only slightly (lifetimes of compounds **241c** and **242c** increased to 2.75 ns after bubbling with N₂). On the other hand, decay of methoxy derivatives were more complicated, varied for both shorter- and longer-wavelength bands and could not be explained by a typical ICT emitting state. Analysing fluorescence dynamics of compounds **242b** at the shorter-wavelength band, as an example, very fast dynamics with the lifetime within the instrument response function (<80 ps) were observed. This decay dynamics are typical for a molecule with a very low quantum yield in moderately polar solvents. Nonetheless, decay at the longer-wavelength contained two components: (i) a very fast (<80 ps, ≈ 90% amplitude) and (ii) longer one (within the order of 10 ns, ≈ 10% amplitude). After bubbling, the longer component prolonged up to 30 ns and returned to 10 ns after exposure to air. These observations implied that methoxy derivatives disponed with two contributions from emissions of different origin. The shorter-wavelength emission originated from fluorescence of the LE with small quantum yield independently on the oxygen in solution. The longer-wavelength emission band consisted of LE fluorescence and long-lived fluorescence from a highly stabilized ICT state strongly dependent on deoxygenation.
<figure><img src="image_119.png" /><figcaption>**Figure 74.** Excited state dynamics of 241 and 242 in THF before and after bubbling with N₂. For compounds 241b, 242a and 242b dynamics were detected at both shorter- and longer-wavelength emission bands.</figcaption></figure>

## AIE properties

For investigation of an AIE properties, fluorescence spectra were measured in THF/water solutions with different ratios. Recorded spectra of all final compounds are displayed in *Figure 75*. The longer-wavelength emission band of methoxy derivatives **a** and **b** vanished after addition of 10% of water with remaining emission from the LE state. This emission band underwent a slight red-shift with increasing amount of water as a result of increasing polarity of solvents mixture. Emission intensities remained unchanged up to 60% of water ratio. Further addition of water resulted in increase of emission intensity. Small blue-shift in emission maxima occurred at 90 and 97% of water content. For diphenylamino derivatives **c**, a slow decrease
in fluorescence intensity and red-shift of emission maxima were observed by up to ~50% of water. Additional water increased emission intensity, followed by a second gradual decrease and blue-shift in the emission maxima.

<figure><img src="image_120.png" /><figcaption>**Figure 75.** Emission spectra of compounds 241 and 242 (c = 1 × 10⁻⁵ M) in THF/water mixture. Integration of emission band vs. water volume percent in mixture. Inserted pictures were taken upon irradiation with UV lamp (λem = 254 nm).</figcaption></figure>
Excited state dynamics of final compounds **241b** and **242b** were studied under the same conditions as described in previous paragraph; obtained spectra are shown in *Figure 76*. Increase in fluorescence lifetime was expected due to the suppressing of nonradiative decays during aggregation. The out-of-plane rotation of acridan unit is expected to lower the luminescence intensity due to its energy consumption. However, aggregation is considered to hinder this process. Indeed, time resolved measurements revealed an increase of the average lifetime for compounds **241b** and **242b** upon increasing water ratio. In more details, the average lifetime of **241b** enhanced from <0.050 to 2.7 ns when going from 20% to 95% water solution. For compound **242b**, average lifetime increased from <0.050 ns up to 3.6 ns.

<figure><img src="image_121.png" /><figcaption>**Figure 76.** Emission dynamics of 241b and 242b ($c = 1 \times 10^{-5}$ M) in THF/water mixture.</figcaption></figure>

### Solid-state emission

Powdered samples of final compounds **241** and **242** were measured to obtaining their solid-state emission spectra. Results of this measurement, i.e. emission maxima are provided in *Table 10* and spectra are displayed in *Figure 77A*. Almost identical spectra were obtained for methoxy derivatives **241a**, **241b** and **242a**, which emitted green light with emission maxima around 470 nm. Red-shift in emission maxima to 508 nm was observed for turquoise light emitting compound **226b**. Both diphenylamino derivatives **c** showed emission maxima of their narrow emission bands in the range of 520–530 nm with green emission.

Spin-coating method was utilized to prepare thin films of final chromophores. Emission spectra of these neat films are provided in *Figure 77C* and *D*. Dual emission covering the vast majority of visible region was observed for chromophores **a** and **b** with peripheral methoxy group. Two distinguishable peaks could be seen in emission spectra of derivatives **225a,b**, whereas for compound **226a,b**, the LE state band appeared as pronounced shoulder superimposed on an emission band of the ICT state. The two emission bands clearly have a different origin, similarly to those obtained in THF. The longer-wavelength fluorescence band
involves a long-lived ICT state, as revealed by emission decays with long dynamics (see Annex 4). On the contrary, diphenylamino derivatives **c** exhibited narrow single peak emission with the maxima appearing slightly over 500 nm. Chromaticity coordinates, which are close to those of pure white light, are also provided in Table 9.

<figure><img src="image_122.png" /><figcaption>**Figure 77.** (A) Normalized emission spectra of solid-state chromophores **241** and **242**. (B) Picture of powdered final compounds under UV lamp ($\lambda_{em}$ = 254 nm). Emission spectra of neat film of compounds **241** (C) and **242** (D).</figcaption></figure>

**4.6 DFT calculation**

Gaussian 16W software was employed to establish the spatial and electronic properties of final compounds **241** and **242**. The initial geometries of studied molecules, HOMO and LUMO energies and ground state dipole moments were calculated at the B3LYP/6-311++G(3d.f.2p) level in vacuum. The electronic absorption spectra were calculated by the TD-DFT (n states = 8) B3LYP/6-311++G(3d,f.2p) method. Results are provided in Table 10. The calculations were performed and evaluated by Prof. Ing. Oldřich Pytela, DrSc. and Prof. Ing. Filip Bureš, Ph.D.
<table><caption>**Table 10.** Results of DFT calculation for compounds **241** and **242**.</caption><thead><tr><th>compd</th><th>E<sub>HOMO-1</sub><br>[eV]</th><th>E<sub>HOMO</sub><br>[eV]</th><th>E<sub>LUMO</sub><br>[eV]</th><th>E<sub>LUMO+1</sub><br>[eV]</th><th>ΔE<sup>a</sup><br>[eV]</th><th>λ<sub>max</sub><br>[nm/eV]</th><th>GoS<sup>b</sup></th></tr></thead><tbody><tr><td><b>241a</b></td><td>-5.98</td><td>-5.10</td><td>-2.35</td><td>-2.35</td><td>2.75/3.63</td><td>352(3.52)</td><td>C<sub>s</sub></td></tr><tr><td><b>241b</b></td><td>-5.89</td><td>-5.06</td><td>-2.45</td><td>-2.45</td><td>2.61/3.44</td><td>381(3.25)</td><td>C<sub>s</sub></td></tr><tr><td><b>241c</b></td><td>-5.48</td><td>-5.08</td><td>-2.31</td><td>-2.31</td><td>2.77/3.17</td><td>434(2.86)</td><td>None</td></tr><tr><td><b>242a</b></td><td>-5.87</td><td>-5.13</td><td>-2.42</td><td>-2.42</td><td>2.71/3.45</td><td>393(3.16)</td><td>C<sub>2v</sub></td></tr><tr><td><b>242b</b></td><td>-5.66</td><td>-5.10</td><td>-2.46</td><td>-2.46</td><td>2.64/3.20</td><td>433(2.86)</td><td>C<sub>2v</sub></td></tr><tr><td><b>242c</b></td><td>-5.31</td><td>-5.16</td><td>-2.36</td><td>-2.36</td><td>2.80/2.95</td><td>474(2.62)</td><td>None</td></tr></tbody></table>

<sup>a</sup>HOMO–LUMO/HOMO–1–LUMO. <sup>b</sup>Group of symmetry.

The calculated optimized structures were in accordance with results drawn from X-ray analysis and side to side comparison of X-ray and DFT structures of **241a** and **242a** is displayed in *Figure 78*. Torsion angle between acridan moiety and rest of the molecule was found to be 86 and 90° for **241a** and **242a**, respectively. An inspection of the calculated molecular geometries also revealed that diphenylamino-substituted derivatives **c** possessed no symmetry, which is in contrast to methoxy derivatives **a** and **b**. No significant fluctuations in HOMO and LUMO levels, and therefore steady HOMO-LUMO gap, were observed when going from weaker donors **a,b** to the stronger diphenylamino **c**, indicating that these frontier molecular orbitals did not contributed to the ICT.
<figure><img src="image_123.png" /><figcaption>**Figure 78.** (A) X-Ray and (B) DFT-optimized geometries of final derivatives 241a and 242a.</figcaption></figure>

Localization of molecular orbital is displayed in Figure 79. Similarly to tris(arylvinyl)pyrimidines, the LUMO was spread over the central pyrimidine ring and attached vinylene linkers. The HOMO was localized on nitrogen atom of acridan units for all final chromophores **241** and **242**. On the other hand, the HOMO-1 occupied peripheral methoxy or diphenylamino electron-donating groups. Position of the HOMO-2 varied depending on the number of C4/C6 branches. For derivatives **241** with one branch, the HOMO-2 was localized again on phenylacridan moiety, whereas for compounds **242** it remained localized like the HOMO-1. The LUMO+1 and LUMO+2 were found localized over the pyrimidine ring or the acridan unit.
<figure><img src="image_124.png" /><figcaption>**Figure 79.** Localization of HOMO-1 (red) and LUMO (blue) in compounds 241 and 242.</figcaption></figure>

Calculated absorption spectra are provided in Annex 2 and the longest-wavelength absorption maxima are summarized in Table 10. A small red-shift was found as compared to corresponding experimental data. However, trends and features of the spectra correspond to the experimental ones recorded in CH<sub>2</sub>Cl<sub>2</sub>. Contributions of different transitions to each band and their oscillator strength are summarized in Annex 3. In the case of compounds 241 and 242, the HOMO → LUMO transition possessed zero oscillator strength and the longest wavelength band were dominated by the HOMO-1 → LUMO transitions. Considering the HOMO-1 localization over the C4/C6 peripheral donors, their donor-acceptor interaction with the central pyrimidine acceptor (LUMO) accounted for the ICT and explained the observed bathochromic shift of the longest-wavelength maxima when going from methoxy to diphenylamino derivatives (a → c). Besides the HOMO-1 → LUMO transition, transitions with significantly lower oscillator strengths were also detected by the DFT calculations, these include the HOMO-1 → LUMO+1 for 241 and the HOMO-2 → LUMO for compounds 242.
## 4.7 Conclusions

A series of six new chromophores with pyrimidine heterocycle as central electron-withdrawing unit was prepared. Acridan moiety was connected to the C2 pyrimidine position via 1,4-phenylene linker and C4(C6) positions were extended by arylvinyl $π$-conjugated system with peripheral methoxy or diphenylamino donors. The first synthetic step, an interconnection of the acridine and phenylene unit, revealed to be challenging, however appropriate reaction conditions were found. The remaining synthesis was straightforward. Final derivatives were obtained by Suzuki-Miyaura C-C reaction of 2-chloro-4-methyl or 2-chloro-4,6-dimethylpyrimidine and ester of 4-acridanphenyl boronic acid followed by Knoevenagel reaction between pyrimidine methyl group(s) and corresponding aromatic aldehyde, with satisfying yields.

DSC analysis showed that peripheral C4/C6 electron-donating units affected the thermal properties only slightly, while the presence of acridan unit caused high thermal stability with temperatures of decomposition reaching almost 400 °C. The X-ray analysis revealed twisted acridan structure with torsion angles around 85° and also confirmed the *E* configuration of C4(C6) double bonds.

Results of photophysical measurements showed significant differences in photophysical behaviour of methoxy (**a** and **b**) and diphenylamino compounds (**c**). Single-band emission, both in solution and solid-state, high fluorescence quantum yield in $CH_2Cl_2$ and strong positive emission solvatochromism were observed for diphenylamino derivates. Meanwhile, methoxy derivatives exhibited very poor fluorescence in $CH_2Cl_2$ solution, which enhanced in nonpolar *n*-heptane and further slightly increased after deoxygenation. Methoxy-substituted compounds also exhibited intense AIE and dual emission in THF solution and solid state. The shorter-wavelength band was attributed to emission from the LE state and the longer-wavelength band was assigned to emission from the ICT/TICT excited state with long lifetime. The colour of the dual emission in thin films was close to white, which makes these compounds potential material for development of single emitter WOLEDs. The anticipated TADF behaviour was not observed, probably due to none oscillator strength of the HOMO → LUMO transition did not possess any oscillator strength, nevertheless unexpected photophysical properties were obtained for methoxy derivatives (**a** and **b**).

DFT calculation showed that, despite the HOMO is being localized on the acridan unit, it was completely isolated and did not affect the fundamental absorption properties. These are fully controlled by the peripheral methoxy or diphenylamino electron-donating groups bearing HOMO-1.
Results discussed in this chapter were published in one article:

[4] M. Fecková, I. K. Kalis, T. Roisnel, P. le Poul, O. Pytela, M. Klikar, F. Robin-le Guen, F. Bureš M. Fakis and S. Achelle: Photophysics of 9,9-dimethylacridan-substituted phenylstyrylpyrimidines exhibiting long-lived intramolecular charge-transfer fluorescence and aggregation induced emission characteristics, Chemistry- A European Journal, **2021**, *27*, 1145–1159. 10.1002/chem.202004328
# CHAPTER V. Solid state emitting phenylpyrimidine platinum complexes

## 5.1 Introduction

As it was discussed in Chapter 2, platinum(II) complexes with pyrimidine-based ligands attracted researchers' interest in past few years for their potential application in PhOLEDs.[178-181] In this type of OLEDs, also known as 2nd generation OLEDs, phosphorescent emitters are used due to their ability to harvest both singlet and triplet excitons for light production.

Inspiration for design of new platinum complexes was drawn from work of Zhao and co-workers.[258] They recently published a study of complex 243 (Figure 80) with strong emission in solid-state and promising electroluminescent properties. It has also been demonstrated that electron-donating groups in para position of phenylpyridine ligand relative to central metal atom enhances the emission properties.[259] With this in mind, five platinum(II) complexes with phenylpyrimidine as cyclometalated ligand, pyridine and Cl⁻ as monodentate ancillary ligands were designed, see Figure 80. Structure of phenylpyrimidine was decorated with electron-donating and electron-withdrawing substituents in conjugated and non-conjugated positions (relative to Pt) to establish structure-photophysical properties relationships.

<figure><img src="image_125.png" /><figcaption>**Figure 80.** Structures of compound 243 and designed Pt complexes.</figcaption></figure>

## 5.2 Synthesis

Ligands **244** for Pt(II) complexes were prepared by Suzuki-Miyaura C-C reaction between 2-chloropyrimidine and corresponding phenylboronic acid (Scheme 6).[128,129] All ligands were obtained in moderate to good yields. Subsequently, ligands underwent a complexation with $K_2PtCl_4$ in a mixture of ethoxyethanol (EGEE) and water (3/1, v/v) under nitrogen atmosphere. After 18 hours, the reaction mixture was cooled to room temperature and water was added until a precipitate was formed, which was collected and dried under vacuum. Without any further purification, µ-chloro bridged intermediate (the precipitate) was dissolved in $CHCl_3$ and underwent so-called “bridge splitting” reaction in the presence of pyridine.[258,260,261] Final Pt-complexes **245** were prepared in satisfying yields.
<figure><img src="image_126.png" /><figcaption>**Scheme 6.** Synthesis of ligands **244** and Pt(II) complexes **245**. Substituents position for **245** are given with regards to platinum atom.</figcaption></figure>

All ligands **244** and final complexes **245** were characterized by ¹H/¹³C NMR spectroscopy and HR-MALDI mass spectrometry.

## 5.3 X-ray analysis

An appropriate crystal of **245a** suitable for X-ray analysis was obtained by slow evaporation of its ethyl acetate/*n*-hexane solution. ORTEP diagram of this yellow prism with orthorhombic symmetry and *Pbca* space group is presented in *Figure 81*. X-ray analysis was performed by Dr. Thierry Roisnel, Université de Rennes 1 (France).

<figure><img src="image_127.png" /><figcaption>**Figure 81.** (A) ORTEP diagram of complex **245a** with thermal ellipsoid at 50% probability. (B) Pt-π interaction in the crystal structure of **245a**.</figcaption></figure>

Square-planar geometry was observed with *trans* N,N *trans* C,Cl organisations of chelating positions. Values of bond lengths between central Pt atom and surrounding ligands were close to similar *trans* N,N *trans* C,Cl Pt complexes found in literature.[258,260,262] The square-planar geometry is slightly distorted with smaller angles between C11-Pt1-N22 (87.13(16)°) and C11-Pt1-N1 (87.48(9)°). Torsion angle of 67.66° was observed between the plane of pyridine ring and square-plane of the remaining molecule, indicating a possible rotation along the Pt-N atom of pyridine axis, which could be responsible for low luminescence in solution at room
temperature by reducing decay from T₁ or ISC, and high luminescence in solid-state, in which this rotational movements is limited.[258] Concerning the supramolecular arrangement in the solid state, possible interaction between molecules in inverted positions was found with the lowest distance between Pt and pyrimidine ligand of 3.49 Å, see *Figure 81B*. Similar value was already reported for electroluminescent Pt complexes that proved to form a stacked dimers by the Pt-π interaction.[263]

## 5.4 Photophysical properties

### Absorption and emission in CH₂Cl₂

Photophysical behaviour of final derivatives **245** was measured in CH₂Cl₂ solutions with analyte concentration *c* = (0.9 – 1.02) × 10⁻⁵ M. Results are summarized in *Table 11*. Deoxygenated solutions were prepared by bubbling with N₂.

<table><caption>**Table 11.** Absorption and emission data of **229** complexes in CH₂Cl₂ and solid state (powdered).</caption><thead><tr><th rowspan="2">Compd</th><th colspan="5">CH₂Cl₂<sup>a</sup></th><th colspan="2">solid state</th></tr><tr><th>λ<sub>max</sub>(abs) (ε)<br/>[nm]<br/>([mM<sup>-1</sup>·cm<sup>-1</sup>])</th><th>λ<sub>max</sub>(em)<br/>[nm]</th><th>τ<br/>[μs]</th><th>Φ<sub>PL</sub><sup>b</sup></th><th>Stokes<br/>shift<br/>[cm<sup>-1</sup>]</th><th>λ<sub>max</sub>, nm</th><th>τ<br/>[μs]</th></tr></thead><tbody><tr><td>245a</td><td>249 (38.8), 286<br/>(13.9)sh, 338<br/>(6.1), 386 (2.0)</td><td>—</td><td>—</td><td>—</td><td>—</td><td>517, 535,<br/>549</td><td>0.51,<br/>2.72</td></tr><tr><td>245b</td><td>256 (43.4), 270<br/>(36.2), 335<br/>(4.5), 382 (2.1)</td><td>—</td><td>—</td><td>—</td><td>—</td><td>478, 505,<br/>549,<br/>590sh</td><td>0.30,<br/>2.58</td></tr><tr><td>245c</td><td>251 (44.4), 283<br/>(14.7)sh, 346<br/>(5.5), 414 (2.6)</td><td>570</td><td>12.9</td><td>0.40</td><td>6610</td><td>591,<br/>630sh</td><td>0.47,<br/>2.05</td></tr><tr><td>245d</td><td>285 (27.0), 292<br/>(35.2), 438<br/>(2.3)</td><td>628</td><td>8.86</td><td>0.05</td><td>6907</td><td>629</td><td>0.40,<br/>2.13</td></tr><tr><td>245e</td><td>264 (24.1), 314<br/>(14.2), 384<br/>(1.8)</td><td>—</td><td>—</td><td>—</td><td>—</td><td>515, 539,<br/>556</td><td>0.34,<br/>1.32</td></tr></tbody></table>

Absorption spectra (*Figure 82A*) contained various bands with the most intense appearing around 250–300 nm attributed to the intramolecular π-π* transition. Position of these bands for complexes **245a–c** lay within the range of a few nm, whereas slight red-shift was found

<footnote><sup>a</sup> All spectra were recorded at room temperature at *c* = (0.9 – 1.02) × 10⁻⁵ M with deoxygenated solutions prepared by bubbling N₂ through the solutions. <sup>b</sup> Photoluminescence quantum yield (±10%) determined relative to 9,10-bisphenylethynylanthracene in cyclohexane (Φ<sub>PL</sub> = 1.00).[257]</footnote>
for compound **245e** (over 10 nm relative to its analogue **245c** with methoxy group outside the conjugated position towards pyrimidine acceptor) and more significant (>30 nm) for compound **245d** with larger π-system.

