supplementary figure 1. sublimation of pha. and of … · sublimation of pha. ... the crystal in...

`

Supplementary Figure 1. Sublimation of PHA. Concomitant sublimation of the two polymorphs and

of PHA. Larger crystals from the yellow form can be seen in the lower left and smaller crystals of the red

form are abundant toward the upper right corner of the photograph.

Supplementary Figure 2. Temperature effects on the appearance of a PHA crystal observed by hot-

stage microscopy. A PHA crystal of form was cooled from room temperature to 85 K (top row; note the

change of the obtuse angle between the two faces of the crystal on cooling) and subsequently heated to 371

K (the middle and bottom rows). To prevent hopping, the crystal in this experiment was covered with a

cover glass. The blue arrows in the top row indicate cracks that appear at low temperature. The red arrows

in the bottom row show the spatial progression of the front of the red phase () in the crystal of the orange

phase (). The white arrows in the bottom row show the uniaxial expansion of the crystal of about 10%.

`

Supplementary Figure 3. Differential scanning calorimetry (DSC) curves of PHA. Thermoanalytical

curves of crystals (black line) and grinded powder (red line) recorded during one heating-cooling cycle 359

K (A) and below 423 K (B).

`

Supplementary Figure 4. Effects of cooling/heating rate on the DSC curves of form (A, B) and form

(C, D) of PHA below room temperature. The rates of temperature change are given in the legend (the

first and the second number in each line correspond to the rates of cooling and heating, respectively).

`

Supplementary Figure 5. Thermogravimetric curve of form PHA (yellow crystals). The heating was

performed at a rate of 10 K min–1

in a dynamic nitrogen atmosphere.

Supplementary Figure 6. High-temperature in situ micro-Raman spectroscopy. (a) Raman spectrum of

form α at 275 K. (b) Micro-photograph of a surface of the single crystal at 275 K. (c) On heating to 383 K

the Raman spectrum shows apparent changes, corresponding to a mixture of forms α, β and γ. (d) Micro-

photograph of the cracked crystal at 383 K. (e) Raman spectrum of form β at 293 K. (f) Micro-photograph

of the crystal showing pronounced mosaic spread at 293 K. Note that probably due to differences in the

sample environment, the temperatures of phase transitions in this experiment are slightly different

compared to those obtained by using other (thermoanalytical) methods.

`

Supplementary Figure 7. High-temperature phase transitions. (a) A two-dimensional projection of the

observed X-ray intensity plotted as function of the diffraction angle and temperature shows that two fist-

order phase transitions occur in a narrow temperature interval (343 K to 358 K). (b) The respective

diffraction patterns provide further evidence of the coexistence of different phases.

`

Supplementary Figure 8. High-temperature phase transitions of PHA in powdered samples. (a) The

Supplementary Figure 3B is shown here again for convenience to facilitate the discussion of the powder

diffraction patterns. On heating, the DSC curve of a single crystalline sample of form α shows two phase

transitions, α↔γ and γ. Powdered samples, however, show only one endothermic peak. (b) Time- and

temperature-resolved XRPD of the high-temperature phase transitions of a powdered PHA sample. From

298 K to 348 K only form α is present (see the peaks highlighted with yellow color). At 353 K the phase

transition α ↔ γ occurs, and the sample exists as a mixture of forms α and γ (see the peaks highlighted with

orange color). At 358 K phase β starts to emerge (red color) and its quantity increases with time. When the

sample is heated to 358 K, a ternary mixture is obtained. Under isothermal conditions, the relative amounts

of forms and increase and that of form gradually decreases, giving a binary mixture of forms and .

At the same time, form gradually transforms to , giving a phase-pure sample of form at the end of the

experiment.

`

Supplementary Figure 9. Rietveld plot of PHA at 358 K. The observed pattern (blue) measured in

Debye-Scherrer geometry, the best Rietveld fit profile (red), and the difference curve between the observed

and calculated profiles (gray). The positions of the Bragg reflections of the three phases are given together

with the ratio of the phases in the mixture. The data were collected at the ID31 High-Resolution Powder

Diffraction Beamline of the European Synchrotron Radiation Facility (ESRF) using wavelength of 0.40000

Å and a crystal analyzer detector.

