Synthesis · Multilevel Chiral Semiconductor Metal-Peptide Framework Thin Film for Highly Circularly Polarized Visible Photodetection

6 structured synthesis routes

Completeness describes how fully the route could be reconstructed from the main article and supporting information.

Partial recipeSource: SI

Route 1: Other

SI p.7 · Fabrication CAS-4 thin film-based photodetector · Figures 4a and 5a

Metal precursorsAu electrode material

Linker precursorsPreformed CAS-4 thin film

AtmosphereNitrogen cleaning before electrode manufacture.

Substrate orientationInterdigital electrode grid shadow mask covering CAS-4 film surface.

Work-upAu electrode patterning by magnetron sputtering; effective irradiation area 8.1 mm2.

Scalability contextMain text shows large-area 5 x 6 pixel photodetector array on SiO2 wafer.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	CAS-4 thin film	Not specified	SI p.7 · Fabrication CAS-4 thin film-based photodetector · Figures 4a and 5a
Other	Au electrode	60 nm in main text	SI p.7 · Fabrication CAS-4 thin film-based photodetector · Figures 4a and 5a

Complete recipeSource: SI

Route 2: Other

SI p.6 · Synthesis of CAS-4 (bulk crystal) · Table S1

Metal precursorscopper acetate, Cu(OAc)2

Linker precursorsGHL tripeptide ligand

SolventsH2O and ethanol, 300 uL each

AtmosphereRoom temperature and air unless otherwise specified; sealed 10 mL glass bottle.

Temperatureroom temperature

Time24

Substrate orientationnot_applicable

Work-upBlue bulk crystals collected for characterization.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper acetate	20 mg, 0.1 mmol	SI p.6 · Synthesis of CAS-4 (bulk crystal) · Table S1
Linker	GHL	34 mg, 0.1 mmol	SI p.6 · Synthesis of CAS-4 (bulk crystal) · Table S1
Solvent	H2O	300 ul	SI p.6 · Synthesis of CAS-4 (bulk crystal) · Table S1
Solvent	ethanol	300 ul	SI p.6 · Synthesis of CAS-4 (bulk crystal) · Table S1

Complete recipeSource: SI

Route 3: Other

SI p.7 · Details of docking experiment · Figures S36-S38

Metal precursorsPreformed CAS-4 thin film

Linker precursorsnot_applicable

SolventsEthanol

AdditivesR- or S-naproxen guest

AtmosphereDried at room temperature in air.

Temperatureroom temperature

Time5 min immersion

Substrate orientationCAS-4 thin-film photodetector substrate

Work-upWashed with ethanol and dried in air before retesting CP photocurrent.

ActivationNo pre-evacuation; article states chiral recognition does not require pre-evacuation of pores.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	CAS-4 thin film sample	Not specified	SI p.7 · Details of docking experiment · Figures S36-S38
Additive	R- or S-Naproxen	1 mmol/mL ethanol solution	SI p.7 · Details of docking experiment · Figures S36-S38
Solvent	ethanol	wash solvent and solution solvent	SI p.7 · Details of docking experiment · Figures S36-S38

Complete recipeSource: SI

Route 4: Drop Cast

SI p.7 · Fabrication of CAS-4 non-oriented thin film · Figures S11, S13, S14, S34

Metal precursorsPre-synthesized CAS-4 crystals

Linker precursorsPre-synthesized CAS-4 crystals

SolventsH2O

Atmosphereambient; not otherwise specified

Temperatureroom temperature

Time20 min sonication; 30 s spin coating

Substrate orientationFunctionalized Si/SiO2 substrate

Work-upSpin-coated after sonication to a uniform dispersion.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	CAS-4 crystals	5 mg	SI p.7 · Fabrication of CAS-4 non-oriented thin film · Figures S11, S13, S14, S34
Solvent	H2O	5 mL	SI p.7 · Fabrication of CAS-4 non-oriented thin film · Figures S11, S13, S14, S34

Complete recipeSource: Both

Route 5: Other

SI p.6 · Synthesis of chiral CAS-4 thin film · Figure 1a; Figure 2

Metal precursorsCu(OAc)2 solution, 1 mM

Linker precursorsTripeptide ligand GHL solution, 20 mM

SolventsH2O/EtOH 1:1; ethanol wash

AdditivesNaOH and 30% hydrogen peroxide for OH-functionalization of Si/SiO2 substrate

AtmosphereDried under nitrogen flux after substrate functionalization; otherwise room temperature and air unless specified.