<figure><img src="image_128.png" /><figcaption>**Figure 82.** (A) Experimental absorption spectra of complexes **245** measured in CH<sub>2</sub>Cl<sub>2</sub> and (B) experimental emission spectra of complexes **245c,d** in CH<sub>2</sub>Cl<sub>2</sub>.</figcaption></figure>

No emission was observed for complexes in their oxygenated solutions. However, deoxygenation of solutions resulted in appearance of emission for derivatives **245c** and **245d** with donating group in *para* position towards central Pt atom (*Figure 82B*). Photoluminescence quantum yields were established as 0.40 and 0.05 for **245c** and **245d**, respectively, with long excited state lifetimes around 10 µs, typical for phosphorescence. This relatively low or none emission of other complexes could be ascribed to possible pyridine ring rotation, which allows non-radiative decay.[258]

*Solid-state emission*

Nevertheless, in the solid state (powder) all complexes exhibited bright emission with a structured spectrum. As mentioned in previous paragraphs, the appearance of emission in the solid-state is caused by restriction of pyridine ring rotation.[258] Concerning the colour of emitted light, complexes **245a** and **245e** without substitution in *para* position (against Pt) produced green light with the most blue-shifted emission bands (see *Figure 83*). Appending cyano group into the *para* position (**245b**) resulted in red-shift of spectra with yellow light emission. Further red-shift was observed for derivatives **245c** and **245d**, which emitted orange and red light, respectively.
<figure><img src="image_129.png" /><figcaption>**Figure 83.** (A) Solid state normalized emission spectra of powdered 245. Pictures of (B) powdered and (C) oxygenated and deoxygenated CH₂Cl₂ solutions of 245 taken under UV-lamp (λ<sub>em</sub> = 254 nm).</figcaption></figure>

**5.5 DFT calculation**

*Figure 84* presents optimized structures of complexes **229**. (TD)-DFT calculations at the PBE0/LANL2DZ level of theory were performed by Prof. Jean-Yves Saillard and Dr. Samia Kahlal, Université de Rennes 1 (France). Relevant data are provided in *Annex 5* and for computational details see *Chapter 6*. The calculated structures are in agreement to X-ray structure of **245a**, with slightly longer metal-ligands bonds, which are usually found for DFT-optimized structures. Torsion angles between pyridine and plane of the molecule were determined in the range of 65–67°, which were comparable to the experimental angle found in crystal structure of **245a** (67.7°). The shortest calculated intermolecular H…H distance was found within the range of 2.7–2.8 Å. This value implied that pyridine rotated between planar structure with effective conjugation and twisted structure with reduced H…H steric repulsion. The energy difference between these two structures is only 0.01 eV indicating that, in solution, pyridine could rotate along the N-Pt axis a several tenths of degrees.
<figure><img src="image_130.png" /><figcaption>**Figure 84.** DFT-optimized geometries of complexes 245.</figcaption></figure>

The Natural Atomic Orbital (NAO) charges and the metal-ligand Wiberg bond indices of the five complexes were very close. The largest difference in atomic charge variation was observed for carbon atom attached to Pt, influenced by electronic effect of substituent in para position. The largest number was found for complexes **245c** and **245d** with electron-donating groups, which favored a more negative polarization of the C-atom. In the case of derivative **245b** with cyano group in alternating position, slightly stronger Pt-Cl bond was observed relative to the remaining complexes. It should be noticed that changes in these values are rather small. However, more substantial differences could be seen in HOMO-LUMO gaps that are in agreement with the experimental spectroscopic data. The smallest gaps were observed for derivatives **245c** and **d** with donating groups in conjugation with central metal. A further insight into the electronic structures was drawn from Kohn-Sham diagrams (Figure 85A) and localization of frontier orbitals (Figure 85B) of final complexes **245**. The results imply that studied complexes behave in three different ways based on the substituent in para position. Firstly, for complexes **245c** and **245d** substituted with electron-donating groups, destabilized HOMO by donors' electron lone pair with significant phenylpyrimidine character was found. Secondly, derivatives **245a** and **245d** without substitution in para position, and therefore without mesomeric effect, exhibited the HOMO with lower, but still substantial, phenylpyrimidine character. And last, complex **245b** with cyano group possessed the HOMO
with stabilization by electron-withdrawing nature of cyano group. The HOMO-LUMO gap of this derivative was not the lowest within the series since the LUMO level was also slightly stabilized.

<figure><img src="image_131.png" /><figcaption>**Figure 85.** (A) Kohn-Sham orbital diagrams of compounds **245** The MO localizations (in %) are given in the following order: Pt/Cl/phenylpyrimidine/pyridine. (B) Frontier orbitals of complexes **245**.</figcaption></figure>

Good agreement was found between the experimental and the TD-DFT calculated absorption spectra of **245**, see *Figure 86A* and *Table 12*. Nature of transition of each absorption bands are also provided in the same table. The longest-wavelength bands corresponded to the HOMO → LUMO transition. *Figure 85* revealed a mixed electron-transfer character, with a dominant intra phenylpyrimidine character. The other bands did not exhibit important
long-range transfers neither significant metal participation. Emission spectra in the solution were also calculated by using the Adiabatic Hessian (AH) method developed by Barone et al., which was recently proven to be efficient for platinum complexes.[264–266] The calculated emission spectra are presented in Figure 86B and the corresponding emission maxima are provided in Table 12. A good agreement was found between the experimental and the calculated data and the transition was found to originate from the excited (HOMO)¹(LUMO)¹ triplet state.

<figure><img src="image_132.png" /><figcaption>**Figure 86.** Calculated (A) absorption spectra of complexes 245 and (B) calculated emission spectra of complexes 245c,d.

**Table 12.** Experimental and calculated photophysical data of complexes 245.</figcaption></figure>

<table><thead><tr><th rowspan="2">Compd.</th><th colspan="3">Absorption</th><th colspan="2">Emission</th></tr><tr><th>λ<sub>max</sub> (ε) exp<br/>[nm]<br/>([mM<sup>-1</sup>·cm<sup>-1</sup>])</th><th>λ<sub>max</sub> (ε) calc<br/>[nm]<br/>([mM<sup>-1</sup>·cm<sup>-1</sup>])</th><th>Nature of the transition</th><th>Exp.<br/>λ<sub>max</sub> [nm]</th><th>Comp. λ<sub>max</sub><br/>[nm]</th></tr></thead><tbody><tr><td rowspan="4">245a</td><td>386 (2.0)</td><td>392 (0.03)</td><td>ILCT<sup>a</sup> + MLCT<sup>b</sup> +LLCT<sup>c</sup></td><td>—</td><td>—</td></tr><tr><td>338 (6.1)</td><td>303 (0.11)</td><td>ILCT<sup>a</sup> + MLCT<sup>b</sup></td><td>—</td><td>—</td></tr><tr><td>286 (13.9)sh</td><td>—</td><td>—</td><td>—</td><td>—</td></tr><tr><td>249 (38.8)</td><td>277 (0.10)</td><td>ILCT<sup>a</sup> + LLCT<sup>d</sup></td><td>—</td><td>—</td></tr><tr><td rowspan="4">245b</td><td>382 (2.1)</td><td>385 (0.04)</td><td>ILCT<sup>a</sup> + MLCT<sup>b</sup> +LLCT<sup>c</sup></td><td>—</td><td>—</td></tr><tr><td>335 (4.5)</td><td>304 (0.11)</td><td>ILCT<sup>a</sup> + MLCT<sup>b</sup></td><td>—</td><td>—</td></tr><tr><td>270 (36.2)</td><td>—</td><td>—</td><td>—</td><td>—</td></tr><tr><td>256 (43.4)</td><td>282 (0.17)</td><td>ILCT<sup>a</sup> + LLCT<sup>d</sup></td><td>—</td><td>—</td></tr><tr><td rowspan="4">245c</td><td>414 (2.6)</td><td>428 (0.04)</td><td>ILCT<sup>a</sup> + MLCT<sup>b</sup> +LLCT<sup>c</sup></td><td>570</td><td>578</td></tr><tr><td>346 (5.5)</td><td>304 (0.12)</td><td>ILCT<sup>a</sup> + MLCT<sup>b</sup></td><td>—</td><td><strong>532</strong></td></tr><tr><td>283 (14.7)sh</td><td>—</td><td>—</td><td>—</td><td>—</td></tr><tr><td>251 (44.4)</td><td>277 (0.13)</td><td>ILCT<sup>a</sup> + LLCT<sup>d</sup></td><td>—</td><td>—</td></tr><tr><td rowspan="4">245d</td><td>438 (2.3)</td><td>485 (0.04)</td><td>ILCT<sup>a</sup> + LLCT<sup>c</sup></td><td>628</td><td><strong>662</strong></td></tr><tr><td>292 (35.2)</td><td>316 (0.19)</td><td>LLCT<sup>d</sup> + MLCT<sup>b</sup></td><td>—</td><td>614</td></tr><tr><td>285 (27.0)</td><td>275 (0.26)</td><td>ILCT<sup>a</sup> + LLCT<sup>d</sup></td><td>—</td><td>—</td></tr><tr><td>384 (1.8)</td><td>380 (0.03)</td><td>ILCT<sup>a</sup> + MLCT<sup>b</sup> +LLCT<sup>c</sup></td><td>—</td><td>—</td></tr><tr><td rowspan="3">245e</td><td>314 (14.2)</td><td>299 (0.12)</td><td>LLCT<sup>d</sup> + MLCT<sup>b</sup></td><td>—</td><td>—</td></tr><tr><td>264 (24.1)</td><td>280 (0.40)</td><td>ILCT<sup>a</sup> + LLCT<sup>d</sup></td><td>—</td><td>—</td></tr></tbody></table>
**5.6 Conclusions**

Five new platinum(II) complexes bearing phenylpyrimidine cyclometalated ligands with various substituents as well as pyridine and chlorine monodentate ligands were prepared. All complexes were obtained in moderate to good yields. X-ray analysis and DFT calculations revealed square-planar structure of the central platinum atom and possible rotation of pyridine along Pt-N axis. This rotation caused low or non-existing emission in the solution with a dramatic enhancement in the solid-state, in which the rotation was restricted. As far as the influence of substitution is concerned, presence of electron-donating group in alternating position towards Pt atom resulted in significant increase in the emission quantum yields. The yield in the solution was found up to 0.4 for complex **245c** and excited state lifetimes around 10 µs and red-shift of the emission spectra was recorded in the solid-state. Strong emission of these complexes in the solid-state makes them promising candidates for their incorporation in OLED devices.

Results discussed in this chapter were published in one article:

[5] M. Fecková, S. Kahlal, T. Roisnel, J.-Y. Saillard, J. Boixel, M. Hruzd, P. Le Poul, S. Gauthier, F. Robin-le Guen, F. Bureš and S. Achelle: Cyclometallated 2-phenylpyrimidine derived platinum complexes: synthesis and photophysical properties, European Journal of Inorganic Chemistry, **2021**, in press. 10.1002/ejic.202100155
GENERAL CONCLUSIONS AND PERSPECTIVES

This dissertation describes results of work concerning pyrimidine-based organic and organometallic luminescent materials suitable for application in OLED technology. The first chapter was dedicated to definition of general concepts and terms, physical quantities and phenomena used for description of luminescence. Basic relationships between structure and luminescence of organic compounds as well as an effect of environment on luminescence were also discussed. Second half of the first chapter contains description of organic semiconductors in the context of OLED technology. The general structure of OLED devices, working principle and ways of OLED's characterisation are also included. In the end, three types of OLED were distinguished based on mechanism how emitters harvest light.

Second chapter began with description of pyrimidine heterocycle and its role in organic materials. Subsequently, fluorescent push-pull chromophores were introduced in context of influence of structural changes on photophysical properties. Short overview of basic synthetic approaches towards building pyrimidine-based chromophores concluded the first part of the second chapter. The main purpose of the second part was to present wide use of pyrimidine containing luminescent materials. Fluorescent probes for detection of solvent polarity, cations, nitrogen explosive and bioimaging were presented. A few examples to achieve white light emission by partial protonation of pyrimidine chromophore were also included. Finally, the end of the second chapter was dedicated to highlight use of pyrimidine organic and organometallic luminophores in OLED devices.

Results of this doctoral work were summarized in three chapters, which were sorted based on the main structural motive, and consequently different photophysical features, of each series. The unified organisation of each chapter starts with the synthesis of target molecules following by results of DSC and X-ray measurements. Subsequent focus was put on photophysical properties of final derivatives and each chapter ended with results of theoretical calculations.

The first series of final derivatives included 2,4-di(arylvinyl)- and 2,4,6-tri(arylvinyl)pyrimidines, from which 23 derivatives were novel structures. Pyrimidine ring was used as a central electron-withdrawing group connected through arylvinylene bridges with mostly electron-donating groups at periphery. Synthesis of these molecules involved Suzuki-Miyaura C-C reaction and Knoevenagel condensation, which allowed preparing derivatives with identical or different substitution on each branch. Vast majority of final molecules exhibited measurable emission and their photophysical properties were mostly affected by electronic nature of C4 and C6 substituents. However, when comparing stronger electron-donor
appended in C2 or C4 and C6, both position and intensity of emission spectra were dictated by the C2 substitution. For all emissive derivative, significant positive emission solvatochromism was observed. Modulation of emission colour between dark blue and yellowish green of one final chromophore was achieved by gradual protonation of its solutions. In collaboration with research group of Prof. Mihalis Fakis, University of Patras (Greece), influence of type of acid on absorption, emission and excited state dynamics were studied for diphenylamino-substituted 4,6-distyryl and 2,4,6-tristyrylpyrimidines. In collaboration with Dr. Claudine Katan and Dr. Arnaud Fihey, Université de Rennes 1 as well as Dr. Jean-Pierre Malval and Dr. Arnaud Spangenberg, Université de Haute Alsace (France), influence of branching number of styrylpyrimidines on their photophysical properties was studied. It should be highlighted that the low symmetry given by the pyrimidine ring resulted in increase of 2PA cross-section up to 500 GM within the same spectral region with each additional branch. Concerning the perspectives of multibranched arylvinylpyrimidines, two series of novel derivatives are proposed, see Figure 87. Based on the fact, that derivatives with the electron-withdrawing CF₃ group in C2 position exhibited the most intense emission and also dual emission during protonation, studying the effect of different electron-withdrawing group in C2 position could potentially lead to interesting results. As a second series styrylpyrimidine-based dendrimers are proposed. The higher number of branches could potentially further increase the 2PA response.

<figure><img src="image_133.png" /><figcaption>**Figure 87.** Proposed structures of novel styrylpyrimidines.</figcaption></figure>

Second project concerned 4-arylvinyl- and 4,6-di(arylvinyl)pyrimidines with phenylacridan structure in C2 position of pyrimidine as potential TADF emitters. Six novel chromophores were prepared and fully characterized. The presence of phenylacridan moiety brought a high thermal robustness into these structures. Final derivatives can be divided into
two groups with different photophysical properties. Firstly, derivatives with diphenylamino
electron-donors in C4/C6 positions exhibited similar properties to those of previously discussed
styrylpyrimidines such as high fluorescence quantum yield in moderately polar solvent
(CH₂Cl₂), strong positive emission solvatochromism, lower fluorescence quantum yield in low
polar solvent (n-heptane) and no change in emission intensity after deoxygenation of their
solution. On the other hand, derivatives with methoxy group showed significant emission in
n-heptane solution with increase upon deoxygenation, aggregation-induced emission and dual
emission of white light in both thin films and solution (THF or acetone). Although, their
anticipated TADF behaviour was not observed, above mention emission phenomena makes
them a very promising materials for fabrication of WOLED device based on single emitter.

Last project included synthesis and study of photophysical properties of platinum complexes with ancillary Cl⁻ and pyridine ligand and cyclometaled 2-phenylpyrimidine ligands with substituents both in alternating and non-alternating position towards platinum atom. All complexes showed luminescence in solid-state, however, derivatives with electron-donating groups in alternating position exhibited the most interesting photophysical properties, which makes them promising candidates for utilization as phosphorescent emitters in OLED. Replacement of chlorine atom by different ligands, substitution of the pyrimidine ring and study of their influence on luminescent properties is currently under investigation by Mariia Hruzd, Université de Rennes 1 (France).

Results discussed in this dissertation work were reported in five articles:

[1] M. Fecková, P. le Poul, F. Robin-le Guen, T. Roisnel, O. Pytela, M. Klikar, F. Bureš and S. Achelle: 2,4-Distyryl- and 2,4,6-tristyrylpyrimidines: Synthesis and Photophysical Properties, Journal of Organic Chemistry, **2018**, *83*, 11712–11726. 10.1021/acs.joc.8b01653

[2] F. Kournoutas, I. K. Kalis, M. Fecková, S. Achelle, M. Fakis: The effect of protonation on the excited state dynamics of pyrimidine chromophores, Journal of Photochemistry & Photobiology A: Chemistry, **2020**, *391*, 112398. 10.1016/j.jphotochem.2020.112398

[3] F. Kournoutas, A. Fihey, J.-P. Malval, A. Spangenberg, M. Fecková, P. le Poul, C. Katan, F. Robin-le Guen, F. Bureš, S. Achelle, M. Fakis: Branching effect on the linear and nonlinear optical properties of styrylpyrimidines, Physical Chemistry Chemical Physics, **2020**, *22*, 4165–4176. 10.1039/c9cp06476a
[4] M. Fecková, I. K. Kalis, T. Roisnel, P. le Poul, O. Pytela, M. Klikar, F. Robin-le Guen, F. Bureš, M. Fakis, S. Achelle: Photophysics of 9,9-Dimethylacridan-Substituted Phenylstyrylpyrimidines Exhibiting Long-Lived Intramolecular Charge-Transfer Fluorescence and Aggregation-Induced Emission Characteristics, Chemistry – A European Journal, **2021**, *27*, 1145–1159. 10.1002/chem.202004328

[5] M. Fecková, S. Kahlal, T. Roisnel, J.-Y. Saillard, J. Boixel, M. Hruzd, P. le Poul, S. Gauthier, F. Robin-le Guen, F. Bureš, S. Achelle: Cyclometallated 2-phenylpyrimidine derived platinum complexes: Synthesis and photophysical properties, European Journal of Inorganic Chemistry, 10.1002/ejic.202100155 Accepted Article

During my doctoral study I also participated on publication of the following articles and review:

[6] J. Tydlitát, M. Fecková, P. le Poul, O Pytela, M. Klikar, J. Rodriguez-Lopez, F. Robin-le Guen, S. Achelle: Influence of Donor-Substituents on Triphenylamine Chromophores Bearing Pyridine Fragments, European Journal of Organic Chemistry, **2019**, *9*, 1921–1930. 10.1002/ejoc.201900026.