`

Supplementary Figure 10. Mechanochemically induced phase transition. (a) Powder diffraction pattern

of the manually powdered sample of form α. (b) Powder diffraction pattern of the same sample after

automatic mechanical grinding (ball-milling). The sample was completely transformed into form β during

the treatment.

`

Supplementary Figure 11. Low-temperature phase transitions of PHA monitored by powder X-ray

diffraction. (a) Two-dimensional projection of the observed X-ray intensity plotted as a function of

temperature showing four phase transitions on cooling to 98 K and subsequent heating. (b) The scattered

intensity changes continuously during the first transition on cooling (α ↔ δ), followed by a sharp change (δ

↔ ε). These phase transitions are reversible on heating. Presumably, the phase transition α ↔ δ is of second

order while δ ↔ ε is of first order. (c) Close inspection of the diffraction patterns during the δ ↔ ε

transition reveals co-existence of phases, in support of a first-order phase transition.

`

Supplementary Figure 12. Rietveld plot of PHA at 90 K. The observed pattern (blue) measured in

Debye-Scherrer geometry, the best Rietveld fit profile (red), and the difference curve between the observed

and the calculated profiles (gray) are shown. The positions of the Bragg reflections of the three phases are

given together with the ratio of the phases in the mixture. The data were collected at the ID31 High-

Resolution Powder Diffraction Beamline of the European Synchrotron Radiation Facility (ESRF) using

wavelength of 0.40000 Å and a crystal analyzer detector.

`

Supplementary Figure 13. Vertical transitions, calculated by the TDDFT method (B3LYP/6–311G(d)

level), and the respective molecular orbital contributions for a molecule of the yellow polymorph (.

Supplementary Figure 14. Vertical transitions, calculated by the TDDFT method (B3LYP/6–311G(d)

level), and the respective molecular orbital contributions for a molecule of the red polymorph (.

Wavelength / nm 800 750 700 650 600 550 500 450 400

Os

cilla

tor

Str

en

gth

(f)

0.2

0.18

0.16

0.14

0.12

0.1

0.08

0.06

0.04

0.02

0

446.9 nm

438.7 nm

381.9 nm

HOMO LUMO

HOMO-1 LUMO

HOMO-2 LUMO

Wavelength / nm 800 750 700 650 600 550 500 450 400

Os

cilla

tor

Str

en

gth

(f)

0.2

0.16

0.12

0.08

0.04

0

390.3 nm

446.0 nm

453.8 nmHOMO LUMO

HOMO-1 LUMO

HOMO-2 LUMO

`

Supplementary Figure 15. Frontier molecular orbitals of a molecule from the yellow polymorph (.

The isodensity surface is plotted at 0.030 e.

Supplementary Figure 16. Frontier molecular orbitals of a molecule from the red polymorph (. The

isodensity surface is plotted at 0.030 e.

HOMO

E = - 6.69 eV

HOMO-1

E = - 6.95 eV

HOMO-2

E = - 7.06 eV

HOMO-3

E = - 7.33 eV

HOMO-4

E = - 7.39 eV

LUMO

E = - 3.14 eV

LUMO+1

E = - 2.57 eV

LUMO+2

E = - 1.92 eV

LUMO+3

E = - 0.669 eV

LUMO+4

E = - 0.661 eV

3.55 eV

HOMO

E = - 6.61 eV

HOMO-1

E = - 6.94 eV

HOMO-2

E = - 7.04 eV

HOMO-3

E = - 7.30 eV

HOMO-4

E = - 7.41 eV

LUMO

E = - 3.21 eV

LUMO+1

E = - 2.59 eV

LUMO+2

E = - 2.00 eV

LUMO+3

E = - 0.713 eV

LUMO+4

E = - 0.609 eV

3.40 eV

`

Supplementary Figure 17. Effect of rotation of the phenyl ring on the TDDFT-calculated vertical

transitions of the four forms of PHA with determined structures. The dihedral angle of the phenyl

group with the ligand was constrained to the value obtained from the crystal structure determination and the

remaining part of the molecule was optimized.

