Synthesis of a Novel Rigid Semi-Alicyclic Dianhydride and Its Copolymerized Transparent Polyimide Films’ Properties

A new series of colorless polyimides (CPIs) with outstanding thermal properties and mechanical properties were fabricated by the copolymerization of a novel dianhydride and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) with 2,2′-bistrifluoromethyl benzidine (TFDB). The novel dianhydride, 10-oxo-9-phenyl-9-(trifluoromethyl)-9,10-dihydroanthracene-2,3,6,7-tetraacid dianhydride (3FPODA), possessed a rigid semi-alicyclic structure, –CF3 and phenyl side groups, and an active carbonyl group. Benefitting from the special structure of 3FPODA, the glass transition temperatures (Tg) of the new CPIs improved from 330 °C to 377 °C, the coefficient of thermal expansion (CTE) decreased from 46 ppm/K to 24 ppm/K, and the tensile strength (TS), tensile modulus (TM), and elongation at break (EB) increased from 84 MPa to 136 MPa, 3.2 GPa to 4.4 GPa, and 2.94% to 4.13% with the increasing amount of 3FPODA, respectively. Moreover, the active carbonyl group of the 3FPODA could enhance the CPI’s adhesive properties. These results render the new dianhydride 3FPODA an ideal candidate monomer for the fabrication of high-performance CPIs.


Introduction
The Polyimides (PIs), a group of high performance polymers with excellent thermal and mechanical properties, as well as a low dielectric constant and outstanding chemical resistance [1][2][3][4][5][6], have been extensively used as flexible substrates in flexible copper clad laminates (FCCL), flexible printed circuit boards (FPCBs), and optoelectronics devices [7][8][9][10][11][12]. FPCBs are generally composed of copper (Cu) foil laminated with PI film, which can enhance the mechanical strength and tenacity of FPCBs so that the electric conductivity properties are retained during bending, sliding, friction and physical shock, etc [13]. To meet the process requirements, a PI is expected to possess extraordinary thermal stability (T g > 350 • C), a low coefficient of thermal expansion (CTE) to match that of copper (17 ppm/K), excellent mechanical properties, and good adhesive properties. However, with the development of the display industry, FPCBs have led to further requirements for PI with respect to optical properties.
The conventional aromatic PIs display a yellow or brown color caused by the formation of the charge transfer complex (CTC) effect between the donor diamine and the acceptor dianhydride moieties [14][15][16]. In order to obtain colorless polyimide (CPI) films, different endeavors have been proposed to achieve the modification of traditional aromatic PI, such as the incorporation of flexible groups [17][18][19], large-scale substituents [20][21][22][23], ring structures [24][25][26], fluorine-containing structures [27][28][29], and twisted or non-planar structures [30,31] in its backbone to limit the formation of the CTC effect to improve the film's transparency. Generally, the decreased CTC effect of PI films will degrade other properties, including its thermal stability and mechanical properties [32]. Therefore, balancing the optical properties with thermal stability and mechanical properties to fabricate CPI with outstanding comprehensive properties is still a challenge. 1 H, 13 C, and 19 F NMR spectra were all created via Bruker DRX-600 spectrometer (Karlsruhe, Germany) with chloroform-d (CDCl3), dichloromethane-d2 (CD2Cl2), and dimethylsulfoxide (DMSO-d6) as deuterated solvents. IR spectra were all measured by PerkinElmer SP one FT-IR (Waltham, MA, USA). Wide-angle X-ray diffraction (WAXD) measurement were carried out on Bruker Bede XRD Di (Karlsruhe, Germany). The optical properties of PI films were recorded on Shimadzu UV-2450 (Kyoto, Japan) from 300 to 800 nm. The refractive index of PI films was measured by ME-Lellipsometer (Wuhan, China). Thermogravimetric analysis (TGA) measurements were performed on PerkinElmer TGA-2 (Waltham, MA, USA) under nitrogen conditions at rate of 10 °C min −1 from room temperature to 800 °C. Dynamic mechanical analyses (DMA) were carried out on PerkinElmer DMA Q800 using tensile mode at a frequency of 1 Hz. Coefficient of thermal expansion (CTE) values were measured by thermal mechanical analysis (TMA) Q400 (USA). Mechanical properties were all measured by stretching machine. Contact angles were measured at room temperature with deionized water as the solvent. According to the stability of the droplets, the measurements were taken over a period of 120 s.