[7] M. Fecková, P. le Poul, F. Bureš, F. Robin-le Guen, S. Achelle: Nonlinear optical properties of pyrimidine chromophores, Dyes and Pigments, *182*, 108659. 10.1016/j.dyepig.2020.108659

[8] S. Achelle, E. V. Verbitskiy, M. Fecková, F. Bureš, A. Barsella, F. Robin-le Guen: V-shaped methylpyrimidinium chromophores for nonlinear optics, Submitted to ChemPlusChem
# CHAPTER VI. Experimental section

## General methods

Starting materials for reactions were purchased from Acros, Alfa-Aesar, Fluka, Penta, Sigma-Aldrich and TCI companies and were used without any further purification. Dry THF was distilled over Na or Na/K alloy and benzophenone under inert atmosphere of nitrogen or argon. Solvents were evaporated on rotary evaporator Heidolph Laboratora 4000 or Büchi R-200 Rotavapor. Cross-coupling reactions and complexations were carried out in vacuum-dried Schlenk flask under nitrogen or argon atmosphere. The remaining reactions and following workups were performed on air. Column chromatography was carried out on silica gel 60; particle size 0.20–0.50 mm, 60–200 mesh ASTM (Acros) or particle size 0.040–0.063 mm, 230–400 mesh ASTM (Merk). Thin-layer chromatography was performed on EMD Silica Gel 60 F254 (Merck) aluminium plates with visualization by UV lamp (254 or 365 nm). ¹H and ¹³C NMR spectra were recorded in CDCl₃ at 20 °C on a Bruker AC-300 (frequencies 300/75 MHz), a Bruker AVANCE III (frequencies 400/100 MHz) and a Bruker Ascend™ (frequencies 500/125 MHz) spectrometers. Chemical shifts (δ) are provided in parts per million compare to signal of (CH₃)₄Si. Signals of (residual) solvents were used as internal standards [CHCl₃ in CDCl₃ 7.25 ppm (¹H) and CDCl₃ 77.16 ppm (¹³C)]. Interaction constants (J) are given in Hz. Observed signals are described with the following abbreviations: s (singlet), d (doublet) and m (multiplet). Acidic impurities in CDCl₃ were removed by its treatment with anhydrous K₂CO₃. IR spectra were recorded on a Perkin-Elmer spectrum 100 spectrometer with an ATR sampling accessory. Mass spectra were measured on a GC/EI-mass spectrometer, which consists of a gas chromatograph Agilent Technologies 6890N (HP-5MS, column length 30 m, I.D. 0.25 mm, film 0.25 µm) and a Network MS detector 5973 (EI 70 eV, range 33–550 Da). High resolution MALDI mass spectra were measured by “dried droplet” method on a LTQ Orbitrap XL MALDI mass spectrometer (Thermo Fisher Scientific, Bremen, Germany) equipped with a nitrogen UV laser (337 nm, 60 Hz) and quadrupole analyser; positive-ion mode over a normal mass range (m/z 50–2000) with a resolution of 100 000 at m/z = 400. trans-2-[3-(4-tert-Butylphenyl)-2-methyl-2-propenylidene]malononitrile (DCTB) was used as a matrix.

## DSC

The thermal properties of final derivatives were studied through DSC measurements with a Mettler-Toledo STARe system DSC 2/700 equipped with a FRS 6 ceramic sensor and HUBER TC100-MT RC 23 cooling system. The thermal behaviour of target compounds
was measured in open aluminous crucible under an inert atmosphere of nitrogen. DSC curve
were determined at a scanning rate of 3 °C×min⁻¹ within the range 25–500 °C.

X-Ray structural analysis

Single-crystal X-ray-diffraction data were obtained from a D8 VENTURE Bruker AXS diffractometer equipped with a (CMOS) PHOTON 100 detector, using Mo-Kα radiation (λ = 0.71073 Å, multilayer monochromator) at T = 150 K. Crystal structure was solved by dual-space algorithm using the SHELXT program,[267] and then refined with full-matrix least-squares methods based on *F*² (SHELXL program).[268] All non-hydrogen atoms were refined with anisotropic atomic displacement parameters. H atoms were finally included in their calculated positions and treated as riding on their parent atom with constrained thermal parameters. Drawing was produced using ORTEP-3. Deposition Numbers 1852296 (232h), 2004147 (242a), 2004148 (241a), 2004149 (242a) and 2039829 (245a). These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via [www.ccdc.cam.ac.uk/data_request/cif](http://www.ccdc.cam.ac.uk/data_request/cif).

Steady state spectroscopy

UV-visible spectra were recorded on a Perkin-Elmer Lambda 25 spectrometer, a Spex Fluoromax-3 Jobin-Yvon Horiba spectrophotometer or a Jasco V-650 UV-Vis. Photoluminescence spectra were obtained using a Horiba Fluoromax spectrophotometer. Both UV-Vis and PL measurements in solution were carried out using standard 10 mm quartz cells. Compound were excited at their longest-wavelength absorption maxima. The Φ<sub>PL</sub> values were calculated using a well-known procedure with 9,10-bis(phenylethynyl)anthracene (Φ<sub>F</sub> = 1.00).[257] Stokes shifts were calculated by considering the longest-wavelength absorption band.

Time resolved spectroscopy

For time resolved fluorescence measurements in the ps-ns timescale, the Time Correlated Single Photon Counting (TCSPC) technique has been used based on a Fluotime 200 spectrometer (Picoquant).[269] The excitation source was a ps diode laser emitting 60 ps pulses at 400 nm and the IRF was ~80 ps. The samples for fluorescence dynamics measurements were dilute solutions with optical density (O.D.) at the excitation wavelength of ~0.1.
## Two-photon absorption

The 2PA measurements were performed with femtosecond mode-locked laser pulses using a Ti: Sapphire laser (Coherent, Chameleon Ultra II: pulse duration: ~140 fs; repetition rate: 80 MHz; wavelength range: 680–1040 nm). A two-photon excited fluorescence method was employed to measure the 2PA cross-sections, δ.[227] The measurements of 2PA cross-sections were performed relative to reference molecules (r) such as fluorescein in water at pH = 11.[227,270] The samples used for the 2PA characterization were 10⁻⁵–10⁻⁴M solutions in CH₂Cl₂. The values of δ for a sample (s) is given by:

$$ \delta_s = \frac{S_s \Phi_r \eta_r c_r}{S_r \Phi_s \eta_s c_s} \delta_r $$

Where S is the detected two-photon excited fluorescence integral area, c is the concentration of the chromophores, Φ is the fluorescence quantum yield of the chromophores and η is the collection efficiency of the experimental set-up which accounts for the wavelength dependence of the detectors and optics as well as the difference in refractive indices between the solvents in which the reference and sample compounds are dissolved. The measurements were conducted in a regime where the fluorescence signal showed a quadratic dependence on the intensity of the excitation beam, as expected for two-photon induced emission. For the calibration of the 2PA spectra, the two-photon excited fluorescence signal of each compound was recorded at the same excitation wavelength as that used for standards (i.e. λ(exc) = 782 nm for fluorescein). The laser intensity was in the range of 0.2–2 x 10⁹ W/cm². The experimental error on the reported cross section is 15 %.

## Calculations

**Compounds 62, 232g,j,k,m:** All calculations were carried out in Gaussian16,[222] at the DFT level of theory. The initial geometry optimizations were carried out by the PM3 method implemented in program ArgusLab[271] and subsequently by the DFT B3LYP method using the 6-311G++(2d,f,p) basic set. The energies of the HOMO and LUMO, their differences and ground-state dipole moments were calculated by the same method.

**Compound 48, 49, 61, 62 and 232i,m:** Density functional theory (DFT) and time-dependent (TD) DFT approaches, as implemented in the Gaussian 16 package,[222] were used to model all chromophores of interest. Calculations have been performed in vacuum (gas phase) to provide general insights regardless of the solvent used, and consist in:
* Molecular structure optimisations, using the PBE0 hybrid functional[226] combined with the 6-31G(d,p) basis set, followed by frequency calculations to identify the nature of the energy minimum as a global minimum.

* Linear optical properties computation, using the range-separated hybrid functional CAM-B3LYP alongside a 6-31G(d,p) basis set.[272] The absorption features are obtained through the first 15 vertical excitations, and the emission energies by optimizing the geometry of the first excited-state, which is then validated by an excited-state frequency calculation. The excitation and emission energies are convoluted into UV-Vis bands by applying Gaussian functions with a Half-width at Half-Height of 0.3 eV.

**Compounds 241–242:** The spatial and electronic properties of the target chromophores were investigated using Gaussian® 16W software[222] package at the DFT level. Initial geometries of molecules **241a-c** and **242a-c** as well as the energies of their frontier molecular orbitals and ground state dipole moments *μ* were calculated at DFT B3LYP/6-311++G(3d,f,2p) level in vacuum. Theoretical electronic absorption spectra were calculated at TD-DFT (nstates = 8) B3LYP/6-311++G(3d,f,2p) level in vacuum.

**Complexes 245:** DFT and TD-DFT calculations were carried out using the Gaussian 16 package,[222] employing the PBE0 functional,[226,273,274] together with the LanL2DZ basis set.[275–278] Solvent (chloroform) effects were included through the PCM approximation.[279,280] The optimized geometries were fully characterized as true minima by analytical frequency calculations (no imaginary values). The composition of the Kohn-Sham orbitals was calculated using the AOMix program.[281] The geometries obtained from DFT calculations were used to perform natural atomic charge analysis with the NBO 6.0 program.[282] Only singlet-singlet transitions were taken into account in the TD-DFT calculations. Only the transitions with non-negligible oscillator strengths are discussed in the paper. The graphical GaussView interface[283] was used for simulating UV-vis spectra. The phosphorescence emission spectra were computed within the Franck-Condon principle by using the Adiabatic Hessian method[264,265] which takes into account vibrational mode mixing and a proper description of both optimized ground and excited (triplet) states potential energy surfaces. A class-based pre-screening[284–286] was applied in order to limit the number of terms involved in the vibronic calculation with the following settings: C1max = 70, C2max = 70, N1max = 100 × 108. The GaussView interface[283] was used for their simulation.
**General method A – Suzuki-Miyaura cross-coupling reaction**

The corresponding acetylene (1.57 equiv) was dissolved in THF (20 mL) and nitrogen was bubbled through the solution for 10 min. Catecholborane (1.9 equiv of 1 M solution in THF) was added and the reaction mixture was heated to reflux for 1.5 h. The second portion of catecholborane (0.7 equiv) was added and heating was continued for 2 h. The reaction mixture was cooled to room temperature and Pd(PPh₃)₄ (0.025 equiv) and corresponding pyrimidine (1 equiv) were added. The solution was stirred for 20 min whereupon 20% aqueous Na₂CO₃ (5 mL) was added and the mixture was stirred under nitrogen at reflux for 15 h. The reaction mixture was cooled and then diluted with CH₂Cl₂ (20 mL). The organic layer was washed with water (3x20 mL), brine (20 mL), separated, dried over MgSO₄ and the solvents were evaporated under reduced pressure. The crude product was purified by column chromatography (SiO₂, indicated solvents).

**General method B – Knoevenagel condensation**

Aldehyde (1 equiv) and corresponding 4-methylpyrimidine (1 equiv) or 4,6-dimethylpyrimidine (0.5 equiv) were added in 5 M aqueous NaOH (15 mL) containing Aliquat 336 (0.1 equiv). The solution was heated to reflux for 3 h and then cooled to room temperature. The precipitate was filtered off, washed with water and purified by recrystallization from CH₂Cl₂/n-heptane and/or by column chromatography (SiO₂, indicated solvents).

**General method C – Suzuki-Miyaura cross-coupling reaction**

Chloropyrimidine (1 equiv) and corresponding boronic acid or boronic acid pinacol ester (1.2 equiv) were dissolved in a mixture of toluene/EtOH (20:3, 23mL) or in THF (20 mL) and nitrogen was bubbled through the solution for 10 min. Pd(PPh₃)₄ (5%) and 20% aqueous Na₂CO₃ were added and then the reaction was stirred at 110 °C for 15h. The reaction mixture was cooled to room temperature and diluted with CH₂Cl₂/aqueous NH₄Cl (1:1, 100 mL). The organic layer was separated and the aqueous one was extracted with CH₂Cl₂ (2 × 50 mL). The combined organic extracts were dried over anhydrous MgSO₄ or Na₂SO₄ and the solvent was evaporated under reduced pressure. The solid residue was purified by column chromatography (SiO₂; indicated solvents).
General method D – synthesis of PtII complexes

K₂PtCl₄ (1 equiv) and ligand **244** (1.2 equiv) were dissolved in a mixture of EGEE/H₂O (3:1, 20 mL). The mixture was bubbled with nitrogen for 10 min and then stirred at 90 °C for 15h. The solution was cooled to room temperature and diluted with H₂O, precipitate was filtrated off and dried under vacuum. µ-Chloro-bridged intermediate was dissolved in CHCl₃ and pyridine was added (2.5 equiv). The mixture was stirred at 50 °C for 15 h. The reaction mixture was cooled to room temperature and diluted with CH₂Cl₂/aqueous NH₄Cl (1:1, 100 mL). The organic layer was separated and the aqueous one was extracted with CH₂Cl₂ (2 × 50 mL). The combined organic extracts were dried over anhydrous MgSO₄ and the solvents were evaporated under reduced pressure. The solid residue was purified by column chromatography (SiO₂; 1:1, EtOAc/CH₂Cl₂).

**229a**

<figure><img src="image_134.png" /></figure>

(E)-2-styryl-4-methylpyrimidine

C₁₃H₁₃N₂

MW = 196.25

Compound **229a** was synthesized from phenylacetylene (176 mg, 1.72 mmol) and 2-chloro-4-methylpyrimidine (142 mg, 1.1 mmol) following the method A. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 8:2). Yield: 70 mg (32 %); white solid. R<sub>f</sub>: 0.4 (SiO₂; petroleum ether:EtOAc, 8:2). Mp: 67.2–69.9 °C. ¹H NMR (300 MHz, CDCl₃): δ = 2.54 (s, 3H), 6.97 (d, ³J<sub>H-H</sub> = 4.8 Hz, 1H), 7.22 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H), 7.30–7.41 (m, 3H), 7.61–7.63 (m, 2H), 7.98 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H), 8.56 (d, ³J<sub>H-H</sub> = 4.8 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 24.41, 118.27, 127.75, 128.90, 129.10, 136.27, 137.95, 156.76, 164.66, 167.14 ppm. Not all carbon atoms were observed. IR (ATR): ν = 2918, 1547, 1440, 1385, 978, 790, 747 cm⁻¹. HR-MALDI-MS (DCTB): *m/z* calculated for C₁₃H₁₃N₂ [*(M+H)⁺*] 197.1073, found 197.1073. Data are in accordance with literature.[²⁸⁷]
**229b**

<figure><img src="image_135.png" /></figure>

(E)-2-(4-methoxystyryl)-4-methylpyrimidine

$C_{14}H_{14}N_2O$

MW = 226.27

Compound **229b** was synthesized from 4-ethynylanisole (311 mg, 2.35 mmol) and 2-chloro-4-methylpyrimidine (193 mg, 1.50 mmol) following the method A. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 7:3). Yield: 206 mg (61 %); brownish solid. R<sub>f</sub>: 0.2 (SiO₂; petroleum ether:EtOAc, 7:3). Mp: 102.3–104.9 °C. ¹H NMR (300 MHz, CDCl₃): δ = 2.53 (s, 3H), 3.83 (s, 3H), 6.90–6.95 (m, 3H), 7.09 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H), 7.55–7.58 (m, 2H), 7.93 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H), 8.54 (d, ³J<sub>H-H</sub> = 5.1 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 24.41, 55.47, 114.38, 117.92, 125.48, 129.06, 129.20, 137.60, 156.72, 160.55, 164.96, 167.08 ppm. IR (ATR): ν = 2937, 1566, 1509, 1249, 1178, 1028, 981, 821, 775 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₁₄H₁₄N₂O [M⁺] 226.1101, found 226.1100.

**229c**

<figure><img src="image_136.png" /></figure>

(E)-2-(4-*N*,*N*-dimethylaminostyryl)-4-methylpyrimidine

$C_{15}H_{17}N_3$

MW = 239.32

Compound **229c** was synthesized from 4-ethynyl-*N*,*N*-dimethylaniline (250 mg, 1.72 mmol) and 2-chloro-4-methylpyrimidine (142 mg, 1.1 mmol) following the method A. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 8:2). Yield: 85 mg (32 %); brown solid. R<sub>f</sub>: 0.3 (SiO₂; petroleum ether:EtOAc, 8:2). Mp: 117.3–119.8 °C. ¹H NMR (300 MHz, CDCl₃): δ = 2.51 (s, 3H), 2.99 (s, 6H), 6.68–6.71 (m, 2H), 6.89 (d, ³J<sub>H-H</sub> = 5.1 Hz, 1H), 7.02 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H), 7.49–7.52 (m, 2H), 7.92 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H), 8.50 (d, ³J<sub>H-H</sub> = 5.1 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 24.34, 40.33, 112.18, 117.34, 122.56, 124.26, 129.17, 138.55, 151.12, 156.55, 165.32, 166.94 ppm. IR (ATR): ν = 2912, 1602, 1523, 1435, 1363, 1167, 987, 805, 768, 750 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₁₅H₁₇N₃ [M⁺] 239.1417, found 239.1415.
**229d**

<figure><img src="image_137.png" /><figcaption>(E)-2-(4-N,N-diphenylaminostyryl)-4-methylpyrimidine</figcaption></figure>

$C_{25}H_{21}N_3$

MW = 363.45

Compound **229d** was synthesized from 4-ethynyl-N,N-diphenylaniline (275 mg, 1.02 mmol) and 2-chloro-4-methylpyrimidine (84 mg, 0.65 mmol) following the method A. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 8:2). Yield: 102 mg (43 %); yellow solid. R<sub>f</sub>: 0.2 (SiO₂; petroleum ether:EtOAc, 8:2). Mp: 120.9–123.5 °C. ¹H NMR (300 MHz, CDCl₃): δ = 2.53 (s, 3H), 6.94 (d, ³J<sub>H-H</sub> = 5.1 Hz, 1H), 7.02–7.15 (m, 10H), 7.25–7.31 (m, 3H), 7.46–7.49 (m, 2H), 7.92 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H), 8.54 (d, ³J<sub>H-H</sub> = 5.1 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 24.41, 117.87, 122.62, 123.65, 125.18, 125.45, 128.75, 129.51, 129.80, 137.58, 147.40, 148.83, 156.70, 164.97, 167.06 ppm. IR (ATR): ν= 3036, 1572, 1487, 1266, 984, 831, 750, 695 cm⁻¹. HR-MALDI-MS (DCTB): *m/z* calculated for C₂₅H₂₁N₃ [M⁺] 363.1730, found 363.1723.