Supplementary Figure 18. Angle between the habit plane (the advancing phase front) and the crystal axes

during the transition → and relation to the molecular packing in phases and .

`

Polymorph,

temperature ORTEP diagram

, 150 K

, 160 K

, 170 K

Supplementary Figure 19. ORTEP diagrams (50% probability) of the polymorphs of PHA at various

temperatures.

`

, 180 K

, 210 K

, 240 K

, 298 K

Supplementary Figure 19 (continued). ORTEP diagrams (50% probability) of the polymorphs of

PHA at various temperatures.

`

, 310 K

, 320 K

, 100 K

, 298 K

Supplementary Figure 19 (continued). ORTEP diagrams (50% probability) of the polymorphs of PHA at

various temperatures.

`

, 358 K

, 90 K

Supplementary Figure 19 (continued). ORTEP diagrams (50% probability) of the polymorphs of

PHA at various temperatures.

`

Supplementary Table 1. Basic crystallographic data and refinement conditions

Parameter -PHA -PHA -PHA -PHA -PHA -PHA

Temp. / K 150 160 170 180 210 240

Formula C17H10F6N2O2

Pd

C17H10F6N2O2

Pd

C17H10F6N2O2

Pd

C17H10F6N2O2

Pd

C17H10F6N2O2

Pd

C17H10F6N2O2

Pd

2θmax / o 58.27 56.71 55.0 54.26 54.26 54.6

Crystal

system

Triclinic Triclinic Triclinic Triclinic Triclinic Triclinic

Space group P1 P1 P1 P1 P1 P1

a, b, c / Å 8.138(4)

13.173(5)

16.240(6)

8.0687(17)

13.159(2)

16.091(3)

8.15370(10)

13.15840(10)

15.9732(2)

8.1833(11)

13.1829(17)

15.912(2)

8.2662(8)

13.1985(12)

15.8437(15)

8.359(2)

13.214(4)

15.787(5)

α, β, γ / ° 85.75(2)

81.91(2)

80.10(2)

85.626(9)

84.562(12)

82.134(13)

86.1960(10)

84.7400(10)

83.0160(10)

86.3760(10)

85.7640(10)

83.5490(10)

86.5980(10)

86.1000(10)

84.0190(10)

86.773(3)

86.328(3)

84.411(3)

V / Å3 1695.6(12) 1681.3(5) 1691.24(3) 1698.5(4) 1712.8(3) 1729.7(9)

Z 4 4 4 4 4 4

ρ / (g cm−3

) 1.938 1.954 1.943 1.934 1.918 1.900

μ / mm-1

1.174 1.184 1.177 1.172 1.162 1.150

GoF 1.086 1.218 1.062 1.051 1.025 1.047

Rint 0.1318 0.1383 0.0280 0.0133 0.0130 0.0229

Final R

indices [I >

2(I)]

R1 = 0.0574

wR2 = 0.1724

R1 = 0.0773

wR2 = 0.2683

R1 = 0.0333

wR2 = 0.0778

R1 = 0.0203

wR2 = 0.0498

R1 = 0.0210

wR2 = 0.0514

R1 = 0.0272

wR2 = 0.0722

R indices (all

data)

R1 = 0.0637

wR2 =

0.1797

R1 = 0.0908

wR2 = 0.2808

R1 = 0.0382

wR2 = 0.0821

R1 = 0.0251

wR2 = 0.0525

R1 = 0.0255

wR2 = 0.0543

R1 = 0.0330

wR2 = 0.0764

-PHA -PHA -PHA β-PHA β-PHA γ-PHA ε-PHA

298 310 320 100 298 358 90

C17H10F6N2O2

Pd

C17H10F6N2O2

Pd

C17H10F6N2O2

Pd

C17H10F6N2O2

Pd

C17H10F6N2O2

Pd

C17H10N2O2F6

Pd

C17H10N2O2F6

Pd

56.74 54.16 53.98 61.43 54.308 12 ( = 0.4 Å) 12 ( = 0.4 Å)