Preparation of PI Films
The copolymerization of CPI films with different dianhydride ratios derived from 3FPODA, 6FDA, and TFDB was prepared through traditional two-step method. The structures of the copolymerized polyimides are shown in Scheme 1. With PI-1 as an example, Polymers 2022, 14, 4132 5 of 12 the specific experimental steps were as follows: TFDB (1.000 g and 3.123 mmol) was deposited in a 50 mL three-necked flask; then, 18 g dried DMAc was added to dissolve the TFDB under the protection of nitrogen conditions. Then, 3FPODA (0.149 g and 0.312 mmol) and 6FDA (1.248 g and 2.811 mmol) were added to the reaction in several portions. Then, stirring of the reaction was continued for 24 h at room temperature. After polycondensation reaction, the Poly (amic acid) (PAA) was obtained. Then, an appropriate amount of acetic anhydride/triethylamine mixture was added to the PAA solution and reacted at 60 • C for 24 h. Consequently, the incompletely cyclic PI solution was obtained. The PI film was obtained by casting the PI solution on a clean glass plate. Then, the coated PI was heated at 80 • C for 1 h to release the solvent, and then sequentially heated at 100 • C for 30 min, 150 • C for 30 min, 200 • C for 30 min, 250 • C for 30 min, and 300 • C for 30 min. IR (cm −1 , film): 1787 (C=O asym. stretching), 1726 (C=O sym. stretching), and 1364 (C-N stretching). The FT-IR spectrum of these PIs are shown below.

Synthesis and Characterization of Monomer
A new rigid semi-alicyclic dianhydride 3FPODA was prepared through five-step synthesis as shown in Scheme 1, including trifluoromethylation, deprotection, phenyl substitution, oxidation, and a dehydration reaction. The geometrical optimization of the monomers 6FDA and 3FPODA was performed using the density functional theory (DFT) at the B3LYP level with the 6-31G (d) basis set and D3 dispersion correction (OPT B3LYP/6-31G(d) EM=GD3BJ) in the Gaussian 16 program. The molecular simulation of the monomers 3FPODA and 6FDA are shown in Figure 1. The monomer 6FODA was obtained by introducing a carbonyl group to the 6FDA, as shown in Figure 1. Compared with 6FDA, the backbone of the 6FODA molecule is approximately in plane due to the introduction of carbonyl groups. Two -CF 3 side group could increase the molecular chain's spacing. Moreover, replacing one of the -CF3 of 6FODA with a benzene ring could result in 3FPODA. Compared with -CF3, the benzene ring has a larger volume and stronger rigidity, thereby further increasing the molecular chain spacing. The structure of 3FPODA was confirmed by FT-IR, 1 H NMR, 13 C NMR, and 19 F NMR spectroscopy (Figures S1-S16). In the 1 H NMR spectrum, there were three peaks at 8.797, 7.561-7.542, and 7.505 ppm. The peak of the benzene ring side group protons was found at 7.561-7.542 ppm and the peaks at 8.797 and 7.505 ppm were attributed to the protons of the benzene ring on the backbone. In the 13 C NMR spectrum, all the signals of the carbons were observed at 58-181 ppm. In addition, in the 19 F NMR spectrum, the peak of a fluorine atom was shown at −65.37 ppm. In the NMR tests, all the observed peaks were consistent with the structure of 3FPODA.

Preparation and Characterization of CPIs
A series of CPIs with 3FPODA ratios of 0, 10 %, 20 %, 30 %, 40 %, and 50 % were coded as PI-0, PI-1, PI-2, PI-3, PI-4, and PI-5, respectively, which were prepared by different ratios of dianhydride from 3FPODA and 6FDA, as well as TFDB as the diamine by a traditional two-step method (Scheme 1). The molecular simulation of the repeating units 3FPODA/TFDB and 6FDA/TFDB are shown in Figure 1. It was found that the repeating unit 6FDA/TFDB has a more twisted structure, while the repeating unit 3FPODA/TFDB

Preparation and Characterization of CPIs
A series of CPIs with 3FPODA ratios of 0, 10%, 20%, 30%, 40%, and 50% were coded as PI-0, PI-1, PI-2, PI-3, PI-4, and PI-5, respectively, which were prepared by different ratios of Polymers 2022, 14, 4132 6 of 12 dianhydride from 3FPODA and 6FDA, as well as TFDB as the diamine by a traditional twostep method (Scheme 1). The molecular simulation of the repeating units 3FPODA/TFDB and 6FDA/TFDB are shown in Figure 1. It was found that the repeating unit 6FDA/TFDB has a more twisted structure, while the repeating unit 3FPODA/TFDB has a higher degree of linearity and rigidity of the main chains. The structures of the PIs were confirmed by FT-IR spectroscopy as shown in Figure 2a. The asymmetric and symmetric stretch peaks of C=O of all the CPIs can be clearly observed around 1787 cm −1 and 1726 cm −1 , and C-N stretching can be found around 1364 cm −1 . The characteristic peaks of amino and carboxyl groups were basically invisible, which indicated that the imidization was finished.

