Spectroscopy — Tunable electrical conductivity in metal-organic framework thin-film devices

5 measurement groups · 23 results

Reported values remain attached to the sample, method, conditions, extraction quality and source location that produced them.

Continuous-wave EPR spectroscopy

Electron paramagnetic resonance

TCNQ@Cu3(BTC)2 powder · Powder

Room-temperature EPR for activated Cu3(BTC)2, methanol-treated Cu3(BTC)2 and methanol/TCNQ-treated Cu3(BTC)2; low-temperature X-band triplet EPR in SI

Temperature: room temperature and 70 K
Context: target compared with pristine/methanol controls
Measurement source: 3 · main text · Fig. 3D; Fig. S8

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Triplet zero-field splitting Dz	0.318 cm^-1	—	—	Text Exact Reported	8 · Triplet state EPR signals · Fig. S8
Triplet zero-field splitting Dz	Dz = 9550 MHz	—	—	Text Exact Reported	8 · Triplet state EPR signals · Fig. S8
Triplet EPR g tensor component	g = [2.369, 2.06, 2.06]	—	—	Text Exact Reported	8 · Triplet state EPR signals · Fig. S8
TCNQ radical-anion signal	no evidence of TCNQ radical anions	—	—	Text Qualitative	3 · main text · Fig. 3D

Infrared spectroscopy

TCNQ@Cu3(BTC)2 powder · Powder

Cu3(BTC)2.xH2O, activated Cu3(BTC)2, TCNQ@Cu3(BTC)2, and TCNQ powder

Context: target compared with pristine controls
Measurement source: 2 · main text · Fig. 3C

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Partial charge transfer inferred from IR C=N shift	~0.4e-	—	—	Text Approximate	2 · main text · Fig. 3C
TCNQ@Cu3(BTC)2 C=N stretch	2204 cm^-1	—	—	Text Exact Reported	2 · main text · Fig. 3C
TCNQ powder C=N stretch	2223 cm^-1	—	—	Text Exact Reported	2 · main text · Fig. 3C

Raman spectroscopy

Cu3(BTC)2.xH2O film on borosilicate before and after TCNQ or H4-TCNQ adsorption · Thin Film

Cu3(BTC)2.xH2O film before and after TCNQ adsorption; TCNQ crystal reference

Geometry: film on borosilicate substrate
Context: target compared with pristine film and TCNQ reference
Measurement source: 2 · main text · Fig. 3B

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
TCNQ C=C stretch after adsorption	1437 cm^-1	—	—	Text Exact Reported	2 · main text · Fig. 3B
TCNQ C=C stretch before interaction	1456 cm^-1	—	—	Text Exact Reported	2 · main text · Fig. 3B
Partial charge transfer inferred from Raman C=C shift	~0.3e-	—	—	Text Approximate	2 · main text · Fig. 3B
New Raman peak after TCNQ adsorption	1296 cm^-1	—	—	Text Exact Reported	2 · main text · Fig. 3B
New Raman peak after TCNQ adsorption	1352 cm^-1	—	—	Text Exact Reported	2 · main text · Fig. 3B
TCNQ nitrile stretch before infiltration	2229 cm^-1	—	—	Text Exact Reported	2 · main text · Fig. 3B
TCNQ nitrile split peak after infiltration	2213 cm^-1	—	—	Text Exact Reported	2 · main text · Fig. 3B inset
TCNQ nitrile split peak after infiltration	2226 cm^-1	—	—	Text Exact Reported	2 · main text · Fig. 3B inset

Transmission UV-vis spectroscopy

UV-visible and optical absorption spectroscopy

Cu3(BTC)2.xH2O film on borosilicate before and after TCNQ or H4-TCNQ adsorption · Thin Film

Cu3(BTC)2.xH2O films before and after TCNQ or H4-TCNQ adsorption; TCNQ dilute solution reference

Geometry: film on borosilicate substrate
Context: guest-loaded target and controls
Measurement source: 2 · main text · Fig. 3A

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
H4-TCNQ UV-vis charge-transfer bands	lacks characteristic bands indicative of charge transfer	—	—	Text Qualitative	3 · main text · Fig. 3A
Charge-transfer absorption band near 700 nm	~700 nm	—	—	Text Approximate	2 · main text · Fig. 3A
Charge-transfer absorption band near 850 nm	~850 nm	—	—	Text Approximate	2 · main text · Fig. 3A
MOF UV-vis peak in TCNQ@Cu3(BTC)2	340 nm	—	—	Text Rounded Reported	2 · main text · Fig. 3A
Neutral TCNQ UV-vis peak in TCNQ@Cu3(BTC)2	410 nm	—	—	Text Rounded Reported	2 · main text · Fig. 3A

X-ray photoelectron spectroscopy (XPS)

X-ray photoelectron spectroscopy

TCNQ-infiltrated Cu3(BTC)2 thin-film device · Thin Film

Cu3(BTC)2-(H2O)x and TCNQ@Cu3(BTC)2 films held in laboratory air for several weeks

Atmosphere: laboratory air exposure before analysis
Geometry: thin films
Context: target compared with pristine film
Measurement source: 4 · X-ray photoelectron spectroscopy · Figs. S3-S4

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Charging shift in pristine Cu3(BTC)2-(H2O)x XPS	+2.74 eV	—	—	Caption Exact Reported	4 · XPS caption · Fig. S3
Copper oxidation state after TCNQ infiltration	Cu remains in +2 state	—	—	Text Exact Reported	3 · main text · Fig. S4
Nitrogen XPS peak in TCNQ@Cu3(BTC)2	prominent N peak present; virtually no N in Cu3(BTC)2-(H2O)x	—	—	Caption Qualitative	4 · XPS caption · Fig. S3C