Triclinic Triclinic Triclinic Triclinic Triclinic Triclinic Triclinic

P1 P1 P1 P1 P1 P1 P1

8.4609(2)

13.2354(3)

15.7602(4)

8.491(2)

13.239(3)

15.740(4)

8.5109(19)

13.239(3)

15.735(4)

11.4476(5)

13.5500(6)

13.6484(6)

7.0160(2)

11.6870(3)

12.4659(3)

4.2736(5)

13.5601(2)

14.8046(3)

7.7972(2)

13.2030(2)

16.4284(3)

86.9550(10)

86.4460(10)

84.6650(10)

87.012(3)

86.459(3)

84.676(3)

87.060(3)

86.565(3)

84.714(3)

116.2290(17)

99.6857(18)

107.0615(17)

63.1390(10)

84.7600(10)

80.9950(10)

83.307(8)

93.959(9)

76.843(7)

94.002(2)

87.307(3)

100.656(3)

`

1751.86(7) 1756.4(7) 1760.4(7) 1702.43(13) 900.38(4) 825.66(10) 1657.03(6)

4 4 4 4 2 2 4

1.876 1.871 1.866 1.930 1.825 Rexp = 1.418

Rwp = 9.895

Rp = 8.580

RBragg = 1.565

No.

parameters =

119

Rexp = 2.008

Rwp = 9.870

Rp = 8.002

RBragg = 1.221

No.

parameters =

49

1.136 1.133 1.130 1.169 1.105

1.090 1.020 1.009 1.028 1.098

0.0205 0.0166 0.0150 0.0333 0.0226

R1 = 0.0291

wR2 = 0.0783

R1 = 0.0301

wR2 = 0.0744

R1 = 0.0329

wR2 = 0.0838

R1 = 0.0528

wR2 = 0.1331

R1 = 0.0669

wR2 = 0.1792

R1 = 0.0359

wR2 = 0.0929

R1 = 0.0412

wR2 = 0.0816

R1 = 0.0459

wR2 = 0.0928

R1 = 0.0668

wR2 = 0.1465

R1 = 0.0744

wR2 = 0.1884

`

Supplementary Table 2. TDDFT-calculated singlet electronic transitions of forms , , , and of PHA.

Only the major orbital contributions are listed.

Wavelength

/ nm

Oscillator

strength, f Frontier molecular orbital contributions

Form

446.9 0.0829 HOMO → LUMO (61%), HOMO-1 → LUMO (2%),

HOMO-2 → LUMO (28%), HOMO-3 → LUMO (3%)


HOMO-2 → LUMO (49%)

381.9 0.1692 HOMO-1 → LUMO (70%), HOMO-2 → LUMO (20%),

HOMO-2 → LUMO +2 (4%)

Form


HOMO-2 → LUMO (31%), HOMO-3 → LUMO (2%)




HOMO-2 → LUMO+2 (3%)

Form


HOMO-2 → LUMO (9%), HOMO-3 → LUMO (4%),

HOMO-2 → LUMO+2 (4%)

446.0 0.0145 HOMO → LUMO (6%), HOMO-1 → LUMO (3%)



HOMO-2 → LUMO+2 (5%), HOMO-2 → LUMO+2 (5%),


Form


HOMO-2→ LUMO +2 (3%), HOMO-3 → LUMO (4%),

HOMO-3→ LUMO (4 %)


HOMO → LUMO (13%)

385.7 0.1718 HOMO-1→ LUMO (78%), HOMO-2 → LUMO (10%),

HOMO-2→ LUMO+2 (5%)

`

Supplementary Table 3. Experimental values of velocity of the phase progression

Phase change Movie code Average velocity

(meter·second–1

)

Sum average velocity

(meter·second–1

)

→

Movie-5a 0.483

0.538

Movie-6a 0.542

Movie-7a 0.588

→

Movie-1b 3.79 × 10

-5

4.34 × 10–5

Movie-2b 3.04 × 10

-5

Movie-3b 6.18 × 10

-5

aMovies were recorded with a high speed camera at rate of 10,000 frames per second.

bMovies were recorded with a digital camera at rate of 30 frames per second.