Preparation and Characterization of CPIs
A series of CPIs with 3FPODA ratios of 0, 10 %, 20 %, 30 %, 40 %, and 50 % were coded as PI-0, PI-1, PI-2, PI-3, PI-4, and PI-5, respectively, which were prepared by different ratios of dianhydride from 3FPODA and 6FDA, as well as TFDB as the diamine by a traditional two-step method (Scheme 1). The molecular simulation of the repeating units 3FPODA/TFDB and 6FDA/TFDB are shown in Figure 1. It was found that the repeating unit 6FDA/TFDB has a more twisted structure, while the repeating unit 3FPODA/TFDB has a higher degree of linearity and rigidity of the main chains. The structures of the PIs were confirmed by FT-IR spectroscopy as shown in Figure 2a. The asymmetric and symmetric stretch peaks of C=O of all the CPIs can be clearly observed around 1787 cm −1 and 1726 cm −1 , and C-N stretching can be found around 1364 cm −1 . The characteristic peaks of amino and carboxyl groups were basically invisible, which indicated that the imidization was finished.

Solubility and WAXD
All the levels of solubility of the CPIs were tested in different organic solvents, as shown in Table S1. At room temperature, these CPIs displayed an outstanding solubility in polar solvents such as NMP and DCM. As listed in Table S1, the solubility levels of the PI-1 to PI-5 were as good as PI-0. Some researchers have revealed that it is possible to increase the free volume of the molecular chain and increase the distance between the molecular chains by introducing solubilizing groups (such as a -CF3 group, carbonyl group, and benzene ring side group) in the main chain. These features of the structures facilitate the easier entrance of small solvent molecules into the molecules and improve their solubility [36][37][38][39]. Therefore, the copolymerized CPIs also have an excellent solubility.
The wide-angle X-ray diffraction (WAXD) test was carried out to further study the change in the average spacing distance of the PIs; the results are shown in Figure 2b. These PI films were amorphous, similar to typical PIs. Based on Bragg's equation, 2dsinθ = nλ (n = 1, λ = 1.54 Å) [35], the average spacing distance (d-spacing) could be calculated according

Solubility and WAXD
All the levels of solubility of the CPIs were tested in different organic solvents, as shown in Table S1. At room temperature, these CPIs displayed an outstanding solubility in polar solvents such as NMP and DCM. As listed in Table S1, the solubility levels of the PI-1 to PI-5 were as good as PI-0. Some researchers have revealed that it is possible to increase the free volume of the molecular chain and increase the distance between the molecular chains by introducing solubilizing groups (such as a -CF 3 group, carbonyl group, and benzene ring side group) in the main chain. These features of the structures facilitate the easier entrance of small solvent molecules into the molecules and improve their solubility [36][37][38][39]. Therefore, the copolymerized CPIs also have an excellent solubility.
The wide-angle X-ray diffraction (WAXD) test was carried out to further study the change in the average spacing distance of the PIs; the results are shown in Figure 2b. These PI films were amorphous, similar to typical PIs. Based on Bragg's equation, 2dsinθ = nλ (n = 1, λ = 1.54 Å) [35], the average spacing distance (d-spacing) could be calculated according to the WAXD peaks. The results are listed in Table S1. The PI-0 to PI-5 possessed d-spacing values in the range of 6.41-6.65 Å. It can be intuitively found that with the increased amount of 3FPODA, the d-spacing of the PIs increased, which agrees with the theory mentioned above.

