates framework crystallinity retained and IRRAS/Raman indicate TCNQ interaction with Cu2+ sites. | 7089 · Results and Discussion · Figure 4a,c |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| CMMT SAM/Au/Si templateresearch_0492__mat__mat_cmmt_sam_au | Thin Film · Composite Component · Composite | COOH-terminated CMMT SAM prepared on Au substrate before SURMOF growth5 nm Ti / 100 nm Au on silicon (100) wafer · CMMT monolayer; Au layer 100 nm on 5 nm Ti adhesion layer | S2 · 1.1 Materials; 1.2 Preparation of the SAMs template · Figure S1 |
| F4-TCNQ-loaded HKUST-1 SURMOF, 5 spray cyclesresearch_0492__mat__mat_f4tcnq_hkust1_surmoF | Thin Film · Target Sample · Guest Loaded | pristine SURMOF activated, then immersed in 2 mM F4-TCNQ ethanol solution for 72 h at room temperature; ethanol rinse and nitrogen dryingCMMT SAM-modified Au/Si · assigned as 44.7 nm based on 5 spray cycles; no direct F4-TCNQ thickness evaluation | S10 · 2.3.1 Thickness evaluation |
| F4-TCNQ-loaded HKUST-1 SURMOF, DCM loading variantresearch_0492__mat__mat_f4tcnq_hkust1_surmoF | Thin Film · Target Sample · Guest Loaded | loaded from dichloromethane solution under otherwise mostly unchanged conditionsCMMT SAM-modified Au/Si · not reported | S11 · 2.5 Results for an alternative solvent |
| F4-TCNQ/HKUST-1 computational modelresearch_0492__mat__mat_f4tcnq_hkust1_model | Model · Model System · Model | DFT-optimised HKUST-1 fragment with F4-TCNQ guests and KMC transport model | S12 · 3.1 Calculation of the binding mechanism · Figure S9 |
| Pristine HKUST-1 SURMOF, 10 spray cyclesresearch_0492__mat__mat_hkust1_surmoF | Thin Film · Pristine Control · Pristine Framework | as-grown HKUST-1 SURMOF; activated at 60 C for 20 min in air before loading experimentsCMMT SAM-modified Au/Si · 69.4 +/- 8.5 nm | S5 · 2.1.1 Thickness evaluation · Figure S3 |
| Pristine HKUST-1 SURMOF, 5 spray cyclesresearch_0492__mat__mat_hkust1_surmoF | Thin Film · Pristine Control · Pristine Framework | as-grown HKUST-1 SURMOF; activated at 60 C for 20 min in air before loading experimentsCMMT SAM-modified Au/Si · 44.7 +/- 3.9 nm | S5 · 2.1.1 Thickness evaluation · Figure S3 |
| Pristine HKUST-1 SURMOF, 7 spray cyclesresearch_0492__mat__mat_hkust1_surmoF | Thin Film · Pristine Control · Pristine Framework | as-grown HKUST-1 SURMOF; activated at 60 C for 20 min in air before loading experimentsCMMT SAM-modified Au/Si · 57.1 +/- 5.6 nm | S5 · 2.1.1 Thickness evaluation · Figure S3 |
| TCNQ-loaded HKUST-1 SURMOF, 10 spray cyclesresearch_0492__mat__mat_tcnq_hkust1_surmoF | Thin Film · Target Sample · Guest Loaded | pristine SURMOF activated, then immersed in 2 mM TCNQ ethanol solution for 72 h at room temperature; ethanol rinse and nitrogen dryingCMMT SAM-modified Au/Si · 62.3 +/- 7.3 nm | S5 · 2.1.1 Thickness evaluation · Figure S3 |
| TCNQ-loaded HKUST-1 SURMOF, 20 spray cyclesresearch_0492__mat__mat_tcnq_hkust1_surmoF | Thin Film · Target Sample · Guest Loaded | TCNQ-loaded SURMOF used for ToF-SIMS depth profileCMMT SAM-modified Au/Si · 20 spray cycles; thickness not reported | S7 · 2.1.3 Time-of-flight secondary ion mass spectrometry · Figure S5 |
| TCNQ-loaded HKUST-1 SURMOF, 5 spray cyclesresearch_0492__mat__mat_tcnq_hkust1_surmoF | Thin Film · Target Sample · Guest Loaded | pristine SURMOF activated, then immersed in 2 mM TCNQ ethanol solution for 72 h at room temperature; ethanol rinse and nitrogen dryingCMMT SAM-modified Au/Si · 33.3 +/- 3.0 nm | S5 · 2.1.1 Thickness evaluation · Figure S3 |
| TCNQ-loaded HKUST-1 SURMOF, 7 spray cyclesresearch_0492__mat__mat_tcnq_hkust1_surmoF | Thin Film · Target Sample · Guest Loaded | pristine SURMOF activated, then immersed in 2 mM TCNQ ethanol solution for 72 h at room temperature; ethanol rinse and nitrogen dryingCMMT SAM-modified Au/Si · 53.2 +/- 4.1 nm | S5 · 2.1.1 Thickness evaluation · Figure S3 |
| TCNQ-loaded HKUST-1 SURMOF on 16-mercaptohexadecanoic acid SAMresearch_0492__mat__mat_tcnq_hkust1_surmoF | Thin Film · Target Sample · Guest Loaded | alternative COOH-terminated SAM template; TCNQ-loaded homogeneous samples16-mercaptohexadecanoic-acid SAM template on Au/Si · not reported | S11 · 2.6 Results for an alternative SAM template |
| TCNQ-loaded HKUST-1 SURMOF, DCM loading variantresearch_0492__mat__mat_tcnq_hkust1_surmoF | Thin Film · Target Sample · Guest Loaded | loaded from dichloromethane solution under otherwise mostly unchanged conditionsCMMT SAM-modified Au/Si · not reported | S11 · 2.5 Results for an alternative solvent |
| TCNQ/HKUST-1 computational modelresearch_0492__mat__mat_tcnq_hkust1_model | Model · Model System · Model | DFT-optimised HKUST-1 fragment with TCNQ guests and KMC transport model | S12 · 3.1 Calculation of the binding mechanism · Figure S9 |