Supplementary Table 4. Velocity of expansion of PHA crystals during the transition of form to form

Movie code (rate) l /mm t /ms Velocity of expansion l /t

(meter·second–1

)

Sum average

velocity

(meter·second–1

)

#Movie-5 (10,000 fpsa) 0.1215 2.8 0.0434

0.0418 #Movie-6 (10,000 fps

a) 0.1333 4.2 0.0316

#Movie-7 (10,000 fpsa) 0.1409 2.8 0.0503

aIn frames per second (fps).

`

Supplementary Table 5. Selected Pd···Pd distances and angles (planes of free phenyl ring to the rest of the

molecule) in the structures of PHA

Polymorph,

temperature

d(Pd···Pd) Å Calculated inter-

planar angle (°)

Inter-planar angle (°) from

X-ray analysisa

α, 150 K 3.874(2)

4.314(2)

43.8 46.89(12) (Pd2), 50.26(13) (Pd1)

α, 160 K 3.755(2)

4.393(2)

48.75(25) (Pd2), 46.27(23) (Pd1)

α, 170 K 3.7573(4)

4.4927(3)

48.38 (8)(Pd2), 51.36(8) (Pd1)

α, 180 K 3.7346(5)

4.5555(6)

47.81(5) (Pd2), 46.53(4) (Pd1)

α, 210 K 3.7370(4)

4.6522(5)

47.54(5) (Pd2), 46.13(5) (Pd1)

α, 240 K 3.7552(9)

4.736(1)

47.53(6) (Pd2), 46.20(6) (Pd1)

α, 298 K 3.7839(3)

4.8166(3)

47.23(8) (Pd2), 46.04(8) (Pd1)

α, 310 K 3.7970(9)

4.833(1)

47.10(8) (Pd2), 45.92(8) (Pd1)

α, 320 K 3.8041(9)

4.846(1)

47.00(9) (Pd2), 45.85(9) (Pd1)

β, 100 K 4.0457(4)

3.2837(5)

4.4696(5)

16.7 20.84(15) (Pd2), 14.03(16) (Pd1)

β, 298 K 3.4889(5)

4.5062(6)

15.56(29)

4.274(3) 63.4 86.11c

3.984(7)

4.332(7)

32.4 51.76 (Pd1B), 47.20 (Pd1A)b,c

aPd1 and Pd2 are two symmetry-independent molecules.

bPd1B and Pd1A are two symmetry-independent molecules.

cThe standard deviations are not available (powder data).

`

Supplementary Methods

Preparation and characterization

Synthesis and crystallization. PHA was prepared according to a previously published procedure1 and

recrystallized by slow evaporation from toluene or butyronitrile. We were not able to control the ratio of the

two forms, which appeared to depend on subtle factors. However, we noticed that impurities, introduced by

the synthetic procedure or by repeated recrystallization favor the crystallization of form . Sublimation

under moderate vacuum also yielded a mixture of smaller crystals of both yellow and red forms

(Supplementary Figure 1). Crystals of either form that were devoid of the other form were obtained at

opposite walls of the vessel (only very fine microcrystalline powder was deposited on the water-cooled cold

finger). Both polymorphs were stable at room temperature.