Optical Properties-1
A high transparency and low YI are the crucial properties of CPI for the fabrication of transparent FPCBs. A picture of these CPIs is shown in Figure 3a. It is obvious that all the PIs are basically colorless. The optical properties of the PIs were measured by UV-Vis spectroscopy. The UV-Visible spectrum of the PIs is shown in Figure 3b. Their crucial optical properties, including their transmittance at 400 nm (T 400 ) and 550 nm (T 550 ), cut-off wavelengths (λ 0 ), yellow index (YI), and b*, are listed in Table 1. As shown in Table 1, PI-1 to PI-5 exhibited a T 400 from 30% to 71%, a T 550 from 89% to 91%, λ 0 from 343 nm to 372 nm, and a YI from 2.83 to 8.63. However, the contrast PI-0 exhibited a T 400 of 80%, T 550 of 91%, and λ 0 of 345 nm and YI 2.04. Compared with PI-0, the cut-off wavelength of PI-1 to PI-5 was red-shifted, the transmittance at 400 nm decreased significantly, and the YI value also increased. In addition, with the increased of 3FPODA content, the change was more obvious. This may be caused by the carbonyl group of the 3FPODA. In the molecular simulation of 3FPODA, as shown in Figure 1, the carbon atom of the carbonyl Polymers 2022, 14, 4132 7 of 12 group was sp 2 -hybridized, forming a conjugate with the benzene ring on both sides. On the one hand, the existence of this conjugated structure could increase the CTC effect, and the absorption peak of the CTC effect was located in the 360-500 nm band [40,41]. As a result, the YI value of the PIs was increased and the T 400 decreased. On the other hand, the π electrons of the conjugated structure underwent electronic transitions, and their energy absorption peaks were located in the 300-380 nm range [42,43], which could red-shift the cut-off wavelength of the CPIs. Therefore, it is crucial to control the amount of 3FPODA to prepare CPIs suitable for transparent FPCBs. It is notable that PI-1 to PI-4 possessed better optical properties and the suitable proportion of 3FPODA should be below 40%. wavelengths (λ0), yellow index (YI), and b*, are listed in Table 1. As shown in Table 1, PI-1 to PI-5 exhibited a T400 from 30 % to 71 %, a T550 from 89 % to 91 %, λ0 from 343 nm to 372 nm, and a YI from 2.83 to 8.63. However, the contrast PI-0 exhibited a T400 of 80 %, T550 of 91 %, and λ0 of 345 nm and YI 2.04. Compared with PI-0, the cut-off wavelength of PI-1 to PI-5 was red-shifted, the transmittance at 400 nm decreased significantly, and the YI value also increased. In addition, with the increased of 3FPODA content, the change was more obvious. This may be caused by the carbonyl group of the 3FPODA. In the molecular simulation of 3FPODA, as shown in Figure 1, the carbon atom of the carbonyl group was sp 2hybridized, forming a conjugate with the benzene ring on both sides. On the one hand, the existence of this conjugated structure could increase the CTC effect, and the absorption peak of the CTC effect was located in the 360-500 nm band [40,41]. As a result, the YI value of the PIs was increased and the T400 decreased. On the other hand, the π electrons of the conjugated structure underwent electronic transitions, and their energy absorption peaks were located in the 300-380 nm range [42,43], which could red-shift the cut-off wavelength of the CPIs. Therefore, it is crucial to control the amount of 3FPODA to prepare CPIs suitable for transparent FPCBs. It is notable that PI-1 to PI-4 possessed better optical properties and the suitable proportion of 3FPODA should be below 40 %.  Table 1. PI-1 to PI-5 displayed refractive indices and birefringence at 550 nm in the range of 1.571-1.580 and 0.0347-0.0496, respectively. However, the contrast PI-0 possessed refractive indices and birefringence at 550 nm of 1.540 and 0.0276, respectively. The refractive indices and birefringence of PI-1 to PI-5 were higher than the contrast PI-0, and increased with the  Furthermore, the refractive indices and the out-of-plane birefringence of the CPIs were tested and are shown in Figure 3c,d. The results were summarized in Table 1. PI-1 to PI-5 displayed refractive indices and birefringence at 550 nm in the range of 1.571-1.580 and 0.0347-0.0496, respectively. However, the contrast PI-0 possessed refractive indices and birefringence at 550 nm of 1.540 and 0.0276, respectively. The refractive indices and birefringence of PI-1 to PI-5 were higher than the contrast PI-0, and increased with the increasing proportion of 3FPODA. This was due to the structure of 3FPODA, which contains linear semi-alicyclic structures and a certain conjugation between the carbonyl and benzene ring on both. Its features increased the regularity of the molecular chain of the PIs, provided them with a higher orientation, and increased their birefringence.