**230a**

<figure><img src="image_138.png" /><figcaption>(E)-2-styryl-4,6-dimethylpyrimidine</figcaption></figure>

$C_{14}H_{14}N_2$

MW = 210.27

Compound **230a** was synthesized from phenylacetylene (161 mg, 1.57 mmol) and 2-chloro-4,6-dimethylpyrimidine (143 mg, 1 mmol) following the method A. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 7:3). Yield: 78 mg (37 %); white solid. R<sub>f</sub>: 0.7 (SiO₂; petroleum ether:EtOAc, 7:3). Mp: 47.5–49.4 °C. ¹H NMR (300 MHz, CDCl₃): δ= 2.50 (s, 6H), 6.86 (s, 1H), 7.21 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H), 7.29–7.41 (m, 3H), 7.61–7.64 (m, 2H), 7.97 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ= 24.13, 117.74, 127.67, 127.91, 128.82, 128.91, 136.37, 137.60, 164.27, 166.60 ppm. IR (ATR): ν= 3057, 1533, 1367, 978, 747, 692 cm⁻¹. HR-MALDI-MS (DCTB): *m/z* calculated for C₁₄H₁₅N₂ [(M+H)⁺] 211.1230, found 211.1227. Data are in accordance with literature.[288]
**230b**

<figure><img src="image_139.png" /><figcaption>(E)-2-(4-methoxystyryl)-4,6-dimethylpyrimidine</figcaption></figure>

$$C_{15}H_{16}N_{2}O$$

$$\text{MW} = 240.30$$

Compound **230b** was synthesized from 4-ethynylanisole (415 mg, 3.14 mmol) and 2-chloro-4,6-dimethylpyrimidine (286 mg, 2 mmol) following the method A. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 7:3). Yield: 257 mg (54 %); brownish solid. R<sub>f</sub>: 0.4 (SiO₂; petroleum ether:EtOAc, 7:3). Mp: 87.9–90.2 °C. ¹H NMR (300 MHz, CDCl₃): δ = 2.48 (s, 6H), 3.82 (s, 3H), 6.82 (s, 1H), 6.89–6.92 (m, 2H), 7.07 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H), 7.54–7.57 (m, 2H), 7.92 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 24.13, 55.44, 114.33, 117.43, 125.62, 129.14, 129.20, 137.35, 160.44, 164.61, 166.57 ppm. IR (ATR): ν = 3004, 1574, 1511, 1242, 1178, 1028, 981, 839, 818, 770 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₁₅H₁₆N₂O [M⁺] 240.1257, found 240.1256.

**230c**

<figure><img src="image_140.png" /><figcaption>(E)-2-(4-*N*,*N*-dimethylaminostyryl)-4,6-dimethylpyrimidine</figcaption></figure>

$$C_{16}H_{19}N_{3}$$

$$\text{MW} = 253.34$$

Compound **230c** was synthesized from 4-ethynyl-*N*,*N*-dimethylaniline (362 mg, 2.50 mmol) and 2-chloro-4,6-dimethylpyrimidine (230 mg, 1.61 mmol) following the method A. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 7:3). Yield: 244 mg (59 %); yellow solid. R<sub>f</sub>: 0.6 (SiO₂; petroleum ether:EtOAc, 7:3). Mp: 112.8–115.2 °C. ¹H NMR (300 MHz, CDCl₃): δ = 2.47 (s, 6H), 3.00 (s, 6H), 6.69–6.72 (m, 2H), 6.78 (s, 1H), 7.01 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H), 7.51–7.54 (m, 2H), 7.91 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 24.21, 40.41, 112.23, 116.89, 123.16, 124.58, 129.12, 138.05, 151.04, 165.14, 166.45 ppm. IR (ATR): ν = 2919, 1580, 1443, 1356, 1165, 986, 820, 748 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₁₆H₁₉N₃ [M⁺] 253.1574, found 253.1562.
**230d**

<figure><img src="image_141.png" /><figcaption>(E)-2-(4-N,N-diphenylaminostyryl)-4,6-dimethylpyrimidine</figcaption></figure>

$C_{26}H_{23}N_3$

$$ \text{MW} = 377.48 $$

Compound 230d was synthesized from 4-ethynyl-N,N-diphenylaniline (790 mg, 2.94 mmol) and 2-chloro-4,6-dimethylpyrimidine (267 mg, 1.87 mmol) following the method A. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 8:2). Yield: 200 mg (28 %); yellow solid. R<sub>f</sub>: 0.4 (SiO₂; petroleum ether:EtOAc, 8:2). Mp: 132.7–135.7 °C. ¹H NMR (300 MHz, CDCl₃): δ = 2.49 (s, 6H), 6.83 (s, 1H), 7.02–7.14 (m, 9H), 7.25–7.30 (m, 4H), 7.46–7.49 (m, 2H), 7.91 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 24.09, 117.34, 122.61, 123.55, 125.09, 125.60, 128.65, 129.45, 129.95, 137.27, 147.39, 148.63, 164.57, 166.49 ppm. IR (ATR): ν = 3030, 1585, 1488, 1273, 749, 692 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₂₆H₂₃N₃ [M⁺] 377.1887, found 377.1888.

**230e**

<figure><img src="image_142.png" /><figcaption>(E)-2-[(6-methoxynaphtalen-2-yl)ethenyl]-4,6-dimethylpyrimidine</figcaption></figure>

$C_{19}H_{18}N_2O$

$$ \text{MW} = 290.36 $$

Compound 230e was synthesized from 2-ethynyl-6-methoxynaphtalene (286 mg, 1.57 mmol) and 2-chloro-4,6-dimethylpyrimidine (143 mg, 1 mmol) following the method A. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 7:3). Yield: 230 mg (79 %); yellowish solid. R<sub>f</sub>: 0.3 (SiO₂; petroleum ether:EtOAc, 7:3). Mp: 133.5–134.9 °C. ¹H NMR (300 MHz, CDCl₃): δ = 2.45 (s, 6H), 3.86 (s, 3H), 6.75 (s, 1H), 7.06–7.13 (m, 2H), 7.26 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H), 7.66–7.77 (m, 3H), 7.88 (s, 1H), 8.09 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 24.00, 55.28, 105.93, 117.43, 119.08, 124.41, 126.98, 127.27, 128.44, 128.92, 129.86, 131.69, 134.93, 137.74, 158.25, 164.30, 166.42 ppm. IR (ATR): ν = 2931, 1582, 1364, 1163, 1027, 860, 803, 665 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₁₉H₁₈N₂O [M⁺] 290.1414, found 290.1414.
**230f**

(E)-2-(4-trifluoromethylstyryl)-4,6-dimethylpyrimidine

<figure><img src="image_143.png" /></figure>

$$C_{15}H_{13}F_{3}N_{2}$$

$$\text{MW} = 278.27$$

Compound 230f was synthesized from 4-trifluoromethylphenylacetylene (426 mg, 2.50 mmol) and 2-chloro-4,6-dimethylpyrimidine (228 mg, 1.59 mmol) following the method A. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 7:3). Yield: 222 mg (50 %); yellowish solid. R<sub>f</sub>: 0.4 (SiO₂; petroleum ether:EtOAc, 7:3). Mp: 94.9–96.5 °C. ¹H NMR (300 MHz, CDCl₃): δ= 2.50 (s, 6H), 6.89 (s, 1H), 7.26 (d, ³J<sub>H-H</sub>= 15.9 Hz, 1H), 7.60–7.71 (m, 4H), 7.97 (d, ³J<sub>H-H</sub>= 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ= 24.13, 118.23, 124.23 (q, ¹J<sub>C-F</sub>= 270 Hz), 125.82 (q, ³J<sub>C-F</sub>= 4 Hz), 127.73, 130.41, 130.47 (q, ²J<sub>C-F</sub>= 32 Hz), 135.85, 139.86 (d, ⁴J<sub>C-F</sub>= 1 Hz), 163.72, 166.80 ppm. IR (ATR): ν=2929, 1583, 1319, 1103, 1064, 831, 714 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₁₅H₁₄F₃N₂ [(M+H)⁺] 279.1104, found 279.1102.

**231a**

(E,E)-2,4-distyrylpyrimidine

<figure><img src="image_144.png" /></figure>

$$C_{20}H_{16}N_{2}$$

$$\text{MW} = 284.35$$

Compound 231a was synthesized from 229a (50 mg, 0.25 mmol) and benzaldehyde (28 mg, 0.25 mmol) following the method B. The crude product was purified by column chromatography (SiO₂; petroleum ether:EtOAc, 8:2). Yield: 41 mg (57 %); white solid. R<sub>f</sub>: 0.4 (SiO₂; petroleum ether:EtOAc, 8:2). Mp: 137 °C. ¹H NMR (300 MHz, CDCl₃): δ= 7.08–7.15 (m, 2H), 7.32–7.41 (m, 7H), 7.63–7.68 (m, 4H), 7.92 (d, ³J<sub>H-H</sub>= 15.9 Hz, 1H), 8.05 (d, ³J<sub>H-H</sub>= 15.9 Hz, 1H), 8.67 (d, ³J<sub>H-H</sub>= 5.1 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ= 115.91, 126.29, 127.82, 127.97, 128.93, 129.02, 129.14, 129.50, 135.92, 136.34, 137.25, 138.08, 157.56, 162.54, 164.87 ppm. Not all carbon atoms were observed. IR (ATR): ν= 3054, 3026, 1637, 1558, 1537, 1388, 975, 876, 738, 688 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₂₀H₁₇N₂ [(M+H)⁺] 285.1386, found 285.1385. Data are in accordance with literature.[206]
**231b**

<figure><img src="image_145.png" /></figure>

(E,E)-2,4-bis(4-methoxystyryl)pyrimidine

$$C_{22}H_{20}N_2O_2$$

$$\text{MW} = 344.41$$

Compound **231b** was synthesized from **229b** (170 mg, 0.75 mmol) and 4-methoxybenzaldehyde (103 mg, 0.75 mmol) following the method B. The crude product was purified by recrystallization from CH₂Cl₂/n-heptane. Yield: 218 mg (84 %); silver solid. Rf: 0.1 (SiO₂; petroleum ether:EtOAc, 7:3). Mp: 185 °C. ¹H NMR (300 MHz, CDCl₃): δ = 3.85 (s, 6H), 6.92–6.98 (m, 5H), 7.07 (d, ³Jₕ-ₕ = 5.1 Hz, 1H), 7.14 (d, ³Jₕ-ₕ = 15.9 Hz, 1H), 7.56–7.62 (m, 4H), 7.85 (d, ³Jₕ-ₕ = 15.9 Hz, 1H), 7.99 (d, ³Jₕ-ₕ = 15.9 Hz, 1H), 8.60 (d, ³Jₕ-ₕ = 5.1 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 55.47, 55.49, 114.36, 114.45, 115.26, 124.08, 125.80, 128.69, 129.14, 129.21, 129.28, 136.71, 137.51, 157.28, 160.51, 160.79, 162.79, 165.05 ppm. IR (ATR): ν = 2964, 1560, 1250, 1177, 1028, 972, 826 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₂₂H₂₁N₂O₂ [(M+H)⁺] 345.1598, found 345.1592.

**231c**

<figure><img src="image_146.png" /></figure>

(E,E)-2,4-bis(4-N,N-dimethylaminostyryl)pyrimidine

$$C_{24}H_{26}N_4$$

$$\text{MW} = 370.49$$

Compound **231c** was synthesized from **229c** (41 mg, 0.17 mmol) and 4-N,N-dimethylaminobenzaldehyde (26 mg, 0.17 mmol) following the method B. The crude product was purified by recrystallization from CH₂Cl₂/n-heptane. Yield: 55 mg (85 %); brown solid. Rf: 0.2 (SiO₂; petroleum ether:EtOAc, 8:2). Mp: 243 °C. ¹H NMR (300 MHz, CDCl₃): δ = 3.02–3.03 (m, 12H), 6.70–6.74 (m, 4H), 6.88 (d, ³Jₕ-ₕ = 15.9 Hz, 1H), 7.01–7.09 (m, 2H), 7.51–7.57 (m, 4H), 7.80 (d, ³Jₕ-ₕ = 15.9 Hz, 1H), 7.96 (d, ³Jₕ-ₕ = 15.9 Hz, 1H), 8.54 (d, ³Jₕ-ₕ = 5.1 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 40.39, 40.45, 112.21, 112.27, 114.34, 121.69, 123.45, 124.06, 124.63, 129.18, 129.26, 137.31, 138.05, 151.07, 151.28, 156.91, 163.32,
165.46 ppm. IR (ATR): ν = 2920, 1602, 1550, 1520, 1359, 1163, 970, 810, 781 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₂₄H₂₆N₄ [M⁺] 370.2152, found 370.2150.

231d

(E,E)-2,4-bis(4-N,N-diphenylaminostyryl)pyrimidine

<figure><img src="image_147.png" /></figure>

C₄₄H₃₄N₄

MW = 618.77

Compound 231d was synthesized from 229d (76 mg, 0.21 mmol) and 4-N,N-diphenylaminobenzaldehyde (58 mg, 0.21 mmol) following the method B. The crude product was purified by recrystallization from CH₂Cl₂/n-heptane. Yield: 51 mg (39 %); yellow solid. R<sub>f</sub>: 0.3 (SiO₂; petroleum ether:EtOAc, 8:2). T<sub>d</sub>: 250 °C. ¹H NMR (300 MHz, CDCl₃): δ = 6.92–6.97 (m, 2H), 7.04–7.15 (m, 19H), 7.29–7.32 (m, 6H), 7.46–7.52 (m, 4H), 7.82 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H), 7.97 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H), 8.59 (d, ³J<sub>H-H</sub> = 5.4 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 115.13, 122.47, 122.71, 123.63, 123.84, 124.12, 125.17, 125.29, 125.90, 128.78, 128.82, 129.35, 129.52, 129.57, 129.98, 136.67, 137.46, 147.30, 147.45, 148.78, 149.14, 157.24, 162.87, 165.12 ppm. IR (ATR): ν = 3034, 2924, 1588, 1556, 1490, 1274, 1174, 972, 831, 751, 693 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₄₄H₃₄N₄ [M⁺] 618.2778, found 618.2779.

232a

(E,E,E)-2,4,6-tristyrylpyrimidine

<figure><img src="image_148.png" /></figure>

C₂₈H₂₂N₂

MW = 386.49

Compound 232a was synthesized from 230a (300 mg, 1.43 mmol) and benzaldehyde (303 mg, 2.85 mmol) following the method B. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 9:1) and then by recrystallization from
CH₂Cl₂/n-heptane. Yield: 155 mg (28 %); white solid. R<sub>f</sub>: 0.4 (SiO₂; petroleum ether:EtOAc, 9:1). Mp: 193 °C. ¹H NMR (300 MHz, CDCl₃): δ = 7.08–7.16 (m, 3H), 7.28–7.43 (m, 10H), 7.62–7.69 (m, 6H), 7.93 (d, ³J<sub>H-H</sub> = 15.9 Hz, 2H), 8.11 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ=113.68, 126.51, 127.73, 127.77, 128.29, 128.84, 128.95, 129.32, 136.03, 136.45, 136.72, 137.87, 162.94, 164.62 ppm. Not all carbon atoms were observed. IR (ATR): ν = 3025, 1635, 1564, 1514, 1368, 963, 739, 689 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₂₈H₂₃N₂ [(M+H)⁺] 387.1856, found 387.1855. Data are in accordance with literature.[208]

**232b**
(E,E,E)-2-styryl-4,6-bis(4-methoxystyryl)pyrimidine
C₃₀H₂₆N₂O₂
MW = 446.54

<figure><img src="image_149.png" /></figure>

Compound **232b** was synthesized from **230a** (78 mg, 0.37 mmol) and 4-methoxybenzaldehyde (102 mg, 0.74 mmol) following the method B. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 8:2) and then by recrystallization from CH₂Cl₂/n-heptane. Yield: 40 mg (24 %); yellowish solid. R<sub>f</sub>: 0.4 (SiO₂; petroleum ether:EtOAc, 8:2). Mp: 128 °C. ¹H NMR (300 MHz, CDCl₃): δ=3.86 (s, 6H), 6.93–7.01 (m, 6H), 7.11 (s, 1H), 7.29–7.44 (m, 4H), 7.58–7.61 (m, 4H), 7.68–7.70 (m, 2H), 7.89 (d, ³J<sub>H-H</sub> = 15.9 Hz, 2H), 8.11 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ=55.51, 113.20, 114.46, 124.39, 127.80, 128.54, 128.86, 128.90, 128.91, 129.25, 136.25, 136.61, 137.65, 160.72, 163.15, 164.55 ppm. IR (ATR): ν=2837, 1604, 1560, 1501, 1251, 1171, 1152, 967, 749 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₃₀H₂₇N₂O₂ [(M+H)⁺] 447.2067, found 447.2064.
**232c** (E,E,E)-2-styryl-4,6-bis(4-N,N-dimethylaminostyryl)pyrimidine

<figure><img src="image_150.png" /></figure>

$C_{32}H_{32}N_4$

MW = 472.62

Compound 232c was synthesized from 230a (150 mg, 0.71 mmol) and 4-N,N-dimethylaminobenzaldehyde (213 mg, 1.43 mmol) following the method B. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 8:2) and then by recrystallization from CH₂Cl₂/n-heptane. Yield: 63 mg (17 %); black solid. Rf: 0.2 (SiO₂; petroleum ether:EtOAc, 8:2). Td: 245 °C. ¹H NMR (300 MHz, CDCl₃): δ= 3.03 (s, 12 H), 6.71–6.74 (m, 4H), 6.91 (d, ³JH-H = 15.9 Hz, 2H), 7.08 (s, 1H), 7.28–7.35 (m, 4H), 7.53–7.56 (m, 4H), 7.68–7.70 (m, 2H), 7.86 (d, ³JH-H = 15.9 Hz, 2H), 8.10 (d, ³JH-H = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 40.39, 112.24, 112.41, 114.20, 114.74, 121.91, 124.28, 127.78, 128.73, 128.81, 129.21, 136.81, 137.25, 151.20, 163.36, 164.33 ppm. IR (ATR): ν = 2892, 1602, 1555, 1503, 1363, 1162, 965, 800, 746 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₃₂H₃₂N₄ [M⁺] 472.2622, found 472.2620.