Thermal analysis and hot-stage microscopy. DSC analysis of PHA samples was carried out on TA DSC-

Q2000 instrument, using ca. 2–4 mg of the samples and empty Tzero aluminium pan as reference. In a

typical measurement, the samples were taken on a Tzero aluminium pan and heated from room temperature

(300.6 K) to the selected temperature at rate of 10 K min–1

. During the experiment the chamber was purged

with nitrogen at a rate of 50 mL min–1

. Low-temperature differential scanning calorimetry (DSC) curves

were recorded between 293 and 148 K in Al capsules using powdered samples with a Mettler Toledo DSC1

STARe system at heating/cooling rate of 5 K min–1

under flow of nitrogen. The thermogravimetric analysis

(TGA) was performed using TA SDT thermal analyzer system in the temperature range 293.15 – 873.15 K

at a heating rate of 10 K min–1

in dynamic atmosphere of nitrogen (rate of 50 mL min–1

). All DSC and TGA

data was analyzed with the Universal Analysis 2000 software, version 4.5A (TA instruments). In the hot-

stage microscopic experiments, the crystals and their phase transformation were observed under polarized

microscope (Q-imaging, Q32643) equipped with a temperature-controlled stage THMS600-PS mounted on

a Linkam temperature control system.

Raman spectroscopy. The spectra were recorded with a Jobin Yvon single grating spectrometer equipped

with a double super razor edge filter and a Peltier-cooled CCD camera. The resolution was 1 cm–1

in Raman

shift (grating 1800 L mm–1

). The spectra were taken in quasi-backscattering geometry using the linearly

polarized 532.0 nm line of a diode laser with power less than 1 mW, focused to a 20 µm spot through a 20-

fold microscope objective on to the top surface of the sample. For the heating experiments, Linkam THS

600 heater was used with a small argon gas flow around the sample placed in a glass capillary.

X-ray diffraction

Single crystal X-ray diffraction. X-ray diffraction data of phases and of PHA were collected on a

Bruker APEX DUO2 diffractometer with monochromated MoK radiation (λ = 0.71069 Å) having CCD as

area detector. Crystals were attached to a loop and/or glued to a thin glass fiber and kept in a temperature-

controlled stream of dry nitrogen during data collection. Variable-temperature unit cell measurements were

performed on a single crystal of PHA ( phase) by varying the temperature with an Oxford Cryosystream

Plus temperature-controlled unit. For the variable-temperature unit cell measurements, the data were first

collected at 300 K and then successive datasets were collected at intervals of 10 K during cooling and

heating. We were not able to collect data below 150 K and above 320 K of form due to disintegration of

the crystals. Due to low diffracting properties and poor crystal quality, the data for form were less than

optimal. The data for form were collected at 298 K (Z′ = 1) and the crystal was cooled to 100 K by flash-

freezing. The unit cell at 100 K (Z′ = 2) was doubled, as confirmed by inspection with the RLATT routine.

The disorder of the trifluoromethyl groups at 298 K was modeled (AFIX 127 and SIMU). The crystal

packing in the two structures is essentially identical, and the powder XRD pattern indicated that the

`

structure at LT is a modulation of the RT structure obtained by distortion of the lattice upon thermal

treatment. At both temperatures, there is a spurious electron density near the palladium atoms that accounts

for ~7% Pd that could not be accounted by a chemically sensible model. The data were corrected for

absorption with SADABS3. The structures were solved by direct methods SHELXS-97

4 and refined

with SHELXL-974 and SHELXL-2013

5. The coordinates and anisotropic thermal displacement parameters

for all non-hydrogen atoms were refined on F2 by weighted full-matrix least-squares. The crystallographic

data are listed in Supplementary Table 1.

Powder X-ray diffraction. High-resolution X-ray powder diffraction patterns were collected on a laboratory

powder diffractometer Stoe Stadi-P with CuKα1 radiation from primary Ge(111)-Johannson-type

monochromator and Dectris-MYTHEN 1K strip PSD with an opening angle of 12º in 2θ in Debye-Scherrer

geometry. Prior to the measurement the samples were manually powdered in a mortar and pestle and sealed

in borosilicate glass capillaries of 0.5 mm diameter (Hilgenberg glass no. 50). The samples were spun

during data collection for better particle statistics. For the temperature-resolved measurements, hot/cold air

blower (Oxford Cryosystems) was used for temperature control. Powder diffraction data of forms and

