Starting materials: PbI2 (99.999% trace metal basis), HI (57 wt % in H2O, with hypophosphorous acid as stabilizer, assay 99.95%), CH3OH (>99.9%), 2-phenylethylamine (PEA, 99%)

Product: Red and laminar crystals.

Description: Dissolve PbI2 (54.6 mg) in 0.5 mL of HI (57%). Place CH3OH (1 ml) on the top of the PbI2 solution. Add 0.030 mL of PEA liquid into the CH3OH layer. Crystals would form in the solution overnight.

Method: Single-crystal X-ray diffraction

Description: Single-crystal X-ray diffraction data were collected using a Bruker D8 ADVANCE Series II at room temperature. The crystal structures were solved and refined by Shelxl and Olex software.

Comment: This is the experimentally resolved structure, which contains a statistical (disordered) representation of the equatorial iodine atoms in the original refinement. This structure is our recommended "best" published experimental structure for phenethylammonium lead iodide at room temperature, supported by a computational comparison of the total energies of various published structures after full structure optimization in Chemistry of Materials, Vol. 34, issue 7, 3109-3122 (2022), https://doi.org/10.1021/acs.chemmater.1c04213. The computationally relaxed (PEA)2PbI4 structure with resolved disorder (i.e., no overlapping iodine positions), optimized using the PBE+Tkatchenko-Scheffler approach, is also available in the HybriD3 database (see datasets linked to the present one.)

Code: FHI-aims

Level of theory: DFT

Exchange-correlation functional: PBE+TS

K-point grid: 2*8*8

Level of relativity: atomic ZORA

Basis set definition: tight

Numerical accuracy: force convergence 5e-3 eV/AA

Comment: The original structure is based on the experimental resolved (PEA)2PbI4 structure from the reference tag, published in https://doi.org/10.1021/acs.inorgchem.7b01094

Starting materials: Lead(II) iodide, 2-phenethylamine (PEA), HI, diethyl ether

Product: orange needle-like crystals

Description: a round bottom flask containing ethanol and PEA was cooled to 0 degree C. To it, a stoichiometric amount of concentrated hydroiodic acid was added. After stirring the solution for 1 hour, all volatiles were removed using a rotary evaporator. The remaining solid is PEAI salt. It was washed with diethyl ether and dried under vacuum at 50°C overnight. Stoichiometric amounts of PbI2 and PEAI were added to concentrated stabilized aqueous HI (concentrations of around 0.25-0.30M of Pb2+). The solution was heated and stirred at 140ºC for an hour, and the clear solutions cooled slowly to room temperature.

Method: Single Crystal X-ray Diffraction

Description: Data was collected with a BrukerX8 CCD area detector diffractometer, with Mo Kα radiation (0.71073Å) at 100 K. SAINT and SADABS packages were used for data reduction and absorption corrections, respectively.

• Rayan C Duke University

Code: Ab Initio, Quantum Espresso

Level of theory: DFT

Exchange-correlation functional: PBE (supplemented by D2 method)

K-point grid: 4x4x1

Level of relativity: Relativistic effects , including SOC, are treated for core orbitals. Splitting due to SOC is averaged in valence region

Basis set definition: SRL pseudopotentials with Opium

Numerical accuracy: Wave functions have energy cutoff of 680 eV

Comment: Energies and structures are relaxed to 3x10^{-9} eV/cell.

• Ruyi Song Chemistry department, Duke university

Code: Ab Initio, Quantum Espresso

Level of theory: DFT

Exchange-correlation functional: PBE supplemented by D2 method

K-point grid: 4x4x1

Level of relativity: Relativistic effects , including SOC, are treated for core orbitals. Splitting due to SOC is averaged in valence region

Basis set definition: SRL pseudopotentials with Opium

Numerical accuracy: Wave functions have energy cut off of 680 eV

Comment: Energies and structures are relaxed to 3x10^{-9} eV/cell.

Code: Ab Initio, Quantum Espresso

Level of theory: DFT

Exchange-correlation functional: PBE supplemented by D2 method

K-point grid: 4x4x1

Level of relativity: Relativistic effects , including SOC, are treated for core orbitals. Splitting due to SOC is averaged in valence region

Basis set definition: SRL pseudopotentials with Opium

Numerical accuracy: Wave functions have energy cut off of 680 eV

Comment: Energies and structures are relaxed to 3x10^{-9} eV/cell.

Code: Ab Initio, Quantum Espresso

Level of theory: DFT

Exchange-correlation functional: PBE supplemented by D2 method

K-point grid: 4x4x1

Level of relativity: Relativistic effects , including SOC, are treated for core orbitals. Splitting due to SOC is averaged in valence region

Basis set definition: SRL pseudopotentials with Opium

Numerical accuracy: wave functions have energy cut off of 680 eV

Comment: energies and structures are relaxed to 3x10^{-9} eV/cell.

