Starting materials: S-1-(1-naphthyl)ethylamine, PbBr2

Product: S-1-(1-naphthyl)ethylammonium lead bromide

Description: A hot solution of PbBr2 (45 mg, 0.12 mmol) and S-1-(1-naphthyl)ethylamine (39 µL, 0.24 mmol ) in 0.5 ml aq. HBr and 1.2 ml deionized water in a sealed vial with an N2 atmosphere was slowly cooled from 95 °C to room temperature over 48 hr. The colorless, plate-like crystals were filtered, washed with diethyl ether, and vacuum-dried.

Method: Single crystal X-ray diffraction

Description: Single crystal X-ray diffraction (XRD) was performed at 298 K on a Rigaku XtaLAB Synergy-S diffractometer using Mo-Kα radiation (λ=0.710 Å) and X-ray tube operating at 50 kV and 30 mA.

• Rayan C Duke University

Starting materials: R-1-(1-naphthyl)ethylamine, PbBr2

Product: R-1-(1-naphthyl)ethylammonium lead bromide

Description: A hot solution of PbBr2 (45 mg, 0.12 mmol) and R-1-(1-naphthyl)ethylamine (39 µL, 0.24 mmol ) in 0.5 ml aq. HBr and 1.2 ml deionized water in a sealed vial with an N2 atmosphere was slowly cooled from 95 °C to room temperature over 48 hr. The colorless, plate-like crystals were filtered, washed with diethyl ether, and vacuum-dried.

Method: Single crystal X-ray diffraction

Description: Single crystal X-ray diffraction (XRD) was performed at 298 K on a Rigaku XtaLAB Synergy-S diffractometer using Mo-Kα radiation (λ=0.710 Å) and X-ray tube operating at 50 kV and 30 mA.

• Rayan C Duke University

Starting materials: (S)-(−)-α-methyl benzylamine, PbI2

Product: (S)-(−)-α-methyl benzylammonium lead iodide (S-MBA2PbI4)

Description: Single crystals of S-MBPI were grown by slowly evaporating a solution of (S)-(−)-α-methyl benzylamine (25 µL, 0.2 mmol) and PbI2 (45 mg, 0.1 mmol) in 1 ml aq. HI and 1 ml methanol at room temperature under N2 atmosphere. The orange-red, needle-like crystals were filtered, washed with diethyl ether, and vacuum-dried.

Method: Single crystal X-ray diffraction

Description: Single crystal X-ray diffraction (XRD) was performed at 298 K on a Rigaku XtaLAB Synergy-S diffractometer using Mo-Kα radiation (λ=0.710 Å) and X-ray tube operating at 50 kV and 30 mA.

• Rayan C Duke University

Starting materials: (S)-(−)-α-methyl benzylamine, PbI2

Product: (S)-(−)-α-methyl benzylammonium lead iodide (S-MBA2PbI4)

Description: Single crystals of S-MBPI were grown by slowly evaporating a solution of (S)-(−)-α-methyl benzylamine (25 µL, 0.2 mmol) and PbI2 (45 mg, 0.1 mmol) in 1 ml aq. HI and 1 ml methanol at room temperature under N2 atmosphere. The orange-red, needle-like crystals were filtered, washed with diethyl ether, and vacuum-dried.

Method: Single crystal X-ray diffraction

Description: Single crystal X-ray diffraction (XRD) was performed at 200 K on a Rigaku XtaLAB Synergy-S diffractometer using Mo-Kα radiation (λ=0.710 Å) and X-ray tube operating at 50 kV and 30 mA.

• Rayan C Duke University

Starting materials: (S)-(−)-α-methyl benzylamine, PbI2

Product: (S)-(−)-α-methyl benzylammonium lead iodide (S-MBA2PbI4)

Description: Single crystals of S-MBPI were grown by slowly evaporating a solution of (S)-(−)-α-methyl benzylamine (25 µL, 0.2 mmol) and PbI2 (45 mg, 0.1 mmol) in 1 ml aq. HI and 1 ml methanol at room temperature under N2 atmosphere. The orange-red, needle-like crystals were filtered, washed with diethyl ether, and vacuum-dried.