**232d** (E,E,E)-2-styryl-4,6-bis(4-N,N-diphenylaminostyryl)pyrimidine

<figure><img src="image_151.png" /></figure>

$C_{52}H_{40}N_4$

MW = 720.90

Compound 232d was synthesized from 230a (300 mg, 1.43 mmol) and 4-N,N-diphenylaminobenzaldehyde (780 mg, 2.85 mmol) following the method B. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 9:1) and then by recrystallization from CH₂Cl₂/n-heptane. Yield: 220 mg (21 %); yellow solid. Rf: 0.4 (SiO₂; petroleum ether:EtOAc, 9:1). Td: 305 °C. ¹H NMR (300 MHz, CDCl₃): δ= 6.98 (d, ³JH-H = 15.9 Hz, 2H), 7.05–7.17 (m, 17H), 7.27–7.43 (m, 12H), 7.48–7.51 (m, 4H), 7.67–7.70 (m, 2H), 7.87 (d, ³JH-H = 15.9 Hz, 2H), 8.10 (d, ³JH-H = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ=
113.14, 122.54, 123.78, 124.41, 125.25, 127.79, 128.58, 128.77, 128.85, 128.88, 129.56, 129.59, 136.14, 136.61, 137.60, 147.34, 149.00, 163.11, 164.55 ppm. IR (ATR): ν = 3033, 1559, 1490, 1274, 969, 748, 693 cm⁻¹. HR-MALDI-MS (DCTB): *m/z* calculated for C₅₂H₄₀N₄ [M⁺] 720.3248, found 720.3252.

**232e**

(E,E,E)-2,4,6-tris(4-methoxystyryl)pyrimidine

$$C_{31}H_{28}N_2O_3$$

$$\text{MW} = 476.57$$

<figure><img src="image_152.png" /></figure>

Compound **232e** was synthesized from **230b** (100 mg, 0.42 mmol) and 4-methoxybenzaldehyde (114 mg, 0.83 mmol) following the general procedure for Knoevenagel condensation. The crude product was purified by recrystallization from CH₂Cl₂/n-heptane. Yield: 156 mg (79 %); yellowish solid. R<sub>f</sub>: 0.4 (SiO₂; petroleum ether:EtOAc, 8:2). Mp: 183 °C. ¹H NMR (300 MHz, CDCl₃): δ = 3.85 (s, 9H), 6.93-7.00 (m, 8H), 7.08 (s, 1H), 7.18 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H), 7.57-7.65 (m, 6H), 7.88 (d, ³J<sub>H-H</sub> = 15.9 Hz, 2H), 8.06 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 55.46, 55.49, 112.83, 114.34, 114.45, 124.50, 126.29, 128.96, 129.21, 129.40, 136.12, 137.30, 160.40, 160.68, 163.08, 164.84 ppm. Not all carbon atoms were observed. IR (ATR): ν = 2933, 1602, 1559, 1506, 1245, 1169, 1028, 959, 868, 810, 767 cm⁻¹. HR-MALDI-MS (DCTB): *m/z* calculated for C₃₁H₂₈N₂O₃ [M⁺] 476.2094, found 476.2094.

**232f**

(E,E,E)-2-(4-methoxystyryl)-4,6-bis(4-N,N-dimethylaminostyryl)pyrimidine

$$C_{33}H_{34}N_4O$$

$$\text{MW} = 502.65$$

<figure><img src="image_153.png" /></figure>

Compound **232f** was synthesized from **230b** (100 mg, 0.42 mmol) and 4-N,N-dimethylaminobenzaldehyde (125 mg, 0.83 mmol) following the method B. The crude product
was purified by recrystallization from CH₂Cl₂/n-heptane. Yield: 154 mg (74 %); red solid. R<sub>f</sub>: 0.3 (SiO₂; petroleum ether:EtOAc, 8:2). T<sub>d</sub>: 250 °C. ¹H NMR (300 MHz, CDCl₃): δ = 3.03 (s, 12H), 3.85 (s, 3H), 6.71–6.74 (m, 4H), 6.88–6.95 (m, 4H), 7.07 (s, 1H), 7.17 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H), 7.52–7.55 (m, 4H), 7.62–7.65 (m, 2H), 7.84 (d, ³J<sub>H-H</sub> = 15.9 Hz, 2H), 8.05 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 40.37, 55.44, 112.13, 112.22, 114.27, 122.04, 124.28, 126.65, 129.15, 129.57, 136.60, 136.80, 151.15, 160.25, 163.31, 164.66 ppm. Not all carbon atoms were observed. IR (ATR): ν = 2924, 1600, 1550, 1497, 1355, 1244, 1142, 971, 806 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₃₃H₃₄N₄O [M⁺] 502.2727, found 502.2731.

**232g** (E,E,E)-2-(4-methoxystyryl)-4,6-bis(4-N,N-diphenylaminostyryl)pyrimidine

$C_{53}H_{42}N_{4}O$

$\text{MW} = 750.93$

<figure><img src="image_154.png" /></figure>

Compound 232g was synthesized from 230b (100 mg, 0.42 mmol) and 4-N,N-diphenylaminobenzaldehyde (228 mg, 0.83 mmol) following the method B. The crude product was purified by recrystallization from CH₂Cl₂/n-heptane. Yield: 225 mg (72 %); yellow solid. R<sub>f</sub>: 0.7 (SiO₂; petroleum ether:EtOAc, 8:2). T<sub>d</sub>: 270 °C. ¹H NMR (300 MHz, CDCl₃): δ = 3.85 (s, 3H), 6.92–7.21 (m, 24H), 7.27–7.32 (m, 6H), 7.48–7.50 (m, 4H), 7.61–7.64 (m, 2H), 7.86 (d, ³J<sub>H-H</sub> = 15.9 Hz, 2H), 8.06 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 55.46, 112.81, 114.33, 122.58, 123.75, 124.55, 125.24, 126.35, 128.74, 129.20, 129.42, 129.55, 129.67, 136.01, 137.25, 147.37, 148.97, 160.39, 163.05, 164.86 ppm. IR (ATR): ν = 3033, 1562, 1489, 1271, 1242, 1168, 972, 818, 749, 691 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₅₃H₄₂N₄O [M⁺] 750.3353, found 750.3361.
**232h** (*E*,*E*,*E*)-2-(*N*-4-*N*,*N*-dimethylaminostyryl)-4,6-bis(4-methoxystyryl)pyrimidine

<figure><img src="image_155.png" /></figure>

$$
\begin{array}{l}
\mathrm{C}_{32}\mathrm{H}_{31}\mathrm{N}_{3}\mathrm{O}_{2} \\
\mathrm{MW} = 489.61
\end{array}
$$

Compound **232h** was synthesized from **230c** (110 mg, 0.43 mmol) and 4-methoxybenzaldehyde (119 mg, 0.87 mmol) following the method B. The crude product was purified by recrystallization from CH₂Cl₂/n-heptane. Yield: 121 mg (57 %); brown solid. Rf: 0.3 (SiO₂; petroleum ether:EtOAc, 8:2). Mp: 200 °C. ¹H NMR (300 MHz, CDCl₃): δ = 3.02 (s, 6H), 3.85 (s, 6H), 6.72–6.75 (m, 2H), 6.93–7.00 (m, 6H), 7.05 (s, 1H), 7.12 (d, ³Jₕ-H = 15.9 Hz, 1H), 7.57–7.61 (m, 6H), 7.87 (d, ³Jₕ-H = 15.9 Hz, 2H), 8.05 (d, ³Jₕ-H = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 40.43, 55.49, 112.25, 112.36, 114.42, 123.71, 124.70, 124.76, 129.03, 129.18, 135.89, 138.09, 151.02, 160.61, 163.00, 165.36 ppm. Not all carbon atoms were observed. IR (ATR): ν = 2924, 1603, 1558, 1502, 1357, 1249, 1168, 1028, 961, 810 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₃₂H₃₁N₃O₂ [M⁺] 489.2411, found 489.2414.

**232i** (*E*,*E*,*E*)-2,4,6-tris(4-*N*,*N*-dimethylaminostyryl)pyrimidine

<figure><img src="image_156.png" /></figure>

$$
\begin{array}{l}
\mathrm{C}_{34}\mathrm{H}_{37}\mathrm{N}_{5} \\
\mathrm{MW} = 515.69
\end{array}
$$

Compound **232i** was synthesized from **230c** (244 mg, 0.96 mmol) and 4-*N*,*N*-dimethylaminobenzaldehyde (287 mg, 1.92 mmol) following the method B. The crude product was purified by recrystallization from CH₂Cl₂/n-heptane. Yield: 212 mg (43 %); brown solid. Rf: 0.1 (SiO₂; petroleum ether:EtOAc, 8:2). Td: 250 °C. ¹H NMR (300 MHz, CDCl₃): δ = 3.02–3.03 (m, 18H), 6.71–6.75 (m, 6H), 6.91 (d, ³Jₕ-Η = 15.9 Hz, 2H), 7.05 (s, 1H), 7.11 (d, ³Jₕ-Η = 15.6 Hz, 1H), 7.53–7.61 (m, 6H), 7.83 (d, ³Jₕ-Η = 15.9 Hz, 2H), 8.03 (d, ³Jₕ-Η = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 40.42, 40.47, 111.65, 112.28, 122.34, 124.16, 124.45, 125.03, 129.14, 136.42, 137.64, 150.92, 151.13, 163.25, 165.19 ppm. Not all carbon atoms
were observed. IR (ATR): ν = 2888, 1599, 1502, 1356, 1167, 965, 797 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₃₄H₃₇N₅ [M⁺] 515.3044, found 515.3044.

**232j**
(E,E,E)-2-(4-N,N-dimethylaminostyryl)-4,6-bis(4-N,N-diphenylaminostyryl)pyrimidine

$C_{54}H_{45}N_{5}$

$$
\text{MW} = 763.97
$$

<figure><img src="image_157.png" /></figure>

Compound 232j was synthesized from 230c (110 mg, 0.43 mmol) and 4-N,N-diphenylaminobenzaldehyde (238 mg, 0.87 mmol) following the method B. The crude product was purified by recrystallization from CH₂Cl₂/n-heptane. Yield: 225 mg (68 %); yellow solid. Rf: 0.6 (SiO₂; petroleum ether:EtOAc, 8:2). Td: 240 °C. ¹H NMR (300 MHz, CDCl₃): δ = 3.02 (s, 6H), 6.72–6.75 (m, 2H), 6.99 (d, ³JH-H = 15.9 Hz, 2H), 7.05–7.16 (m, 18H), 7.27–7.32 (m, 8H), 7.48–7.50 (m, 4H), 7.57–7.60 (m, 2H), 7.85 (d, ³JH-H = 15.9 Hz, 2H), 8.04 (d, ³JH-H = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ= 40.43, 112.24, 112.30, 122.62, 123.70, 124.76, 124.78, 125.20, 128.71, 129.19, 129.53, 129.78, 135.79, 138.05, 147.38, 148.87, 150.99, 162.96, 165.36 ppm. Not all carbon atoms were observed. IR (ATR): ν = 3034, 1564, 1490, 1361, 1273, 1167, 971, 810, 749, 692 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₅₄H₄₅N₅ [M⁺] 763.3670, found 763.3673.
**232k** (E,E,E)-2-(4-N,N-diphenylaminostyryl)-4,6-bis(4-methoxystyryl)pyrimidine

<figure><img src="image_158.png" /></figure>

$$C_{42}H_{35}N_3O_2$$

$$\text{MW} = 613.75$$

Compound **232k** was synthesized from **230d** (70 mg, 0.19 mmol) and 4-methoxybenzaldehyde (51 mg, 0.37 mmol) following the method B. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 8:2). Yield: 83 mg (73 %); yellow solid. R<sub>f</sub>: 0.5 (SiO₂; petroleum ether:EtOAc, 8:2). T<sub>d</sub>: 310 °C. ¹H NMR (300 MHz, CDCl₃): δ = 3.86 (s, 6H), 6.93–7.20 (m, 16H), 7.27–7.32 (m, 4H), 7.53–7.60 (m, 6H), 7.87 (d, ³J<sub>H-H</sub> = 15.9 Hz, 2H), 8.05 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ= 55.50, 112.77, 114.44, 122.76, 123.56, 124.53, 126.38, 128.76, 128.94, 129.21, 129.50, 130.27, 136.09, 137.23, 147.50, 148.60, 160.66, 163.07, 164.89 ppm. IR (ATR): ν = 3033, 1562, 1506, 1279, 1248, 1031, 972, 808, 752, 695 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₄₂H₃₅N₃O₂ [M⁺] 613.2724, found 613.2728.

**232l** (E,E,E)-2-(4-N,N-diphenylaminostyryl)-4,6-bis(4-N,N-dimethylaminostyryl)pyrimidine

<figure><img src="image_159.png" /></figure>

$$C_{44}H_{41}N_5$$

$$\text{MW} = 639.83$$

Compound **232l** was synthesized from **230d** (70 mg, 0.19 mmol) and 4-N,N-dimethylaminobenzaldehyde (56 mg, 0.37 mmol) following the method B. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 8:2) and then by recrystallization from CH₂Cl₂/n-heptane. Yield: 62 mg (52 %); yellow solid. R<sub>f</sub>: 0.5 (SiO₂; petroleum ether:EtOAc, 8:2). T<sub>d</sub>: 195 °C. ¹H NMR (300 MHz, CDCl₃): δ= 3.03 (s, 12H), 6.71–
6.74 (m, 4H), 6.90 (d, $ ^{3}J_{H-H} $ = 15.9 Hz, 2H), 7.03–7.08 (m, 5H), 7.13–7.19 (m, 5H), 7.28–7.31 (m, 4H), 7.52–7.55 (m, 6H), 7.83 (d, $ ^{3}J_{H-H} $ = 15.9 Hz, 2H), 8.03 (d, $ ^{3}J_{H-H} $ = 15.9 Hz, 1H) ppm. $ ^{13}C$ NMR (75 MHz, CDCl$_{3}$): $ \delta $=40.41, 112.03, 112.24, 122.11, 122.86, 123.46, 124.31, 125.07, 126.79, 128.72, 129.17, 129.48, 130.53, 136.60, 136.77, 147.55, 148.41, 151.15, 163.31, 164.71 ppm. IR (ATR): $ \nu $=2853, 1602, 1553, 1492, 1358, 1276, 974, 808, 751, 696 cm$^{-1}$. HR-MALDI-MS (DCTB): m/z calculated for C$_{44}$H$_{41}$N$_{5}$ [M$^{+}$] 639.3357, found 639.3359.

232m

(E,E,E)-2,4,6-tris(4-N,N-diphenylaminostyryl)pyrimidine

<figure><img src="image_160.png" /></figure>

C$_{64}$H$_{49}$N$_{5}$

<figure><img src="image_161.png" /></figure>

MW = 888.11

Compound **232m** was synthesized from **230d** (33 mg, 0.09 mmol) and 4-N,N-diphenylaminobenzaldehyde (48 mg, 0.17 mmol) following the method B. The crude product was purified by recrystallization from CH$_{2}$Cl$_{2}$/n-heptane. Yield: 44 mg (57 %); yellow solid. R$_{f}$: 0.8 (SiO$_{2}$; petroleum ether:EtOAc, 8:2). T$_{d}$: 310 °C. $ ^{1}H$ NMR (300 MHz, CDCl$_{3}$): $ \delta $= 6.97 (d, $ ^{3}J_{H-H} $ = 15.9 Hz, 2H), 7.04–7.20 (m, 26H), 7.27–7.32 (m, 12H), 7.47–7.55 (m, 6H), 7.85 (d, $ ^{3}J_{H-H} $ = 15.9 Hz, 2H), 8.04 (d, $ ^{3}J_{H-H} $ = 15.9 Hz, 1H) ppm. $ ^{13}C$ NMR (75 MHz, CDCl$_{3}$): $ \delta $= 112.70, 122.57, 122.76, 123.54, 123.75, 124.35, 124.57, 125.11, 125.23, 126.42, 128.74, 129.49, 129.54, 129.65, 130.28, 135.99, 137.20, 147.35, 147.49, 148.58, 148.95, 163.05, 164.90 ppm. IR (ATR): $ \nu $= 3034, 1588, 1558, 1489, 1273, 1174, 970, 750, 693 cm$^{-1}$. HR-MALDI-MS (DCTB): m/z calculated for C$_{64}$H$_{49}$N$_{5}$ [M$^{+}$] 887.3983, found 887.3982.
**232n** (*E*,*E*,*E*)-2-[(6-methoxynaphtalen-2-yl)ethenyl]-4,6-bis(4-methoxystyryl)pyrimidine

<figure><img src="image_162.png" /></figure>

$C_{35}H_{30}N_2O_3$

Compound **232n** was synthesized from **230e** (56 mg, 0.19 mmol) and 4-methoxybenzaldehyde (52 mg, 0.38 mmol) following the method B. The crude product was purified by recrystallization from CH₂Cl₂/n-heptane. Yield: 77 mg (77 %); yellowish solid. R<sub>f</sub>: 0.3 (SiO₂; petroleum ether:EtOAc, 8:2). T<sub>d</sub>: 290 °C. ¹H NMR (300 MHz, CDCl₃): δ= 3.86 (s, 6H), 3.94 (s, 3H), 6.94–7.19 (m, 9H), 7.38 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H), 7.59–7.61 (m, 4H), 7.74–7.98 (m, 6H), 8.24 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ= 55.51, 106.14, 113.09, 114.46, 119.23, 124.46, 124.78, 127.39, 127.80, 128.58, 128.95, 129.14, 129.24, 130.05, 132.07, 135.08, 136.18, 137.88, 158.40, 160.69, 163.12, 164.73 ppm. IR (ATR): ν= 2935, 1601, 1559, 1505, 1366, 1246, 1169, 1027, 959, 838, 809 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₃₅H₃₀N₂O₃ [M⁺] 526.2251, found 526.2252.

**232o** (*E*,*E*,*E*)-2-[(6-methoxynaphtalen-2-yl)ethenyl]-4,6-bis(4-*N*,*N*-dimethylaminostyryl)pyrimidine

<figure><img src="image_163.png" /></figure>

$C_{37}H_{36}N_4O$

Compound **232o** was synthesized from **230e** (53 mg, 0.18 mmol) and 4-*N*,*N*-dimethylaminobenzaldehyde (54 mg, 0.36 mmol) following the method B. The crude product was purified by recrystallization from CH₂Cl₂/n-heptane. Yield: 70 mg (70 %); orange solid. R<sub>f</sub>: 0.2 (SiO₂; petroleum ether:EtOAc, 8:2). T<sub>d</sub>: 250 °C. ¹H NMR (300 MHz, CDCl₃): δ= 3.03 (s, 12H), 3.94 (s, 3H), 6.72–6.75 (m, 4H), 6.92 (d, ³J<sub>H-H</sub> = 15.9 Hz, 2H), 7.07–7.18 (m, 3H),
7.38 (d, $^3J_{H-H}$ = 15.9 Hz, 1H), 7.54–7.57 (m, 4H), 7.74–7.90 (m, 5H), 7.99 (s, 1H), 8.23 (d, $^3J_{H-H}$ = 15.9 Hz, 1H) ppm. $^{13}$C NMR (75 MHz, CDCl₃): $\delta$= 40.38, 55.49, 106.12, 112.24, 112.35, 119.13, 122.02, 124.30, 124.85, 127.32, 128.18, 128.44, 129.19, 130.03, 132.25, 134.97, 136.67, 137.39, 151.16, 158.30, 163.35, 164.54 ppm. Not all carbon atoms were observed. IR (ATR): $v$ = 2853, 1600, 1552, 1357, 1144, 969, 851, 804 cm⁻¹. HR-MALDI-MS (DCTB): *m/z* calculated for C₃₇H₃₆N₄O [M⁺] 552.2884, found 552.2889.