Code: Ab Initio, Quantum Espresso

Level of theory: DFT

Exchange-correlation functional: PBE supported by D2 method

K-point grid: 4x4x1

Level of relativity: relativistic effects , including SOC, are treated for core orbitals. Splitting due to SOC is averaged in valence region

Basis set definition: SRL pseudopotentials with Opium

Numerical accuracy: wave functions have energy cut off of 680 eV

Comment: energies and structures are relaxed to 3x10^{-9} eV/cell.

Code: Ab Initio, Quantum Espresso

Level of theory: DFT

Exchange-correlation functional: PBE supplemented by D2 method

K-point grid: 4x4x4

Level of relativity: relativistic effects , including SOC, are treated for core orbitals. Splitting due to SOC is averaged in valence region

Basis set definition: SRL pseudopotentials with Opium

Numerical accuracy: wave functions have energy cut off of 680 eV

Comment: energies and structures are relaxed to 3x10^{-9} eV/cell.

Starting materials: HI, phenylethylamine, PbAc2•3H2O, IPA

Product: yellow crystals

Description: First, PEAI was synthesized by adding HI (48 wt.% in water) to phenylethylamine at a molar ration of 1:1. This was performed at 0º C. Water was evaporated in a hood (at ~100º C) until PEAI crystals formed. Solution then cooled, powder product was filtered, washed with diethyl ether, and dried at 80º C in a vacuum oven for ~24 hours. Next, (PEA)2PbI4 was synthesized. Fluoride-doped tin oxide (FTO) glass substrate was coated with a film of lead acetate by drop-casting PbAc2•3H2O (100 mg/mL). This was dried for 30 minutes at 60º C. The PbAc2 film was placed into PEAI solution in IPA, having various concentrations at room temperature. The lead-coated side was facing down in the vial. After the reaction (~20 hrs), the substrate was removed, dipped into IPA again to remove extra solution, and dried under a stream of N2.

Method: Single Crystal X-ray Diffraction

Description: Single crystal was attached to tip of MiTeGen MicroMount, under a stream of N2 at 100 K. Data was recorded with Bruker Quazar SMART APEXII diffractometer with Mo Kα (λ = 0.71073 Å) radiation.

Comment: See page 2119 of the publication for details about X-ray diffraction measurement

Starting materials: HI (Sigma Aldrich, 57% w/w), chloroform (Fisher, HPLC grade), tributylphosphate (Acros Organics, 99+%), PbI2 (Strem, 99.999+%), phenylethylamine (PEA, Sigma-Aldrich, >99.5%), diethyl ether (Fisher, ACS grade, anhydrous, stabilized with BHT)

Product: orange crystals

Description: 7 ml Unstabilized HI was treated with 10% v/v solution of tributylphosphate in chloroform. The aqueous phase (HI) was extracted. PbI2 (.231 g) was dissolved in the HI solution by heating to 100º C under N2 flow. In it, 0.13 ml PEA is added. The reaction is then cooled to room temperature, at a constant rate of 2 ºC/h. Then, the mixture is cooled at 4ºC for 30 minutes, filtered, washed with diethyl ether, and dried overnight under vacuum at 50 °C.

Method: Single crystal X-Ray Diffraction

Description: SCXRD data are collected on a Bruker Kappa APEX II DUO diffractometer with a CCD area detector employing graphite-monochromated Mo Kα radiation (λ = 0.710 73 Å). Crystals for SCXRD measured at 100 K are cooled by an Oxford Cryostream.

Starting materials: HI (Sigma Aldrich, 57% w/w), chloroform (Fisher, HPLC grade), tributylphosphate (Acros Organics, 99+%), PbI2 (Strem, 99.999+%), phenylethylamine (PEA, Sigma-Aldrich, >99.5%), diethyl ether (Fisher, ACS grade, anhydrous, stabilized with BHT)

Product: orange crystals

Description: 7 ml Unstabilized HI was treated with 10% v/v solution of tributylphosphate in chloroform. The aqueous phase (HI) was extracted. PbI2 (.231 g) was dissolved in the HI solution by heating to 100º C under N2 flow. In it, 0.13 ml PEA is added. The reaction is then cooled to room temperature, at a constant rate of 2 ºC/h. Then, the mixture is cooled at 4ºC for 30 minutes, filtered, washed with diethyl ether, and dried overnight under vacuum at 50 °C.

Method: Single crystal X-Ray Diffraction

Description: SCXRD data are collected on a Bruker Kappa APEX II DUO diffractometer with a CCD area detector employing graphite-monochromated Mo Kα radiation (λ = 0.710 73 Å).

Code: CRYSTAL09

Level of theory: DFT

Exchange-correlation functional: PBESOL-D2

Basis set definition: cc-p VDZ

Comment: PEA cations were arranged in eclipsed conformation

Code: Crystal09

Level of theory: DFT

Exchange-correlation functional: PBESOL-D2

Basis set definition: cc-p VDZ

Code: Quantum Espresso

Level of theory: DFT

K-point grid: 6x6x1

Basis set definition: ultra-soft pseudopotentials

Comment: Energy cutoff was 80 Ry. Force on each atom was less than 0.5 eV/nm.