Method: Single crystal X-ray diffraction

Description: Single crystal X-ray diffraction (XRD) was performed at 100 K on a Rigaku XtaLAB Synergy-S diffractometer using Mo-Kα radiation (λ=0.710 Å) and X-ray tube operating at 50 kV and 30 mA.

• Rayan C Duke University

Starting materials: 1-(1-naphthyl)ethylamine (98%), PbBr2

Product: 1-(1-naphthyl)ethylammoium lead bromide

Description: A hot solution of 1-(1-naphthyl)ethylamine (39 µL, 0.24 mmol ) and PbBr2 (45 mg, 0.12 mmol) in 0.5 ml of aq. HBr and 1.2 ml methanol is cooled from 95 °C to room temperature over 48 hr. The colorless plate-like crystals were filtered, washed with diethyl ether, and vacuum-dried.

Method: Single crystal X-ray diffraction

Description: Single crystal X-ray diffraction (XRD) was performed at 298 K on a Bruker APEX II CCD diffractometer using Mo-Kα radiation (λ=0.710 Å) and X-ray tube operating at 50 kV and 30 mA

• Rayan C Duke University

Starting materials: (S)-(−)-1-(1-naphthyl)ethylamine (≥99%), PbI2

Product: S-NEA2Pb2I6 (S-NPI)

Description: Single crystals of 1D S-NEA2Pb2I6 (S-NPI) were obtained by cooling a hot aq. HI solution of S-1-(1-naphthyl)ethylamine (0.25 mmol) and PbI2 (0.125 mmol) from 90 °C to room-temperature in 48 hr. The pale-yellow, needle-like crystals were filtered, washed with diethyl ether, and vacuum-dried.

Method: Single crystal X-ray diffraction

Description: Single crystal X-ray diffraction (XRD) was performed at 298 K on a Bruker APEX II CCD diffractometer using Mo-Kα radiation (λ=0.710 Å) and X-ray tube operating at 50 kV and 30 mA

• Rayan C Duke University

Code: FHI-aims

Level of theory: DFT

Exchange-correlation functional: PBE

K-point grid: 2×4×4

Level of relativity: atomic ZORA

Basis set definition: NAO

External repositories:

• https://dx.doi.org/10.17172/NOMAD/2020.08.11-1

• Rayan C Duke University

Code: FHI-aims

Level of theory: DFT

Exchange-correlation functional: PBE

K-point grid: 2×4×4

Level of relativity: atomic ZORA

Basis set definition: NAO

External repositories:

• https://dx.doi.org/10.17172/NOMAD/2020.08.11-1

• Rayan C Duke University

Code: FHI-aims

Level of theory: DFT

Exchange-correlation functional: HSE06

K-point grid: 3×4×4

Level of relativity: atomic ZORA with SOC

Basis set definition: NAO

Geometry used in the calculation

• Rayan C Duke University

Code: FHI-aims

Level of theory: DFT

Exchange-correlation functional: PBE

K-point grid: 2×4×4

Level of relativity: atomic ZORA

Basis set definition: NAO

External repositories:

• https://dx.doi.org/10.17172/NOMAD/2020.08.11-1

• Rayan C Duke University

Code: FHI-aims

Level of theory: DFT

Exchange-correlation functional: HSE06

K-point grid: 3×4×4

Level of relativity: atomic ZORA with SOC

Basis set definition: NAO

Geometry used in the calculation

• Rayan C Duke University

Code: FHI-aims

Level of theory: DFT

Exchange-correlation functional: PBE

K-point grid: 2×4×4

Level of relativity: atomic ZORA

Basis set definition: NAO

External repositories:

• https://dx.doi.org/10.17172/NOMAD/2020.08.11-1

• Rayan C Duke University

Code: FHI-aims

Level of theory: DFT

Exchange-correlation functional: HSE06

K-point grid: 3×4×4

Level of relativity: atomic ZORA with SOC

Basis set definition: NAO

Geometry used in the calculation

External repositories:

• https://dx.doi.org/10.17172/NOMAD/2020.08.11-1

• Rayan C Duke University

Code: FHI-aims

Level of theory: DFT

Exchange-correlation functional: PBE

K-point grid: 2×4×4

Level of relativity: atomic ZORA

Basis set definition: NAO

External repositories:

• https://dx.doi.org/10.17172/NOMAD/2020.08.11-1

• Rayan C Duke University

Code: FHI-aims

Level of theory: DFT

Exchange-correlation functional: HSE06

K-point grid: 3×4×4

Level of relativity: atomic ZORA with SOC

Basis set definition: NAO

Geometry used in the calculation

External repositories:

• https://dx.doi.org/10.17172/NOMAD/2020.08.11-1

• Rayan C Duke University

Code: FHI-aims

Level of theory: DFT

Exchange-correlation functional: HSE06

K-point grid: 3×4×4

Level of relativity: atomic ZORA with SOC

Basis set definition: NAO

Starting materials: (S)-(−)-1-(1-naphthyl)ethylamine (>99%, Sigma Aldrich), lead bromide (PbBr2, 99.99%, TCI chemicals) , and hydrobromic acid (HBr) (48 wt% in H2O, >99.99%, Sigma Aldrich)

Product: [S-(−)-1-(1-naphthyl)ethylammonium]2PbBr4

Description: To grow S-NPB perovskite crystals, stoichiometric amounts of PbBr2 (90 mg, 0.24 mmol) and (S)-(−)-1- (1-naphthyl)ethylamine (78 µL, 0.48 mmol) were dissolved in aq. HBr (1.0 mL) and deionized water (2.4 mL) in a sealed vial at 95 °C. The hot solution was slowly cooled to room temperature (21 °C) over a period of 24 h in a water bath, resulting in the formation of colorless plate-like S-NPB single crystals.

Method: Thermal transition behavior

Description: DSC: Differential Scanning Calorimetry: DSC measurements were performed using a TA Discovery DSC instrument using various ramping rates and temperature ranges (as described in the main text) using a hermetically sealed aluminum pan and lid. Prior to experiments, the DSC setup was calibrated with metallic indium (melting temperature: 156.6 °C; enthalpy of melting: 28.71 J g−1), which upon repeating the experiment showed an acceptable temperature offset of 0.2 °C and melting enthalpy offset of 0.04%. Calibration and the above measurement were carried out at a ramp rate of 5 °C min−1. DSC analyses of crystalline S-NPB and rac-NPB perovskites were carried out by hermetically sealing corresponding crystals (≈5.0 mg) in aluminum pan/lid, and ramping temperature from 25 to 250 °C at a ramp rate of 5 °C min−1. For measurement of S-NPB and R-NPB glasses, samples were prepared by melting S-/R-NPB crystals (≈5.0 mg) in an open aluminum pan and quickly placing it on a metallic steel bench to quench to room temperature. After hermetic sealing, the glassy samples were exposed to a heating cycle with ramp rates of 5°C min−1 over a temperature range from 25 to 185 °C and heated isothermally at 185 °C for a minute, before cooling back to room temperature at ramp rates of 1, 5, and 20 °C min−1. Since the glass transition occurred over a temperature range, the Tg was determined using the midpoint halfheight method. The Tx, Tm, and Td temperatures were calculated using the intersection between the corresponding DSC peak onset with its horizontal baseline. For Tm, the onset temperature signifies the melting temperature of the sample under consideration, whereas the peak temperature corresponds to complete melting of the sample inside the apparatus. The enthalpy of crystallization and melting were calculated by measuring the area under the curve relating heat flow (W g−1)/ramp rate (°C s−1) and temperature. Thermogravimetric Analysis: TGA measurements were performed on a TA Q50 instrument using a 5 °C min−1 ramping rate from 25 to 300 °C under nitrogen gas flow (40 mL min−1) with samples (≈4.5 mg) of single crystals of S-NPB and rac-NPB perovskite. Glassy S-NPB perovskite sample (3.9 mg) for TGA measurement was prepared by scratching off the melt-quenched glass prepared on soda lime glass substrates