Thermal Properties
The thermal properties, including the T g values and CTE values, were the critical indexes governing the ability of the CPIs to satisfy the process of creating a transparent FPCB. The thermal properties of these CPIs were evaluated by thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and thermal mechanical analysis (TMA). The results are shown in Figure 4, and the thermal indices (T g , T d1 , T d5 , and CTE) are listed in Table 2. PI-1 to PI-5 possessed T g values in the range of 342-382 • C, while the T g of the contrast PI-0 was 330 • C. It can be found from the DMA curves in Figure 4b that the T g of all the copolymerized PIs were higher than the reference PI-0, and the T g of the CPIs increased along with the increase in the amount of 3FPODA. This evidenced that the addition of 3FPODA could increase the T g of CPIs. As shown in Figure 1, the repeating unit of 3FPODA/TFDB possessing a semi-alicyclic ring structure in its backbone enabled it to be more rigid than the repeating unit of 6FDA/TFDB. Importantly, the T g of the CPIs depends on the degree of rigidity of the molecular chain and the CTC effect between the inter or intra molecular chains formed between the dianhydride and diamine residues [44]. The conjugation of 3FPODA between the carbonyl group and the benzene ring next to it could enhance the CTC effect's influence on the inter or intra molecular chains' ability to increase the T g of the CPIs. Furthermore, the phenyl side group could restrict the movement of molecular segments and increased the rigidity of the polymer. Thus, the addition of 3FPODA in the CPI ensured that its T g was higher than the PI based on pure 6FDA.   The thermal stabilities of these PIs are shown in Table 2 and Figure 4a. The decom-  The thermal stabilities of these PIs are shown in Table 2 and Figure 4a. The decomposition temperatures (T d1 ) at a 1% weight loss of PI-1 to PI-5 were in the range of 480-499 • C. In addition, the T d5 values were between 542-552 • C. Whereas the T d1 and T d5 values of the contrast PI-0 were 485 • C and 520 • C, respectively. This indicated that the addition of 3FPODA can improve the thermal stabilities of the PIs. As mentioned above, the rigid structure of 3FPODA enhanced the inter-chain interactions, thereby increasing their thermal stabilities.
The results of the TMA test are shown in Table 2 and Figure 4c. The CTE values of PI-1 to PI-5 were between 23-42 ppm/K. Whereas the CTE value of PI-0 was 46 ppm/K. This demonstrates that the addition of 3FPODA reduced the CTE value of the CPIs and enhanced their dimensional stability. As shown in Figure 1, the semi-alicyclic ring structure and carbonyl group of 3FPODA granted the repeating unit of 3FPODA/TFDB a more rigid and higher linearity than 6FDA/TFDB. Notably, the incorporation of carbonyl group on the backbone prevented the molecular rotation from decreasing the CTE values. Furthermore, the phenyl side group could restrict the movement of the molecular segments to further reduce the CTE of the CPIs [45].

Mechanical Properties
The mechanical properties of the PIs were measured by a tensile test shown in Figure 4d and the mechanical indices (T S , T M , and E B ) are summarized in Table 2. PI-1 to PI-5 possessed T S values of 76-136 MPa, E B of 2.05-4.13%, and T M of 3.6-4.5 GPa. As a reference, PI-0 possessed a T S of 84 MPa, an E B of 2.94%, and a T M of 3.2 GPa. From the stress-strain curve, it was found that the addition of 3FPODA enhanced the mechanical properties of the CPI films. As mentioned above, the repeating unit of 3FPODA/TFDB possessed a much more rigid, regular, and highly linear structure than 6FDA/TFDB, which effectively enhanced its mechanical properties [46]. Therefore, the tensile modulus results demonstrated that the increasing amount of 3FPODA increased the rigidity of the PI backbone and significantly enhanced its tensile modulus.