**232p**

(E,E,E)-2-[(6-methoxynaphtalen-2-yl)ethenyl]-4,6-bis(4-*N*,*N*-diphenylaminostyryl)pyrimidine

C₅₇H₄₄N₄O

MW = 552.71

<figure><img src="image_164.png" /></figure>

Compound **232p** was synthesized from **230e** (37 mg, 0.12 mmol) and 4-*N*,*N*-diphenylaminobenzaldehyde (69 mg, 0.25 mmol) following the method B. The crude product was purified by recrystallization from CH₂Cl₂/*n*-heptane. Yield: 30 mg (30 %); orange solid. *R*<sub>f</sub>: 0.6 (SiO₂; petroleum ether:EtOAc, 8:2). *T*<sub>d</sub>: 220 °C. ¹H NMR (300 MHz, CDCl₃): $\delta$= 3.94 (s, 3H), 6.97–7.17 (m, 22H), 7.28–7.40 (m, 8H), 7.49–7.52 (m, 4H), 7.74–7.79 (m, 2H), 7.84–7.92 (m, 3H), 7.98 (s, 1H), 8.23 (d, $^3J_{H-H}$ = 15.9 Hz, 1H) ppm. $^{13}$C NMR (75 MHz, CDCl₃): $\delta$= 55.50, 106.12, 113.03, 119.21, 122.57, 123.76, 124.49, 124.78, 125.25, 127.37, 127.83, 128.57, 128.76, 129.13, 129.55, 129.64, 130.04, 132.07, 135.06, 136.07, 137.83, 147.38, 148.98, 158.39, 163.10, 164.76 ppm. IR (ATR): $v$ = 3034, 1588, 1558, 1490, 1268, 1174, 969, 849, 751, 694 cm⁻¹. HR-MALDI-MS (DCTB): *m/z* calculated for C₅₇H₄₄N₄O [M⁺] 800.3510, found 800.3518.
**232q** (*E*,*E*,*E*)-2-(4-trifluoromethylstyryl)-4,6-bis(4-methoxystyryl)pyrimidine

<figure><img src="image_165.png" /></figure>

$$C_{31}H_{25}F_{3}N_{2}O_{2}$$

$$\text{MW} = 514.54$$

Compound **232q** was synthesized from **230f** (90 mg, 0.32 mmol) and 4-methoxybenzaldehyde (88 mg, 0.65 mmol) following the method B. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 7:3). Yield: 71 mg (43 %); yellowish solid. *R*<sub>f</sub>: 0.7 (SiO₂; petroleum ether:EtOAc, 7:3). *T*<sub>d</sub>: 280 °C. ¹H NMR (300 MHz, CDCl₃): *δ* = 3.86 (s, 6H), 6.94–7.02 (m, 6H), 7.13 (s, 1H), 7.38 (d, ³*J*<sub>H-H</sub> = 15.9 Hz, 1H), 7.58–7.61 (m, 4H), 7.65–7.68 (m, 2H), 7.76–7.79 (m, 2H), 7.91 (d, ³*J*<sub>H-H</sub> = 15.9 Hz, 2H), 8.11 (d, ³*J*<sub>H-H</sub> = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): *δ* = 55.51, 113.62, 114.50, 124.17, 124.29 (q, ¹*J*<sub>C-F</sub> = 270 Hz), 125.83 (q, ³*J*<sub>C-F</sub> = 4 Hz), 127.82, 128.81, 129.28, 130.43 (q, ²*J*<sub>C-F</sub> = 32 Hz), 131.07, 135.81, 136.48, 140.07, 160.80, 163.24, 163.95 ppm. IR (ATR): *ν* = 2838, 1568, 1325, 1251, 1107, 976, 818 cm⁻¹. HR-MALDI-MS (DCTB): *m/z* calculated for C₃₁H₂₅F₃N₂O₂ [M⁺] 514.1863, found 514.1861.

**232r** (*E*,*E*,*E*)-2-(4-trifluoromethylstyryl)-4,6-bis(4-*N*,*N*-dimethylaminostyryl)pyrimidine

<figure><img src="image_166.png" /></figure>

$$C_{33}H_{31}F_{3}N_{4}$$

$$\text{MW} = 540.62$$

Compound **232r** was synthesized from **230f** (90 mg, 0.32 mmol) and 4-*N*,*N*-dimethylaminobenzaldehyde (97 mg, 0.65 mmol) following the method B. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 8:2). Yield: 69 mg (40 %); orange solid. *R*<sub>f</sub>: 0.3 (SiO₂; petroleum ether:EtOAc, 8:2). Mp: 210 °C. ¹H NMR (300 MHz, CDCl₃): *δ* = 3.04 (s, 12H), 6.72–6.75 (m, 4H), 6.91 (d, ³*J*<sub>H-H</sub> = 15.9 Hz, 2H), 7.10 (s, 1H), 7.37 (d, ³*J*<sub>H-H</sub> = 15.9 Hz, 1H), 7.53–7.56 (m, 4H), 7.64–7.67 (m, 2H), 7.76–7.79 (m, 2H), 7.86 (d, ³*J*<sub>H-H</sub> = 15.9 Hz, 2H), 8.09 (d, ³*J*<sub>H-H</sub> = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): *δ* = 40.39,
112.22, 112.88, 121.69, 124.14, 124.33 (q, ¹J<sub>C-F</sub> = 270 Hz), 125.78 (q, ³J<sub>C-F</sub> = 4 Hz), 127.78, 129.24, 130.24 (q, ²J<sub>C-F</sub> = 32 Hz), 131.42, 135.37, 136.97, 140.24, 151.24, 163.46, 163.78 ppm.
IR (ATR): ν = 2892, 1494, 1318, 1116, 1065, 974, 809 cm⁻¹. HR-MALDI-MS (DCTB): m/z
calculated for C₃₃H₃₁F₃N₄ [M⁺] 540.2495, found 540.2501.

**232s** (E,E,E)-2-(4-trifluoromethylstyryl)-4,6-bis(4-N,N-dimethylaminostyryl)pyrimidine

<figure><img src="image_167.png" /></figure>

C₅₃H₃₉F₃N₄
MW = 788.90

Compound 232s was synthesized from 230f (90 mg, 0.32 mmol) and 4-N,N-diphenylaminobenzaldehyde (177 mg, 0.65 mmol) following the method B. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 9:1). Yield: 70 mg (28 %); yellow solid. Rf: 0.7 (SiO₂; petroleum ether:EtOAc, 9:1). Td: 300 °C. ¹H NMR (300 MHz, CDCl₃): δ = 7.00 (d, ³Jₕ-ₕ = 15.9 Hz, 2H), 7.08-7.19 (m, 18H), 7.30-7.43 (m, 8H), 7.50-7.53 (m, 4H), 7.66-7.69 (m, 2H), 7.78-7.80 (m, 2H), 7.90 (d, ³Jₕ-ₕ = 15.9 Hz, 2H), 8.12 (d, ³Jₕ-ₕ = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ= 113.57, 123.83, 124.03, 124.14, 124.50 (q, ¹Jₐ-ₐ = 276 Hz), 125.28, 125.80 (q, ³Jₐ-ₐ = 4 Hz), 127.79, 128.79, 129.41, 129.56, 130.36 (q, ²Jₐ-ₐ = 32 Hz), 131.11, 135.72, 136.32, 140.05 (q, ⁴Jₐ-ₐ = 1 Hz), 147.29, 149.08, 163.16, 163.91 ppm. IR (ATR): ν = 3033, 1559, 1490, 1320, 1066, 968, 751 cm⁻¹. HR-MALDI-MS (DCTB): m/z calculated for C₅₃H₃₉F₃N₄ [M⁺] 788.3121, found 788.3111.

**233a** (E)-2-chloro-4-(4-N,N-dimethylaminostyryl)-6-methylpyrimidine

<figure><img src="image_168.png" /></figure>

C₁₅H₁₆ClN₃
MW = 273.76

Compound 233a was synthesized from 4-ethynyl-N,N-dimethylaniline (250 mg, 1.72 mmol) and 2,4-dichloro-6-methylpyrimidine (179 mg, 1.1 mmol) following the method A. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 8:2). Yield: 156 mg (52 %); brown solid. Rf: 0.4 (SiO₂; petroleum ether:EtOAc, 8:2). Mp: 163.4-
165.7 °C. ¹H NMR (300 MHz, CDCl₃): δ= 2.49 (s, 3H), 3.03 (s, 6H), 6.68–6.78 (m, 3H), 6.99 (s, 1H), 7.47–7.50 (m, 2H), 7.83 (d, ³Jₕ-ₕ = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 24.04, 40.30, 112.12, 115.63, 119.24, 123.31, 129.64, 139.55, 151.63, 161.09, 166.25, 169.95 ppm. IR (ATR): ν = 2913, 2193, 1566, 1258, 979, 809, 750, 765 cm⁻¹. HR-MALDI-MS (DCTB): *m/z* calculated for C₁₅H₁₆ClN₃ [M⁺] 273.1027, found 273.1023.

**233b**

<figure><img src="image_169.png" /></figure>

(E)-2-chloro-4-(4-methoxystyryl)-6-methylpyrimidine

C₁₄H₁₃ClN₂O

MW = 260.72

Compound **233b** was synthesized from 4-ethynylanisole (311 mg, 2.35 mmol) and 2,4-dichloro-6-methylpyrimidine (245 mg, 1.5 mmol) following the method A. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 7:3). Yield: 215 mg (55 %); yellowish solid. *R*<sub>f</sub>: 0.4 (SiO₂; petroleum ether:EtOAc, 7:3). Mp: 78.9–81.8 °C. ¹H NMR (300 MHz, CDCl₃): δ= 2.51 (s, 3H), 3.85 (s, 3H), 6.83 (d, ³Jₕ-ₕ = 15.9 Hz, 1H), 6.90–6.95 (m, 2H), 7.04 (s, 1H), 7.51–7.56 (m, 2H), 7.86 (d, ³Jₕ-ₕ = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 24.08, 55.53, 114.56, 116.24, 122.03, 128.17, 129.58, 138.70, 161.18, 161.21, 165.61, 170.54 ppm. IR (ATR): ν= 2924, 1570, 1512, 1256, 1178, 1020, 967, 819 cm⁻¹. HR-MALDI-MS (DCTB): *m/z* calculated for C₁₄H₁₃ClN₂O [M⁺] 260.0711, found 260.0710.

**234a**

<figure><img src="image_170.png" /></figure>

(E,E)-2-(4-methoxystyryl)-4-(4-*N*,*N*-dimethylaminostyryl)-6-methylpyrimidine

C₂₄H₂₅N₃O

MW = 371.47

Compound **234a** was synthesized from 4-ethynylanisole (91 mg, 0.69 mmol) and **233a** (120 mg, 0.44 mmol) following the method A. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 7:3). Yield: 65 mg (40 %); orange solid. *R*<sub>f</sub>: 0.3 (SiO₂; petroleum ether:EtOAc, 7:3). Mp: 79.9–81.5 °C. ¹H NMR (300 MHz, CDCl₃): δ = 2.51 (s, 3H), 3.02 (s, 6H), 3.84 (s, 3H), 6.70–6.73 (m, 2H), 6.83–6.94 (m, 4H), 7.13 (d, ³Jₕ-ₕ = 15.9 Hz, 1H), 7.50–7.53 (m, 2H), 7.58–7.61 (m, 2H), 7.81 (d, ³Jₕ-ₕ = 15.9 Hz, 1H), 7.99 (d,
$^3J_{H-H}$ = 15.9 Hz, 1H) ppm. $^{13}$C NMR (75 MHz, CDCl$_3$): $\delta$=24.34, 40.37, 55.45, 112.20, 114.30, 114.42, 121.59, 124.10, 126.10, 129.14, 129.18, 129.38, 137.08, 151.22, 160.35, 163.16, 164.61, 166.67 ppm. Not all carbon atoms were observed. IR (ATR): $v$ = 2922, 1602, 1509, 1352, 1242, 1169, 973, 809 cm$^{-1}$. HR-MALDI-MS (DCTB): m/z calculated for C$_{24}$H$_{25}$N$_3$O [M$^+$] 371.1992, found 371.1988.

**234b** (E,E)-2-(4-N,N-dimethylaminostyryl)-4-(4-methoxystyryl)-6-methylpyrimidine
C$_{24}$H$_{25}$N$_3$O
MW = 371.47

<figure><img src="image_171.png" /></figure>

Compound **234b** was synthesized from 4-ethynyl-N,N-dimethylaniline (155 mg, 1.06 mmol) and **233b** (177 mg, 0.68 mmol) following the method A. The crude product was purified by column chromatography (SiO$_2$, petroleum ether:EtOAc, 7:3). Yield: 190 mg (75 %); brown solid. R$_{f}$: 0.2 (SiO$_2$; petroleum ether:EtOAc, 7:3). Mp: 123.5–125.7 °C. $^{1}$H NMR (300 MHz, CDCl$_3$): $\delta$ = 2.52 (s, 3H), 3.01 (s, 6H), 3.84 (s, 3H), 6.70–6.73 (m, 2H), 6.90–6.95 (m, 4H), 7.07 (d, $^3J_{H-H}$ = 15.9 Hz, 1H), 7.54–7.58 (m, 4H), 7.83 (d, $^3J_{H-H}$ = 15.9 Hz, 1H), 7.99 (d, $^3J_{H-H}$ = 15.9 Hz, 1H) ppm. $^{13}$C NMR (75 MHz, CDCl$_3$): $\delta$ = 24.37, 40.40, 55.47, 112.22, 114.34, 114.40, 123.30, 124.45, 124.62, 128.94, 129.14, 136.03, 138.13, 151.01, 160.59, 162.46, 165.20, 166.94 ppm. Not all carbon atoms were observed. IR (ATR): $v$ = 2918, 1599, 1509, 1351, 1249, 1162, 970, 808 cm$^{-1}$. HR-MALDI-MS (DCTB): m/z calculated for C$_{24}$H$_{25}$N$_3$O [M$^+$] 371.1992, found 371.1993.
**235a** (E,E,E)-2-(4-methoxystyryl)-4-(4-N,N-dimethylaminostyryl)-6-(4-N,N-diphenylaminostyryl)pyrimidine

$$C_{43}H_{38}N_{4}O$$

$$\text{MW} = 626.79$$

<figure><img src="image_172.png" /></figure>

Compound 235a was synthesized from 234a (45 mg, 0.12 mmol) and 4-N,N-diphenylaminobenzaldehyde (33 mg, 0.12 mmol) following the method B. The crude product was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 8:2). Yield: 46 mg (61 %); orange solid. R<sub>f</sub>: 0.5 (SiO₂; petroleum ether:EtOAc, 8:2). T<sub>d</sub>: 240 °C. ¹H NMR (300 MHz, CDCl₃): δ = 3.03 (s, 6H), 3.85 (s, 3H), 6.71–6.74 (m, 2H), 6.88–7.20 (m, 14H), 7.27–7.32 (m, 4H), 7.48–7.55 (m, 4H), 7.62–7.65 (m, 2H), 7.85 (d, ³J<sub>H-H</sub> = 15.9 Hz, 2H), 8.05 (d, ³J<sub>H-H</sub> = 15.9 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 40.40, 55.47, 112.23, 112.49, 114.31, 121.88, 122.64, 123.71, 124.21, 124.74, 125.21, 126.51, 128.71, 129.18, 129.22, 129.50, 129.54, 129.80, 135.73, 136.92, 137.04, 147.40, 148.87, 151.22, 160.32, 162.75, 163.63, 164.77 ppm. IR (ATR): ν = 2925, 1561, 1490, 1247, 1170, 1144, 971, 694 cm⁻¹. HR-MALDI-MS (DCTB): *m/z* calculated for C₄₃H₃₈N₄O [M⁺] 626.3040, found 626.3038.

**235b** (E,E,E)-2-(4-N,N-dimethylaminostyryl)-4-(4-methoxystyryl)-6-(4-N,N-diphenylaminostyryl)pyrimidine

$$C_{43}H_{38}N_{4}O$$

$$\text{MW} = 626.79$$

<figure><img src="image_173.png" /></figure>

Compound 235b was synthesized from 234b (150 mg, 0.40 mmol) and 4-N,N-diphenylaminobenzaldehyde (110 mg, 0.40 mmol) following the method B. The crude product
was purified by column chromatography (SiO₂, petroleum ether:EtOAc, 7:3). Yield: 84 mg (33 %); orange solid. R<sub>f</sub>: 0.5 (SiO₂; petroleum ether:EtOAc, 7:3). T<sub>d</sub>: 210 °C. <sup>1</sup>H NMR (300 MHz, CDCl₃): δ = 3.02 (s, 6H), 3.85 (s, 3H), 6.72–6.75 (m, 2H), 6.93–7.16 (m, 14H), 7.27–7.32 (m, 4H), 7.48–7.51 (m, 2H), 7.57–7.60 (m, 4H), 7.82–7.90 (m, 2H), 8.05 (d, <sup>3</sup>J<sub>H-H</sub> = 15.9 Hz, 1H) ppm. <sup>13</sup>C NMR (75 MHz, CDCl₃): δ = 40.44, 55.50, 112.26, 112.33, 114.43, 122.63, 123.72, 124.18, 124.36, 124.74, 124.78, 125.22, 128.40, 128.72, 129.05, 129.19, 129.37, 129.54, 129.77, 135.87, 138.09, 147.39, 148.90, 151.01, 160.60, 162.95, 163.03, 165.37 ppm. IR (ATR): ν = 2921, 1500, 1359, 1248, 1166, 971, 809, 693 cm<sup>-1</sup>. HR-MALDI-MS (DCTB): m/z calculated for C<sub>43</sub>H<sub>38</sub>N<sub>4</sub>O [M<sup>+</sup>] 626.3040, found 626.3058.