Starting materials: (S)-(−)-1-(1-naphthyl)ethylamine (>99%, Sigma Aldrich), lead bromide (PbBr2, 99.99%, TCI chemicals) , and hydrobromic acid (HBr) (48 wt% in H2O, >99.99%, Sigma Aldrich)

Product: [S-(−)-1-(1-naphthyl)ethylammonium]2PbBr4

Description: To grow S-NPB perovskite crystals, stoichiometric amounts of PbBr2 (90 mg, 0.24 mmol) and (S)-(−)-1- (1-naphthyl)ethylamine (78 µL, 0.48 mmol) were dissolved in aq. HBr (1.0 mL) and deionized water (2.4 mL) in a sealed vial at 95 °C. The hot solution was slowly cooled to room temperature (21 °C) over a period of 24 h in a water bath, resulting in the formation of colorless plate-like S-NPB single crystals.

Method: Differential Scanning Calorimetry

Description: DSC: Differential Scanning Calorimetry: DSC measurements were performed using a TA Discovery DSC instrument using various ramping rates and temperature ranges (as described in the main text) using a hermetically sealed aluminum pan and lid. Prior to experiments, the DSC setup was calibrated with metallic indium (melting temperature: 156.6 °C; enthalpy of melting: 28.71 J g−1), which upon repeating the experiment showed an acceptable temperature offset of 0.2 °C and melting enthalpy offset of 0.04%. Calibration and the above measurement were carried out at a ramp rate of 5 °C min−1. DSC analyses of crystalline S-NPB and rac-NPB perovskites were carried out by hermetically sealing corresponding crystals (≈5.0 mg) in aluminum pan/lid, and ramping temperature from 25 to 250 °C at a ramp rate of 5 °C min−1. For measurement of S-NPB and R-NPB glasses, samples were prepared by melting S-/R-NPB crystals (≈5.0 mg) in an open aluminum pan and quickly placing it on a metallic steel bench to quench to room temperature. After hermetic sealing, the glassy samples were exposed to a heating cycle with ramp rates of 5°C min−1 over a temperature range from 25 to 185 °C and heated isothermally at 185 °C for a minute, before cooling back to room temperature at ramp rates of 1, 5, and 20 °C min−1. Since the glass transition occurred over a temperature range, the Tg was determined using the midpoint halfheight method. The Tx, Tm, and Td temperatures were calculated using the intersection between the corresponding DSC peak onset with its horizontal baseline. For Tm, the onset temperature signifies the melting temperature of the sample under consideration, whereas the peak temperature corresponds to complete melting of the sample inside the apparatus. The enthalpy of crystallization and melting were calculated by measuring the area under the curve relating heat flow (W g−1)/ramp rate (°C s−1) and temperature. Thermogravimetric Analysis: TGA measurements were performed on a TA Q50 instrument using a 5 °C min−1 ramping rate from 25 to 300 °C under nitrogen gas flow (40 mL min−1) with samples (≈4.5 mg) of single crystals of S-NPB and rac-NPB perovskite. Glassy S-NPB perovskite sample (3.9 mg) for TGA measurement was prepared by scratching off the melt-quenched glass prepared on soda lime glass substrates

Starting materials: (S)-(−)-1-(1-naphthyl)ethylamine (>99%, Sigma Aldrich), lead bromide (PbBr2, 99.99%, TCI chemicals) , and hydrobromic acid (HBr) (48 wt% in H2O, >99.99%, Sigma Aldrich)

Product: [S-(−)-1-(1-naphthyl)ethylammonium]2PbBr4

Description: To grow S-NPB perovskite crystals, stoichiometric amounts of PbBr2 (90 mg, 0.24 mmol) and (S)-(−)-1- (1-naphthyl)ethylamine (78 µL, 0.48 mmol) were dissolved in aq. HBr (1.0 mL) and deionized water (2.4 mL) in a sealed vial at 95 °C. The hot solution was slowly cooled to room temperature (21 °C) over a period of 24 h in a water bath, resulting in the formation of colorless plate-like S-NPB single crystals.