Temperature80 C for substrate OH-functionalization; room temperature for LPE-LBL growth

TimeSubstrate functionalization 0.5 h; each growth cycle: 10 min Cu(OAc)2 immersion plus 15 min GHL immersion; 20 cycles total.

Substrate orientationFunctionalized Si/SiO2 substrate; quartz also used for optical thin-film preparation/baseline measurements.

Oxidant / reductant30% hydrogen peroxide in 3:1 2 mM NaOH/H2O2 substrate-treatment solution

Work-upRinse with deionized water after functionalization; ethanol wash after each LPE-LBL step to remove residual reactants.

ActivationNo pore activation reported for the thin film.

Scalability contextMain article describes wafer-scale multilevel chiral MOF thin film and shows a wafer-scale array device.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(OAc)2	1 mM	SI p.6 · Synthesis of chiral CAS-4 thin film · Figure 1a; Figure 2
Linker	tripeptide ligand GHL	20 mM	SI p.6 · Synthesis of chiral CAS-4 thin film · Figure 1a; Figure 2
Solvent	H2O and EtOH	1:1 mixture	SI p.6 · Synthesis of chiral CAS-4 thin film · Figure 1a; Figure 2
Base	NaOH solution	mixed with 30% hydrogen peroxide at 3:1 · 2 mM	SI p.6 · Synthesis of chiral CAS-4 thin film · Figure 1a; Figure 2
Oxidant	30% hydrogen peroxide	NaOH/H2O2 ratio 3:1 · 30%	SI p.6 · Synthesis of chiral CAS-4 thin film · Figure 1a; Figure 2
Solvent	ethanol	wash after each step; substrate stored in ethanol	SI p.6 · Synthesis of chiral CAS-4 thin film · Figure 1a; Figure 2

Partial recipeSource: SI

Route 6: Other

SI pp.5-6 · Synthesis of Glycyl-L-histidyl-L-lysine and Glycyl-D-histidyl-L-lysine

Metal precursorsnone

Linker precursorsResin-bound sequence assembled from glycine and D- or L-His/L-Lys/C-terminal residues.

SolventsDMF; MeOH; TFA/TIS/EDT/H2O cleavage cocktail.

AdditivesDMAP, DIC, pyridine/Ac2O, piperidine, HBTU/HOBt, DIEA.

AtmosphereN2 bubbling during piperidine/DMF deprotection cycles; otherwise room temperature and air unless specified.

Temperatureroom temperature; Kaiser test at 105 C

TimeInitial resin swelling 0.5 h; glycine coupling 3 h; capping 0.5 h; deprotection 10 min then 5 min; amino acid coupling 40 min per residue; cleavage 2 h.

Substrate orientationnot_applicable

Oxidant / reductantnone specified

Work-upDMF wash cycles, MeOH washes, Kaiser-test validation, final cleavage.

Show 8 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	Glycine	5 equiv	SI pp.5-6 · Synthesis of Glycyl-L-histidyl-L-lysine and Glycyl-D-histidyl-L-lysine
Additive	DMAP	5 equiv	SI pp.5-6 · Synthesis of Glycyl-L-histidyl-L-lysine and Glycyl-D-histidyl-L-lysine
Additive	DIC	5 equiv	SI pp.5-6 · Synthesis of Glycyl-L-histidyl-L-lysine and Glycyl-D-histidyl-L-lysine
Solvent	DMF	15 mL for swelling; 5 mL x 5 wash cycles; 3 h coupling solvent	SI pp.5-6 · Synthesis of Glycyl-L-histidyl-L-lysine and Glycyl-D-histidyl-L-lysine
Base	20% piperidine/DMF	10 mL then 10 mL · 20%	SI pp.5-6 · Synthesis of Glycyl-L-histidyl-L-lysine and Glycyl-D-histidyl-L-lysine
Additive	HBTU/HOBt	3 equiv each	SI pp.5-6 · Synthesis of Glycyl-L-histidyl-L-lysine and Glycyl-D-histidyl-L-lysine
Base	DIEA	10 equiv	SI pp.5-6 · Synthesis of Glycyl-L-histidyl-L-lysine and Glycyl-D-histidyl-L-lysine
Acid	TFA/TIS/EDT/H2O	95:2:2:1 v/v	SI pp.5-6 · Synthesis of Glycyl-L-histidyl-L-lysine and Glycyl-D-histidyl-L-lysine