**239** 2-[[4-(9,9-dimethyl-9,10-dihydroacridine)phenyl]-4-methypyrimidine

<figure><img src="image_174.png" /></figure>

$C_{26}H_{23}N_3$

MW = 377.48

Compound 239 was synthesized from 2-chloro-4-methylpyrimidine (83 mg, 0.64 mmol) and boronic acid pinacol ester 238 (265 mg, 0.64 mmol) following the method C. Yield 138 mg (57 %); pale yellow solid; R<sub>f</sub> = 0.2 (SiO<sub>2</sub>; hexane/EtOAc 9:1); <sup>1</sup>H NMR (400 MHz, CDCl<sub>3</sub>) δ = 8.71 (d, <sup>3</sup>J<sub>H-H</sub> = 5 Hz, 1H), 8.69–8.67 (m, 2H), 7.48–7.46 (m, 4H), 7.13 (d, <sup>3</sup>J<sub>H-H</sub> = 5 Hz, 1H), 6.99–6.91 (m, 4H), 6.36–6.34 (m, 2H), 2.64 (s, 3H), 1.71 (s, 6H) ppm. <sup>13</sup>C NMR (125 MHz, CDCl<sub>3</sub>) δ = 167.69, 164.00, 157.13, 143.48, 140.82, 137.95, 131.63, 130.92, 130.11, 126.50, 125.40, 120.74, 119.04, 114.24, 36.11, 31.46, 24.62 ppm. HR-MALDI-MS (DCTB) m/z calculated for C<sub>25</sub>H<sub>20</sub>N<sub>3</sub> [M-CH<sub>3</sub><sup>+</sup>] 362.1652, found 362.1640.
**240** 2-[4-(9,9-dimethyl-9,10-dihydroacridine)phenyl]-4,6-dimethypyrimidine

<figure><img src="image_175.png" /></figure>

$C_{27}H_{25}N_3$

$$MW = 391.51$$

Compound **240** was synthesized from 2-chloro-4,6-dimethylpyrimidine (111 mg, 0.78 mmol) and boronic acid pinacol ester **238** (321 mg, 0.78 mmol) following the method C. Yield 166 mg (54 %); pale yellow solid; R<sub>f</sub> = 0.3 (SiO<sub>2</sub>; hexane/EtOAc 9:1); <sup>1</sup>H NMR (400 MHz, CDCl<sub>3</sub>) δ = 8.73–8.71 (m, 2H), 7.54–7.51 (m, 4H), 7.07 (s, 1H), 7.04–6.97 (m, 4H), 6.42–6.40 (m, 2H), 2.66 (s, 6H), 1.78 (s, 6H) ppm. <sup>13</sup>C NMR (125 MHz, CDCl<sub>3</sub>) δ = 167.21, 163.87, 143.22, 131.58, 130.99, 130.04, 126.49, 125.40, 120.69, 118.42, 114.26, 36.11, 31.52, 24.36 ppm. HR-MALDI-MS (DCTB) *m/z* calcd for C<sub>26</sub>H<sub>22</sub>N<sub>3</sub> [M-CH<sub>3</sub><sup>+</sup>] 376.1808, found 376.1796.

**241a** (E)-2-[4-(9,9-dimethyl-9,10-dihydroacridine)phenyl]-4-[(4-methoxyphenyl)ethenyl]pyrimidine

<figure><img src="image_176.png" /></figure>

$C_{34}H_{29}N_3O$

$$MW = 495.61$$

Compound **241a** was synthesized from compound **239** (138 mg, 0.36 mmol) and 4-methoxybenzaldehyde (50 mg, 0.36 mmol) following the method B. The crude product was purified by recrystallization. Yield 126 mg (70 %); yellowish solid; R<sub>f</sub> = 0.5 (SiO<sub>2</sub>; CH<sub>2</sub>Cl<sub>2</sub>); mp: 204°C. <sup>1</sup>H NMR (500 MHz, CDCl<sub>3</sub>) δ = 8.78–8.75 (m, 3H), 8.02 (d, <sup>3</sup>J<sub>H-H</sub> = 16 Hz, 1H), 7.63–7.61 (m, 2H), 7.50–7.47 (m, 4H), 7.23–7.22 (m, 1H), 7.04 (d, <sup>3</sup>J<sub>H-H</sub> = 16 Hz, 1H), 6.99–6.93 (m, 6H), 6.38–6.37 (m, 2H), 3.87 (s, 3H), 1.72 (s, 6H) ppm. <sup>13</sup>C NMR (125 MHz, CDCl<sub>3</sub>) δ = 163.95, 163.09, 160.89, 157.81, 143.49, 140.85, 138.12, 137.14, 131.60, 130.99, 130.12, 129.41, 128.57, 126.53, 125.40, 123.79, 120.74, 116.53, 114.49, 114.27, 55.54, 36.13, 31.46 ppm. HR-MALDI-MS (DCTB) *m/z* calcd for C<sub>33</sub>H<sub>26</sub>N<sub>3</sub>O [M-CH<sub>3</sub><sup>+</sup>] 480.2070, found 480.2058.
**241b** (E)-2-[4-(9,9-dimethyl-9,10-dihydroacridine)phenyl]-4-[(6-methoxynaphtalen-2-yl)ethenyl]pyrimidine

$C_{38}H_{31}N_3O$

$MW = 545.67$

<figure><img src="image_177.png" /></figure>

Compound 241b was synthesized from compound 239 (102 mg, 0.27 mmol) and 6-methoxy-2-naphtalenaldehyde (51 mg, 0.27 mmol) following the method B. The crude product was purified by column chromatography (hexane/EtOAc 7:3). Yield 109 mg (74 %); yellowish solid; R<sub>f</sub> = 0.5 (SiO<sub>2</sub>; hexane/EtOAc 7:3); mp: 199 °C. <sup>1</sup>H NMR (400 MHz, CDCl<sub>3</sub>) δ = 8.81–8.78 (m, 3H), 8.20 (d, <sup>3</sup>J<sub>H-H</sub> = 16 Hz, 1H), 7.99 (br s, 1H), 7.83–7.77 (m, 3H), 7.52–7.47 (m, 4H), 7.28–7.16 (m, 4H), 7.01–6.93 (m, 4H), 6.41–6.38 (m, 2H), 3.95 (s, 3H), 1.73 (s, 6H) ppm. <sup>13</sup>C NMR (100 MHz, CDCl<sub>3</sub>) δ = 164.02, 162.96, 158.72, 157.92, 143.60, 140.89, 138.11, 137.76, 135.40, 131.61, 131.25, 131.03, 130.18, 130.13, 129.13, 129.05, 127.62, 126.54, 125.40, 125.26, 124.42, 120.77, 119.53, 116.69, 114.31, 106.16, 55.53, 36.15, 31.47 ppm. HR-MALDI-MS (DCTB) *m/z* calcd for C<sub>37</sub>H<sub>28</sub>N<sub>3</sub>O [M-CH<sub>3</sub><sup>+</sup>] 530.2227, found 530.2221.

**241c** (E)-2-[4-(9,9-dimethyl-9,10-dihydroacridine)phenyl]-4-[(4-*N*,*N*-diphenylaminophenyl)ethenyl]pyrimidine

$C_{45}H_{36}N_4$

$MW = 632.79$

<figure><img src="image_178.png" /></figure>

Compound 241c was synthesized from compound 239 (228 mg, 0.60 mmol) and 4-diphenylaminobenzaldehyde (164 mg, 0.60 mmol) following the method B. The crude product was purified by column chromatography (CH<sub>2</sub>Cl<sub>2</sub>). Yield 182 mg (48 %); yellow solid; R<sub>f</sub> = 0.8 (SiO<sub>2</sub>; CH<sub>2</sub>Cl<sub>2</sub>); mp: 375 °C (dec.). <sup>1</sup>H NMR (400 MHz, CDCl<sub>3</sub>) δ = 8.87–8.84 (m, 3H),
8.09 (d, $^3J_{H-H}$ = 16 Hz, 1H), 7.61–7.56 (m, 6H), 7.41–7.01 (m, 18H), 6.49–6.47 (m, 2H), 1.81 (s, 6H) ppm. $^{13}$C NMR (100 MHz, CDCl$_3$) $\delta$ = 163.92, 163.08, 157.70, 149.22, 147.21, 143.50, 140.85, 138.13, 137.04, 131.53, 130.97, 130.13, 129.56, 129.16, 128.90, 126.51, 125.35, 123.86, 123.76, 122.38, 120.74, 116.43, 114.28, 36.10, 31.44 ppm. HR-MALDI-MS (DCTB) *m/z* calcd for C$_{44}$H$_{33}$N$_4$ [M-CH$_3^+$] 617.2700, found 617.2689.

**242a** (E,E)-2-[4-(9,9-dimethyl-9,10-dihydroacridine)phenyl]-4,6-bis[(4-methoxyphenyl)ethenyl]pyrimidine

$C_{43}H_{37}N_3O_2$

$$MW = 627.77$$

<figure><img src="image_179.png" /></figure>

Compound **242a** was synthesized from compound **230** (158 mg, 0.40 mmol) and 4-methoxybenzaldehyde (110 mg, 0.81 mmol) following the method B. The crude product was purified by recrystallization. Yield 186 mg (73 %); yellow solid; R$_f$ = 0.4 (SiO$_2$; CH$_2$Cl$_2$); mp: 201 °C. $^1$H NMR (500 MHz, CDCl$_3$) $\delta$ = 8.85–8.83 (m, 2H), 8.04 (d, $^3J_{H-H}$ = 16 Hz, 2H), 7.63–7.62 (m, 4H), 7.52–7.48 (m, 4H), 7.19 (s, 1H), 7.06 (d, $^3J_{H-H}$ = 16 Hz, 2H), 7.00–6.93 (m, 8H), 6.41–6.39 (m, 2H), 3.87 (s, 6H), 1.73 (s, 6H) ppm. $^{13}$C NMR (125 MHz, CDCl$_3$) $\delta$ = 163.69, 163.45, 160.74, 143.27, 140.90, 138.60, 136.50, 131.49, 131.17, 130.07, 129.33, 128.80, 126.53, 125.40, 124.20, 120.70, 114.46, 114.33, 114.17, 55.52, 36.13, 31.51 ppm. HR-MALDI-MS (DCTB) *m/z* calcd for C$_{42}$H$_{34}$N$_3$O$_2$ [M-CH$_3^+$] 612.2646, found 612.2637.
**242b** (E,E)-2-[4-(9,9-dimethyl-9,10-dihydroacridine)phenyl]-4,6-bis[(6-methoxynaphtalen-2-yl)ethenyl]pyrimidine

$C_{51}H_{41}N_3O_2$

$$MW = 727.89$$

<figure><img src="image_180.png" /></figure>

Compound 242b was synthesized from compound 240 (100 mg, 0.26 mmol) and 6-methoxy-2-naphtalenaldehyde (96 mg, 0.51 mmol) following the method B. The crude product was purified by recrystallization. Yield 133 mg (72 %); yellow solid; R<sub>f</sub> = 0.3 (SiO<sub>2</sub>; hexane/EtOAc 8:2); mp: 271 °C. <sup>1</sup>H NMR (500 MHz, CDCl<sub>3</sub>) δ = 8.90–8.88 (m, 2H), 8.22 (d, <sup>3</sup>J<sub>H-H</sub> = 16 Hz, 2H), 7.99 (s, 2H), 7.84–7.77 (m, 6H), 7.54–7.49 (m, 4H), 7.27–7.24 (m, 3H), 7.19–7.15 (m, 4H), 7.02–6.94 (m, 4H), 6.44–6.42 (m, 2H), 3.94 (s, 6H), 1.74 (s, 6H) ppm. <sup>13</sup>C NMR (125 MHz, CDCl<sub>3</sub>) δ = 163.74, 163.39, 158.60, 143.35, 140.92, 138.54, 137.18, 135.29, 131.52, 131.42, 131.22, 130.12, 130.10, 129.04, 127.57, 126.56, 125.59, 125.43, 124.44, 120.73, 119.48, 114.58, 114.34, 106.10, 55.52, 36.15, 31.53 ppm. HR-MALDI-MS (DCTB) *m/z* calcd for C<sub>50</sub>H<sub>38</sub>N<sub>3</sub>O<sub>2</sub> [M-CH<sub>3</sub><sup>+</sup>] 712.2959, found 712.2944.

**242c** (E,E)-2-[4-(9,9-dimethyl-9,10-dihydroacridine)phenyl]-4,6-bis[(4-N,N-diphenylaminophenyl)ethenyl]pyrimidine

$C_{65}H_{51}N_5$

$$MW = 902.13$$

<figure><img src="image_181.png" /></figure>

Compound 242c was synthesized from compound 240 (196 mg, 0.50 mmol) and 4-diphenylaminobenzaldehyde (274 mg, 1.00 mmol) following the general procedure for Knoevenagel condensation. The crude product was purified by column chromatography (hexane/CH<sub>2</sub>Cl<sub>2</sub> 1:1) and recrystallization. Yield 110 mg (22 %); yellow solid; R<sub>f</sub> = 0.6 (SiO<sub>2</sub>;
hexane/CH₂Cl₂ 1:1); mp: 233°C. ¹H NMR (500 MHz, CDCl₃) δ = 8.85–8.84 (m, 2H), 8.02 (d, ³Jₘₕ = 16 Hz, 2H), 7.55–7.49 (m, 8H), 7.33–7.30 (m, 8H), 7.21–7.16 (m, 9H), 7.12–7.05 (m, 10H), 7.00–6.94 (m, 4H), 6.42–6.40 (m, 2H), 1.74 (s, 6H) ppm. ¹³C NMR (125 MHz, CDCl₃) δ = 163.74, 163.44, 149.05, 147.81, 147.29, 143.25, 140.90, 138.66, 136.40, 131.49, 131.17, 130.07, 129.56, 129.47, 128.84, 126.52, 125.38, 125.26, 124.23, 123.93, 123.80, 122.51, 120.69, 114.34, 114.11, 36.13, 31.50 ppm. HR-MALDI-MS (DCTB) *m/z* calcd for C₆₄H₄₈N₅ [M-CH₃⁺] 886.3904, found 886.3892.

**244a**

<figure><img src="image_182.png" /></figure>

2-phenylpyrimidine

C₁₀H₈N₂

MW = 156.18

Compound 244a was synthesized from 2-chloropyrimidine (458 mg, 4 mmol) and phenylboronic acid (586 mg, 4.8 mmol) following the method C and purified by column chromatography (8:2, petroleum ether/EtOAc) Yield 524 mg (84 %); pale orange solid. R<sub>f</sub> = 0.5 (8:2, petroleum ether/EtOAc). ¹H NMR (300 MHz, CDCl<sub>3</sub>) δ = 8.81 (d, ³J<sub>H-H</sub> = 5 Hz, 2H), 8.46–8.42 (m, 2H), 7.52–7.47 (m, 3H), 7.19 (t, ³J<sub>H-H</sub> = 5 Hz, 1H) ppm. 13C NMR (75 MHz, CDCl<sub>3</sub>) δ = 164.50, 157.04, 137.44, 130.68, 128.48, 128.08, 118.94, ppm. Data are in accordance with literature.[289]

**244b**

<figure><img src="image_183.png" /></figure>

2-(3-cyanophenyl)pyrimidine

C₁₁H₇N₃

MW = 181.19

Compound 244b was synthesized from 2-chloropyrimidine (458 mg, 4 mmol) and 3-cyanophenylboronic acid (706 mg, 4.8 mmol) following the general procedure for the synthesis of ligands and purified by column chromatography (7:3, petroleum ether/EtOAc) Yield 508 mg (70 %); white solid. R<sub>f</sub> = 0.5 (7:3, petroleum ether/EtOAc). ¹H NMR (300 MHz, CDCl₃) δ = 8.84 (d, ³Jₘₕ = 5 Hz, 2H), 8.79–8.78 (m, 1H), 8.71–8.68 (m, 1H), 7.78–7.75 (m, 1H), 7.63–7.58 (m, 1H), 7.28 (t, ³Jₘₕ = 5 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃) δ = 162.80, 157.60, 138.91, 133.99, 132.36, 132.12, 129.57, 120.14, 118.80, 113.09 ppm. HR-MALDI-MS (DCTB) *m/z* calcd for C₁₁H₈N₃ [M+H⁺] 182.0713, found 182.0713. Data are in accordance with literature.[289]
**244c**

<figure><img src="image_184.png" /></figure>

2-(3-methoxyphenyl)pyrimidine

$C_{11}H_{10}N_2O$

MW = 186.21

Compound 244c was synthesized from 2-chloropyrimidine (606 mg, 5.29 mmol) and 3-methoxyphenylboronic acid (965 mg, 6.35 mmol) following the general procedure for the synthesis of ligands and purified by column chromatography ($CH_2Cl_2$) Yield 651 mg (66 %); pale orange solid. $R_f$ = 0.2 ($CH_2Cl_2$). ¹H NMR (300 MHz, $CDCl_3$) $\delta$ = 8.81 (d, ³$J_{H,H}$ = 5 Hz, 2H), 8.07-8.00 (m, 2H), 7.43-7.38 (m, 1H), 7.19 (t, ³$J_{H,H}$ = 5 Hz, 1H), 7.07-7.03 (m, 1H), 3.91 (s, 3H) ppm. ¹³C NMR (75 MHz, $CDCl_3$) $\delta$ = 164.66, 160.12, 157.28, 139.12, 129.71, 120.81, 119.26, 117.58, 112.68, 55.50 ppm. HR-MALDI-MS (DCTB) m/z calcd for $C_{11}H_{11}N_2O$ [M+H⁺] 187.0866, found 187.0866. Data are in accordance with literature.[289]

**244d**

<figure><img src="image_185.png" /></figure>

2-(3-N,N-diphenylaminophenyl)pyrimidine

$C_{22}H_{17}N_3$

MW = 323.39

Compound 244d was synthesized from 2-chloropyrimidine (96 mg, 0.83 mmol) and 3-N,N-diphenylaminophenylboronic acid (289 mg, 1 mmol) following the general procedure for the synthesis of ligands and purified by column chromatography ($CH_2Cl_2$) Yield 122 mg (45 %); white solid. $R_f$ = 0.6 ($CH_2Cl_2$). ¹H NMR (300 MHz, $CDCl_3$) $\delta$ = 8.75-8.73 (m, 2H), 8.22-8.21 (m, 1H), 8.10-8.07 (m, 1H), 7.40-7.35 (m, 1H), 7.28-7.19 (m, 4H), 7.17-6.99 (m, 8H) ppm. ¹³C NMR (75 MHz, $CDCl_3$) $\delta$ = 164.70, 157.31, 148.50, 148.00, 139.14, 129.67, 129.40, 126.98, 124.32, 124.17, 122.86, 119.22 ppm. HR-MALDI-MS (DCTB) m/z calcd for $C_{22}H_{17}N_3$ [M⁺] 323.1417, found 323.1405.

**244e**

<figure><img src="image_186.png" /></figure>

2-(4-methoxyphenyl)pyrimidine

$C_{11}H_{10}N_2O$

MW = 186.21
Compound **244e** was synthesized from 2-chloropyrimidine (615 mg, 5.36 mmol) and 4-methoxyphenylboronic acid (978 mg, 6.44 mmol) following the general procedure for the synthesis of ligands and purified by column chromatography ($CH_2Cl_2$). Yield 706 mg (71 %); pale yellow solid. $R_f$ = 0.2 ($CH_2Cl_2$). $ ^1H$ NMR (300 MHz, $CDCl_3$) $\delta$ = 8.75 (d, $ ^3J_{H-H}$ = 5 Hz, 2H), 8.41–8.37 (m, 2H), 7.11 (t, $ ^3J_{H-H}$ = 5 Hz, 1H), 7.03–6.98 (m, 2H), 3.88 (s, 3H) ppm. $ ^{13}C$ NMR (75 MHz, $CDCl_3$) $\delta$ = 164.61, 162.03, 157.21, 130.37, 129.87, 118.41, 114.03, 55.43 ppm. HR-MALDI-MS (DCTB) *m/z* calcd for $C_{11}H_{11}N_2O$ [M+H$^+$] 187.0866, found 187.0866. Data are in accordance with literature.[289]

**245a**

<figure><img src="image_187.png" /></figure>

$C_{15}H_{12}ClN_3Pt$

MW = 464.81

Compound **245a** was synthesized from $K_2PtCl_4$ (100 mg, 0.24 mmol) and **244a** (46 mg, 0.29 mmol) following the general procedure for the synthesis of $Pt^{II}$ complexes. Yield 40 mg (36 %) yellow solid. $R_f$ = 0.5 (1:1, EtOAc/$CH_2Cl_2$). $ ^1H$ NMR (300 MHz, $CDCl_3$) $\delta$ = 9.87–9.73 (m, $ ^3J_{H-Pt}$ = 38 Hz, 1H), 9.08–8.91 (m, $ ^3J_{H-Pt}$ = 47 Hz, 2H), 8.79–8.77 (m, 1H), 7.94–7.85 (m, 2H), 7.47–7.42 (m, 2H), 7.17–7.05 (m, 3H), 6.47–6.28 (m, $ ^3J_{H-Pt}$ = 49 Hz, 1H) ppm. $ ^{13}C$ NMR (75 MHz, $CDCl_3$) $\delta$ = 175.83, 158.56, 157.56 (m, $ ^2J_{C-Pt}$ = 8 Hz), 154.18 (m, $ ^2J_{C-Pt}$ = 6 Hz), 141.66, 141.09, 138.13 (m, $ ^2J_{C-Pt}$ = 6 Hz), 132.46 (m, $ ^3J_{C-Pt}$ = 29 Hz), 130.37 (m, $ ^3J_{C-Pt}$ = 23 Hz), 127.79 (m, $ ^3J_{C-Pt}$ = 23 Hz), 126.22 (m, $ ^3J_{C-Pt}$ = 26 Hz), 124.23, 117.65 (m, $ ^4J_{C-Pt}$ = 14 Hz) ppm. HR-MALDI-MS (DCTB) *m/z* calcd for $C_{15}H_{12}ClN_3Pt$ [M$^+$] 464.0362, found 464.0365.