were collected (at 358 K and 90 K, respectively) at the ID31 high-resolution powder diffraction beamline of

the European Synchrotron Radiation Facility (ESRF) using radiation with = 0.40000 Å and a crystal

analyzer detector. The powder data analysis (pattern indexing, profile fitting, crystal structure solution and

refinement) was performed with the program TOPAS 4.26. Patterns of the polymorphs with unknown

crystal structures (, and ) were indexed with the singular value decomposition method7, which resulting

in triclinic unit cells. Precise lattice parameters of all polymorphs were determined by Pawley fits8, using

the fundamental parameter approach for peak fitting, applied on each diffraction pattern collected in the

studied temperature range. During the full profile decomposition, the lattice parameters, stain and crystal

size contributions were refined. Chebyshev polynomials were used to model the background. The crystal

structures of forms and were solved by the global optimization method of simulated annealing (SA) in

real space9,. The structure solution was performed in the Pī space group using two rigid bodies for and

four for in the respective asymmetric units. For the definition of the connectivity between the atoms

within the rigid body of the complex the z matrix notation was used. During the SA runs three rotations,

three translations and three torsions angles variations for each rigid body were allowed. An overall

temperature factor within a limited range was included in the SA process. Taken that was found in a

mixture together with and , their crystal structures were included in the course of structure solution in

real space with all their parameters kept fixed. Once a global minimum was found, the crystal structures

were subjected to Rietveld refinement10

, in which bond lengths and angles of similar chemical character

(e.g. aromatic, C—F bonds, C—N bonds etc.) were refined to a single joint value, together with free

refinement of all profile and lattice parameters. The anisotropy of width and asymmetry of the Bragg

reflections was successfully modeled by applying symmetry adapted spherical harmonics of eight’s order to

Gaussian, Lorentzian and exponential distributions which were then convoluted with geometrical and

instrumental contributions to the final peak profile. Despite the use of capillaries in Debye-Scherrer

geometry, a small amount of preferred orientation was detected and was adequately described by the use of

symmetry adapted spherical harmonics. The final Rietveld plots for and using the powder patterns

collected using high-resolution synchrotron radiation are given in Supplementary Figures 9 and 12 and the

crystallographic details are given in Supplementary Table 1.

Computational analysis Theoretical calculations of all the polymorphs of PHA were performed using Density functional theory

(DFT)11

with the Gaussian 09 program suite12

. In all cases, X-ray structures were used as initial input for

gas phase structural optimization. Becke three parameter exchange functional in conjunction with

LeeYangParr correlation (B3LYP) was employed for all calculations13,14

. The double zeta (LANL2DZ)

basis set was used for Pd atom, while the 6–31G(d) basis set was used on all the other lighter atoms (F, C,

`

H, N, O). All the optimizations were performed with tight SCF convergence criteria and using geometrical

constraints by restricting the rotation of free phenyl group. Vertical transitions of the PHA molecules were

simulated by performing time-dependent density functional theory (TDDFT) calculations on optimized

geometry, using 6–311G(d) basis set for lighter atoms and LANL2DZ for Pd atom. Solvent effects (toluene,

dielectric constant, ɛ = 2.37) were evaluated using polarizable continuum model (PCM) implemented in

Gaussian 0915

. The gas-phase conformational energy changes of the PHA rotamers and the respective

geometries were inspected by relaxed potential energy surface (PES) scan. Specifically, geometries of each

rotamer were obtained by 360° rotation of the free phenyl group with a gradual increment of 10° using

Pd1—N2—C7—C12 dihedral angle as variable). All computed structures were visualized and analyzed by

ChemCraft (ver. 1.7)16

.

Supplementary References

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Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg,

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functional of the electron density. Phys. Rev. B 37, 785–789 (1988).

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16. ChemCraft 1.6; Plimus: San Diego, CA (http://www.chemcraftprog.com, ver. 1.7).

supplementary figure 1. sublimation of pha. and of … · sublimation of pha. ... the crystal in...

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