• Rayan C Duke University

Code: VESTA

Level of theory: DFT

Exchange-correlation functional: PBE+SOC+vdW

K-point grid: 6x6x1

Basis set definition: PAW

Numerical accuracy: Plane-wave cutoff energy: 500 eV

Comment: The structure data in this publication had some unclear details; therefore, the structure published in this database is based off of the structure information in the publication with some added assumptions.

Starting materials: hydriodic acid (57% w/w in water, Alpha Aesar), phenethylamine (PEA), lead oxide (PbO, 99%, Sigma-Aldrich)

Product: Orange (PEA)2PbI4 crystals

Description: In 30 mL HI solution, PEA, and PbO (ratio: 1.72: 3.45 mmol) were dissolved. The solution was heated at 110º C for 4 hours and subsequently cooled to room temperature. Once the solution cooled, single crystals formed.

Method: Single crystal X-ray diffraction

Code: FHI-aims

Level of theory: DFT

Exchange-correlation functional: PBE (with TS scheme to account for the Van der Waals effect)

K-point grid: 2*4*4

Basis set definition: tight

Numerical accuracy: force convergence 5e-3 eV/AA

Comment: See Table S2 of Wright et al. (https://doi.org/10.1021/acs.chemmater.1c04213). This is the lowest-energy structure among multiple possible atomic structure models for (PEA)2PbI4 investigated in this reference. This structure was constructed based on the experimental c(2*2)*2 (PEA)2PbI4 published by Du. et al. (doi: 10.1021/acs.inorgchem.7b01094.)

• Rayan C Duke University

Code: FHI-aims

Level of theory: DFT

Exchange-correlation functional: PBE (with TS scheme to account for the Van der Waals effect)

K-point grid: 2*4*4

Basis set definition: tight

Numerical accuracy: force convergence 5e-3 eV/AA

Comment: See Table S2 of Wright et al. (https://doi.org/10.1021/acs.chemmater.1c04213). This structure was constructed based on the experimental (PEA)2PbI4 structure published by Febriansyah et al. (doi: 10.1021/acs.chemmater.8b04064.)

• Rayan C Duke University

Code: FHI-aims

Level of theory: DFT

Exchange-correlation functional: PBE (with TS scheme to account for the Van der Waals effect)

K-point grid: 2*4*4

Basis set definition: tight

Numerical accuracy: force convergence 5e-3 eV/AA

Comment: See Table S2 of Wright et al. (https://doi.org/10.1021/acs.chemmater.1c04213). This structure was constructed based on the experimental T= 100 k (PEA)2PbI4 structure published by Straus et al. (doi: 10.1021/acs.jpclett.9b00247.)

• Rayan C Duke University

Code: FHI-aims

Level of theory: DFT

Exchange-correlation functional: PBE (with TS scheme to account for the Van der Waals effect)

K-point grid: 2*4*4

Basis set definition: tight

Numerical accuracy: force convergence 5e-3 eV/AA

Comment: See Table S2 of Wright et al. (https://doi.org/10.1021/acs.chemmater.1c04213). This structure was constructed based on the experimental T= 300 k (PEA)2PbI4 structure published by Straus et al. (doi: 10.1021/acs.jpclett.9b00247.)

• Rayan C Duke University

Code: FHI-aims

Level of theory: DFT

Exchange-correlation functional: PBE

K-point grid: 4*4*2

Level of relativity: atomic ZORA with SOC

Basis set definition: tight

Numerical accuracy: force convergence 5e-3 eV/AA

Comment: This is a variant of structure 1885, rotated to use the c axis instead of the a axis as the out of plane axis. This structure is constructed based on the experimental c(2*2)*2 (PEA)2PbI4 published by Du. et al. (doi: 10.1021/acs.inorgchem.7b01094.)

• Rayan C Duke University

Code: FHI-aims

Level of theory: DFT

Exchange-correlation functional: PBE (with TS scheme to account for the Van der Waals effect)

K-point grid: 4*4*2

Basis set definition: tight

Numerical accuracy: force convergence 5e-3 eV/AA

Comment: This is a hypothetical, computationally generated structure that is intentionally NOT consistent with the experimental structure of (PEA)2PbI4. Rather, the organic molecule configuration of this structure is borrowed from (PEA)2PbBr4 structure (data ID 1890) but inorganic component is PbI4, then computationally fully optimized using DFT-PBE+TS.

• Rayan C Duke University

Starting materials: hydriodic acid (57% w/w in water, Alpha Aesar), phenethylamine (PEA), lead oxide (PbO, 99%, Sigma-Aldrich)

Product: Orange (PEA)2PbI4 crystals

Description: In 30 mL HI solution, PEA, and PbO (ratio: 1.72: 3.45 mmol) were dissolved. The solution was heated at 110º C for 4 hours and subsequently cooled to room temperature. Once the solution cooled, single crystals formed.

Method: Single crystal X-ray diffraction

Code: VESTA

Level of theory: DFT

Exchange-correlation functional: PBE+SOC+vdW

K-point grid: 6x6x1

Basis set definition: PAW

Numerical accuracy: Plane-wave cutoff energy: 500 eV

Comment: The structure data in this publication had some unclear details; therefore, the structure published in this database is based off of the structure information in the publication with some added assumptions.