Method: Thermogravimetric Analysis

Description: Thermogravimetric Analysis: TGA measurements were performed on a TA Q50 instrument using a 5 °C min−1 ramping rate from 25 to 300 °C under nitrogen gas flow (40 mL min−1) with samples (≈4.5 mg) of single crystals of S-NPB and rac-NPB perovskite. Glassy S-NPB perovskite sample (3.9 mg) for TGA measurement was prepared by scratching off the melt-quenched glass prepared on soda lime glass substrates.

Starting materials: (S)-(−)-1-(1-naphthyl)ethylamine (>99%, Sigma Aldrich), lead bromide (PbBr2, 99.99%, TCI chemicals) , and hydrobromic acid (HBr) (48 wt% in H2O, >99.99%, Sigma Aldrich)

Product: [S-(−)-1-(1-naphthyl)ethylammonium]2PbBr4

Description: To grow S-NPB perovskite crystals, stoichiometric amounts of PbBr2 (90 mg, 0.24 mmol) and (S)-(−)-1- (1-naphthyl)ethylamine (78 µL, 0.48 mmol) were dissolved in aq. HBr (1.0 mL) and deionized water (2.4 mL) in a sealed vial at 95 °C. The hot solution was slowly cooled to room temperature (21 °C) over a period of 24 h in a water bath, resulting in the formation of colorless plate-like S-NPB single crystals.

Method: Glass transition temperature

Description: DSC: Differential Scanning Calorimetry: DSC measurements were performed using a TA Discovery DSC instrument using various ramping rates and temperature ranges (as described in the main text) using a hermetically sealed aluminum pan and lid. Prior to experiments, the DSC setup was calibrated with metallic indium (melting temperature: 156.6 °C; enthalpy of melting: 28.71 J g−1), which upon repeating the experiment showed an acceptable temperature offset of 0.2 °C and melting enthalpy offset of 0.04%. Calibration and the above measurement were carried out at a ramp rate of 5 °C min−1. DSC analyses of crystalline S-NPB and rac-NPB perovskites were carried out by hermetically sealing corresponding crystals (≈5.0 mg) in aluminum pan/lid, and ramping temperature from 25 to 250 °C at a ramp rate of 5 °C min−1. For measurement of S-NPB and R-NPB glasses, samples were prepared by melting S-/R-NPB crystals (≈5.0 mg) in an open aluminum pan and quickly placing it on a metallic steel bench to quench to room temperature. After hermetic sealing, the glassy samples were exposed to a heating cycle with ramp rates of 5°C min−1 over a temperature range from 25 to 185 °C and heated isothermally at 185 °C for a minute, before cooling back to room temperature at ramp rates of 1, 5, and 20 °C min−1. Since the glass transition occurred over a temperature range, the Tg was determined using the midpoint halfheight method. The Tx, Tm, and Td temperatures were calculated using the intersection between the corresponding DSC peak onset with its horizontal baseline. For Tm, the onset temperature signifies the melting temperature of the sample under consideration, whereas the peak temperature corresponds to complete melting of the sample inside the apparatus. The enthalpy of crystallization and melting were calculated by measuring the area under the curve relating heat flow (W g−1)/ramp rate (°C s−1) and temperature. Thermogravimetric Analysis: TGA measurements were performed on a TA Q50 instrument using a 5 °C min−1 ramping rate from 25 to 300 °C under nitrogen gas flow (40 mL min−1) with samples (≈4.5 mg) of single crystals of S-NPB and rac-NPB perovskite. Glassy S-NPB perovskite sample (3.9 mg) for TGA measurement was prepared by scratching off the melt-quenched glass prepared on soda lime glass substrates