Surface Properties
The results of the contact angle test are shown in Figure 5 and Table 2. PI-1 to PI-5 displayed contact angles of 65.4 • to 83.3 • , and the contact angle of PI-0 was 88.4 • . The results demonstrated that the incorporation of 3FPODA enhanced the hydrophilicity of the surface caused by increasing the hydrophilic performance of the polar carbonyl group in the 3FPODA. At present, the commonly used method of preparing the FCCL of the FPCB is to combine PI film with copper foil with an adhesive. The enhanced hydrophilic surface of the CPIs' surfaces could contribute to the spread and bonding of the adhesive. Moreover, the reactivity of the carbonyl group of 3FPODA could react with the adhesive and further improve the adhesive properties and the bonding strength of the CPI and the adhesive, which could prevent the cracking of the interface. The mechanical properties of the PIs were measured by a tensile test shown in Figure  4d and the mechanical indices (TS, TM, and EB) are summarized in Table 2. PI-1 to PI-5 possessed TS values of 76-136 MPa, EB of 2.05-4.13 %, and TM of 3.6-4.5 GPa. As a reference, PI-0 possessed a TS of 84 MPa, an EB of 2.94 %, and a TM of 3.2 GPa. From the stressstrain curve, it was found that the addition of 3FPODA enhanced the mechanical properties of the CPI films. As mentioned above, the repeating unit of 3FPODA/TFDB possessed a much more rigid, regular, and highly linear structure than 6FDA/TFDB, which effectively enhanced its mechanical properties [46]. Therefore, the tensile modulus results demonstrated that the increasing amount of 3FPODA increased the rigidity of the PI backbone and significantly enhanced its tensile modulus.

Surface Properties
The results of the contact angle test are shown in Figure 5 and Table 2. PI-1 to PI-5 displayed contact angles of 65.4 º to 83.3 º, and the contact angle of PI-0 was 88.4 º. The results demonstrated that the incorporation of 3FPODA enhanced the hydrophilicity of the surface caused by increasing the hydrophilic performance of the polar carbonyl group in the 3FPODA. At present, the commonly used method of preparing the FCCL of the FPCB is to combine PI film with copper foil with an adhesive. The enhanced hydrophilic surface of the CPIs' surfaces could contribute to the spread and bonding of the adhesive. Moreover, the reactivity of the carbonyl group of 3FPODA could react with the adhesive and further improve the adhesive properties and the bonding strength of the CPI and the adhesive, which could prevent the cracking of the interface.

Conclusions
In conclusion, a novel, rigid, semi-alicyclic dianhydride, 3FPODA, and a series of modified PIs with different amounts of 3FPODA, were reported. The incorporation of rigid, semi-alicyclic 3FPODA, which possessed -CF3 and phenyl side groups and a carbonyl group, contributed to the increased rigidity and linearity of the molecular chain of

Conclusions
In conclusion, a novel, rigid, semi-alicyclic dianhydride, 3FPODA, and a series of modified PIs with different amounts of 3FPODA, were reported. The incorporation of rigid, semi-alicyclic 3FPODA, which possessed -CF 3 and phenyl side groups and a carbonyl group, contributed to the increased rigidity and linearity of the molecular chain of the CPIs compared to 6FDA. These features endowed the CPIs with better thermal and mechanical properties. According to the copolymerization results, PI-4 possessed the best comprehensive performance with λ 0 of 371 nm, a T 400 of 31%, a T 550 of 90%, a T g of 377 • C, a CTE value of 24 ppm/K, a T S of 136 MPa, an E B of 4.13%, and a T M of 4.4 GPa. These excellent property indexes were crucial for CPIs ability to prepare a transparent FPCB. Moreover, the polar carbonyl group of 3FPODA improved the adhesive properties of the CPIs, which improved the interface inertia of the ordinary PI. Thus, this work provided an effective strategy to modify traditional CPIs towards acquiring outstanding thermal and mechanical properties and good adhesive properties, which satisfies the requirement of a transparent FPCB.
Supplementary Materials: The following supporting information can be downloaded at: https:// www.mdpi.com/article/10.3390/polym14194132/s1, Figure S1: The 1 H NMR spectrum of compound 2; Figure S2: The 13 C NMR spectrum of compound 2; Figure S3: The 19 F NMR spectrum of compound 2; Figure S4: The 1 H NMR spectrum of compound 3; Figure S5: The 13 C NMR spectrum of compound 3; Figure S6: The 19 F NMR spectrum of compound 3; Figure S7: The 1 H NMR spectrum of compound 4; Figure S8: The 13 C NMR spectrum of compound 4; Figure S9: The 19 F NMR spectrum of compound 4; Figure S10: The 1 H NMR spectrum of compound 5; Figure S11: The 13 C NMR spectrum of compound 5; Figure S12: The 19 F NMR spectrum of compound 5; Figure S13: The 1 H NMR spectrum of compound 6 (3FPODA); Figure S14: The 13 C NMR spectrum of compound 6 (3FPODA); Figure S15: The 19 F NMR spectrum of compound 6 (3FPODA); Figure S16 Institutional Review Board Statement: Not applicable.

Data Availability Statement:
The data presented in this study are available on request from the corresponding author.

Conflicts of Interest:
The authors declare no conflict of interest.