**245b**

<figure><img src="image_188.png" /></figure>

$C_{16}H_{11}ClN_4Pt$

MW = 489.82

Compound **245b** was synthesized from $K_2PtCl_4$ (200 mg, 0.48 mmol) and **244b** (105 mg, 0.58 mmol) following the general procedure for the synthesis of $Pt^{II}$ complexes. Yield 40 mg (36 %) yellowish solid. $R_f$ = 0.6 (1:1, EtOAc/$CH_2Cl_2$). $ ^1H$ NMR (300 MHz, $CDCl_3$) $\delta$ = 9.93–9.79 (m, $ ^3J_{H-Pt}$ = 38 Hz, 1H), 9.01–8.86 (m, 3H), 8.22–8.03 (m, 1H), 8.00–7.91 (m, 1H), 7.53–7.49 (m, 2H), 7.31–7.24 (m, 2H), 6.60–6.42 (m, $ ^3J_{H-Pt}$ = 49 Hz, 1H) ppm. (75 MHz, $CDCl_3$) $\delta$ = 158.96, 157.84, 153.99 (m, $ ^2J_{C-Pt}$ = 6 Hz), 148.15, 138.67, 134.89 (m, $ ^3J_{C-Pt}$ = 29 Hz), 131.14,
130.69, 129.88, 126.58 (m, ³J<sub>C-Pt</sub> = 25 Hz), 119.63, 118.72 (m, ⁴J<sub>C-Pt</sub> = 14 Hz), 107.38 ppm (One quaternary carbon is not observed due to the low solubility of this complex). HR-MALDI-MS (DCTB) *m/z* calcd for C<sub>16</sub>H<sub>11</sub>ClN<sub>4</sub>Pt [M<sup>+</sup>] 489.0315, found 489.0317.

245c

<figure><img src="image_189.png" /></figure>

C<sub>16</sub>H<sub>14</sub>ClN<sub>3</sub>OPt

MW = 494.84

Compound 245c was synthesized from K₂PtCl₄ (100 mg, 0.24 mmol) and 244c (54 mg, 0.29 mmol) following the general procedure for the synthesis of PtII complexes. Yield 55 mg (46%) orange solid. R<sub>f</sub> = 0.6 (1:1, EtOAc/CH₂Cl₂). ¹H NMR (300 MHz, CDCl₃) δ = 9.85–9.70 (m, ³J<sub>H-Pt</sub> = 34 Hz, 1H), 9.07–8.91 (m, ³J<sub>H-Pt</sub> = 45 Hz, 2H), 8.77–8.74 (m, 1H), 7.93–7.87 (m, 1H), 7.46–7.41 (m, 3H), 7.10–7.07 (m, 1H), 6.76–6.72 (m, 1H), 6.36–6.17 (m, ³J<sub>H-Pt</sub> = 48 Hz, 1H), 3.62 (s, 3H) ppm. ¹³C NMR (75 MHz, CDCl₃) δ = 175.63, 158.33, 157.63 (m, ²J<sub>C-Pt</sub> = 10 Hz), 157.14, 154.17 (m, ²J<sub>C-Pt</sub> = 6 Hz), 142.08, 138.04 (m, ²J<sub>C-Pt</sub> = 6 Hz), 131.96, 131.04 (m, ³J<sub>C-Pt</sub> = 28 Hz), 126.17 (m, ³J<sub>C-Pt</sub> = 26 Hz), 120.07 (m, ³J<sub>C-Pt</sub> = 31 Hz), 117.69 (m, ⁴J<sub>C-Pt</sub> = 17 Hz), 111.38 (m, ³J<sub>C-Pt</sub> = 25 Hz) 55.55 ppm. HR-MALDI-MS (DCTB) *m/z* calcd for C<sub>16</sub>H<sub>14</sub>ClN<sub>3</sub>OPt [M<sup>+</sup>] 494.0468, found 494.0472.

245d

<figure><img src="image_190.png" /></figure>

C<sub>27</sub>H<sub>21</sub>ClN<sub>4</sub>Pt

MW = 632.02

Compound 245d was synthesized from K₂PtCl₄ (100 mg, 0.24 mmol) and 244d (94 mg, 0.29 mmol) following the general procedure for the synthesis of PtII complexes. Yield 115 mg (76%) orange solid. R<sub>f</sub> = 0.8 (1:1, EtOAc/CH₂Cl₂). ¹H NMR (300 MHz, CDCl₃) δ = 9.86–9.74 (m, ³J<sub>H-Pt</sub> = 34 Hz, 1H), 9.07–8.92 (m, ³J<sub>H-Pt</sub> = 44 Hz, 2H), 8.70–8.68 (m, 1H), 7.91–7.86 (m, 1H), 7.70–7.69 (m, 1H), 7.45–7.41 (m, 2H), 7.23–7.18 (m, 4H), 7.10–7.06 (m, 5H), 7.98–6.88 (m, 3H), 6.40–6.22 (m, ³J<sub>H-Pt</sub> = 48 Hz, 1H) ppm. ¹³C NMR (75 MHz, CDCl₃) δ = 175.26, 158.43, 157.64 (m, ²J<sub>C-Pt</sub> = 10 Hz), 154.11, 147.84, 144.50, 142.58, 138.09, 135.36, 131.19 (m, ³J<sub>C-Pt</sub> = 28 Hz), 129.77 (m, ³J<sub>C-Pt</sub> = 31 Hz), 129.28, 126.16 (m, ³J<sub>C-Pt</sub> = 26 Hz), 124.49 (m, ³J<sub>C-Pt</sub> = 24 Hz).
Hz), 123.54, 122.36, 117.73 (m, $ ^{4}J_{C-Pt} $ = 13 Hz) ppm. HR-MALDI-MS (DCTB) m/z calcd for C$_{27}$H$_{22}$ClN$_{4}$Pt [M$^{+}$] 632.1175, found 632.1094.

245e

<figure><img src="image_191.png" /></figure>

C$_{16}$H$_{14}$ClN$_{3}$OPt

MW = 494.84

Compound **245e** was synthesized from K$_{2}$PtCl$_{4}$ (100 mg, 0.24 mmol) and **244e** (54 mg, 0.29 mmol) following the general procedure for the synthesis of PtII complexes. Yield 54 mg (45 %) yellow solid. R$_{f}$ = 0.4 (1:1, EtOAc/CH$_{2}$Cl$_{2}$). ¹H NMR (300 MHz, CDCl$_{3}$) δ = 9.78–9.64 (m, ³J$_{H-Pt}$ = 39 Hz, 1H), 9.08–8.89 (m, ³J$_{H-Pt}$ = 46 Hz, 2H), 8.72–8.69 (m, 1H), 7.93–7.87 (m, 1H), 7.84–7.82 (m, 1H), 7.47–7.42 (m, 2H), 7.02–6.99 (m, 1H), 6.71–6.68 (m, 1H), 5.95–5.76 (m, ³J$_{H-Pt}$ = 56 Hz, 1H), 3.68 (s, 3H) ppm. ¹³C NMR (75 MHz, CDCl$_{3}$) δ = 175.20, 162.79, 158.57, 157.50 (m, ²J$_{C-Pt}$ = 11 Hz), 154.17 (m, ²J$_{C-Pt}$ = 6 Hz), 142.79, 138.13 (m, ²J$_{C-Pt}$ = 6 Hz), 134.41, 129.56 (m, ³J$_{C-Pt}$ = 27 Hz), 126.17 (m, ³J$_{C-Pt}$ = 26 Hz), 116.50 (m, ³J$_{C-Pt}$ = 24 Hz), 116.43 (m, ⁴J$_{C-Pt}$ = 19 Hz), 108.86, 55.17 ppm. HR-MALDI-MS (DCTB) m/z calcd for C$_{16}$H$_{14}$ClN$_{3}$OPt [M$^{+}$] 494.0468, found 494.0476.
ANNEXES

*Annex 1. Calculated absorption and emission data for compounds 48, 49, 61, 62, 232i and 232m. f is oscillator strength.*

<table><thead><tr><th rowspan="2">Compd</th><th colspan="2">Absorption:<br>λ<sub>abs</sub> (nm)/f<br>(orbitals contributions)</th><th colspan="2">Emission:<br>λ<sub>em</sub> (nm)/f</th></tr><tr><th>PBE0</th><th>CAM-B3LYP</th><th>PBE0</th><th>CAM-B3LYP</th></tr></thead><tbody><tr><td>48</td><td>357 / 1.05<br>(HOMO → LUMO)</td><td>326 / 1.17<br>(HOMO → LUMO)</td><td>376 / 1.11</td><td>363 / 1.22</td></tr><tr><td>49</td><td>402 / 0.93<br>(HOMO → LUMO)</td><td>348 / 1.20<br>(HOMO → LUMO)</td><td>538 / 0.07</td><td>387 / 1.21</td></tr><tr><td>61 Confo1</td><td>403 / 1.60<br>(HOMO → LUMO)<br>316 / 0.79<br>(HOMO-1 → LUMO+1)</td><td>351 / 2.24<br>(HOMO → LUMO)<br>313 / 0.14<br>(HOMO-1 → LUMO)</td><td>427 / 1.65</td><td>377 / 2.27</td></tr><tr><td>61 Confo2</td><td>390 / 1.09<br>(HOMO → LUMO)<br>343 / 0.58<br>(HOMO → LUMO+1)<br>329 / 0.37<br>(HOMO-1 → LUMO)<br>(HOMO → LUMO+1)</td><td>344 / 1.67<br>(HOMO → LUMO)<br>305 / 0.57<br>(HOMO-1 → LUMO)<br>(HOMO → LUMO+1)</td><td>421 / 1.11</td><td>373 / 1.66</td></tr><tr><td>62 Confo1</td><td>442 / 1.71<br>(HOMO → LUMO)<br>346 / 0.51<br>(HOMO-1 → LUMO+1)</td><td>370 / 2.49<br>(HOMO → LUMO)<br>335 / 0.16<br>(HOMO-1 → LUMO)<br>(HOMO → LUMO+1)</td><td>481 / 1.47</td><td>396 / 2.54</td></tr><tr><td>62 Confo2</td><td>428 / 1.34<br>(HOMO → LUMO)<br>393 / 0.22<br>(HOMO-1 → LUMO)<br>371 / 0.30<br>(HOMO-1 → LUMO+1)<br>366 / 0.16<br>(HOMO → LUMO+1)</td><td>364 / 1.89<br>(HOMO → LUMO)<br>331 / 0.53<br>(HOMO-1 → LUMO)<br>(HOMO → LUMO+1)</td><td>471 / 1.15</td><td>390 / 1.92</td></tr><tr><td>232i Confo1</td><td>416 / 0.43<br>(HOMO → LUMO)<br>389 / 1.11<br>(HOMO-1 → LUMO)<br>374 / 0.66<br>(HOMO-2 → LUMO)<br>(HOMO → LUMO+1)<br>342 / 0.40<br>(HOMO-2 → LUMO+1)<br>(HOMO-1 → LUMO+1)</td><td>351 / 1.81<br>(HOMO → LUMO)<br>331 / 1.33<br>(HOMO-2 → LUMO)<br>(HOMO → LUMO+1)<br>308 / 0.34<br>(HOMO-1 → LUMO)<br>(HOMO → LUMO)</td><td>504 / 0.05</td><td>378 / 1.90</td></tr><tr><td>232i Confo2</td><td>405 / 0.27<br>(HOMO → LUMO)<br>376 / 1.27<br>(HOMO-1 → LUMO)<br>(HOMO → LUMO+1)<br>373 / 0.80<br>(HOMO-1 → LUMO)<br>(HOMO → LUMO+1)</td><td>344 / 1.34<br>(HOMO → LUMO)<br>(HOMO-1 → LUMO)<br>329 / 2.09<br>(HOMO → LUMO+1)<br>306 / 0.29<br>(HOMO-2 → LUMO+1)<br>(HOMO → LUMO)</td><td>490 / 0.06</td><td>374 / 1.38</td></tr></tbody></table>
<table><tbody><tr><td></td><td>358 / 0.29<br>(HOMO-2 → LUMO+1)<br>(HOMO-2 → LUMO)<br>(HOMO-1 → LUMO+1)</td><td></td><td></td><td></td></tr><tr><td rowspan="5">232i Confo3</td><td>410 / 0.39<br>(HOMO → LUMO)</td><td>347 / 1.67<br>(HOMO → LUMO+1)</td><td>500 / 0.07</td><td>377 / 1.68</td></tr><tr><td>382 / 0.76<br>(HOMO-1 → LUMO)</td><td>329 / 1.70<br>(HOMO → LUMO+1)<br>(HOMO-2→LUMO)</td><td></td><td></td></tr><tr><td>371 / 1.19<br>(HOMO-2 → LUMO)<br>(HOMO → LUMO+1)</td><td>307 / 0.36<br>(HOMO-1 → LUMO)<br>(HOMO → LUMO)</td><td></td><td></td></tr><tr><td>350 / 0.55<br>(HOMO-1 → LUMO+1)</td><td></td><td></td><td></td></tr><tr><td>444 / 0.97<br>(HOMO → LUMO)</td><td>369 / 2.26<br>(HOMO → LUMO)<br>(HOMO-1 → LUMO)</td><td>536 / 0.06</td><td>400 / 2.17</td></tr><tr><td rowspan="5">232m Confo1</td><td>428 / 0.75<br>(HOMO-1 → LUMO)</td><td>353 / 1.41<br>(HOMO-2 → LUMO)<br>(HOMO → LUMO+1)</td><td></td><td></td></tr><tr><td>414 / 0.68<br>(HOMO-2 → LUMO)</td><td>322 / 0.14<br>(HOMO-2 → LUMO)<br>(HOMO → LUMO+1)</td><td></td><td></td></tr><tr><td>380 / 0.42<br>(HOMO → LUMO+1)<br>(HOMO-2 → LUMO)<br>(HOMO-1 → LUMO+1)</td><td></td><td></td><td></td></tr><tr><td>431 / 0.65<br>(HOMO → LUMO)</td><td>363 / 1.73<br>(HOMO-1 → LUMO)<br>(HOMO → LUMO)<br>(HOMO-2 → LUMO+1)</td><td>525 / 0.07</td><td>395 / 1.72</td></tr><tr><td>418 / 1.33<br>(HOMO-1 → LUMO)<br>(HOMO → LUMO+1)</td><td>352 / 2.14<br>(HOMO → LUMO+1)<br>(HOMO → LUMO+2)</td><td></td><td></td></tr><tr><td rowspan="5">232m Confo2</td><td>410 / 0.76<br>(HOMO → LUMO+1)<br>(HOMO-1 → LUMO)</td><td></td><td></td><td></td></tr><tr><td>437 / 0.87<br>(HOMO → LUMO)<br>(HOMO-1 → LUMO)</td><td>365 / 2.09<br>(HOMO → LUMO)<br>(HOMO-1 → LUMO)</td><td>535 / 0.07</td><td>396 / 2.06</td></tr><tr><td>420 / 0.65<br>(HOMO-1 → LUMO)<br>(HOMO → LUMO)</td><td>352 / 1.77<br>(HOMO-2 → LUMO)<br>(HOMO → LUMO+1)</td><td></td><td></td></tr><tr><td>412 / 1.12<br>(HOMO-2 → LUMO)<br>(HOMO → LUMO+1)</td><td></td><td></td><td></td></tr><tr><td>384 / 0.28<br>(HOMO-2 → LUMO)<br>(HOMO-1 → LUMO+1)</td><td></td><td></td><td></td></tr></tbody></table>
<figure><img src="image_192.png" /><figcaption>**Annex 2.** Overlap of normalized TD-DFT calculated (red) and experimental (black) electronic absorption spectra of 241 and 242. The vertical red lines represent oscillator strengths.</figcaption></figure>
<table><caption>Annex 3. TD-DFT calculated parameter of 241 and 242.</caption><thead><tr><th>Compd</th><th>λ nm (eV)</th><th>f</th><th>orbitals contribution</th></tr></thead><tbody><tr><td rowspan="5">241a</td><td>511 (2.42)</td><td>0.0001</td><td>HOMO→LUMO</td></tr><tr><td>358 (3.46)</td><td>1.1470</td><td>HOMO→LUMO+1</td></tr><tr><td>338 (3.67)</td><td>0.0565</td><td>HOMO-1→LUMO</td></tr><tr><td>318 (3.89)</td><td>0.3929</td><td>HOMO-1→LUMO+1<br>HOMO-4→LUMO</td></tr><tr><td>539 (2.30)<br>382 (3.25)</td><td>0.0000<br>1.1391</td><td>HOMO→LUMO<br>HOMO-1→LUMO</td></tr><tr><td rowspan="4">241b</td><td>351 (3.53)</td><td>0.1550</td><td>HOMO-1→LUMO+1<br>HOMO-3→LUMO<br>HOMO-1→LUMO+2</td></tr><tr><td>510 (2.43)</td><td>0.0000</td><td>HOMO→LUMO<br>HOMO→LUMO+1</td></tr><tr><td>435 (2.85)</td><td>0.9606</td><td>HOMO-1→LUMO</td></tr><tr><td>362 (3.43)<br>344 (3.61)<br>340 (3.65)</td><td>0.0940<br>0.0181<br>0.0013</td><td>HOMO-1→LUMO+1<br>HOMO-1→LUMO+2<br>HOMO→LUMO+2<br>HOMO-1→LUMO+3</td></tr><tr><td rowspan="4">242a</td><td>517 (2.40)<br>406 (3.05)</td><td>0.0000<br>1.1153</td><td>HOMO→LUMO<br>HOMO-1→LUMO</td></tr><tr><td>376 (3.30)</td><td>0.1756</td><td>HOMO-2→LUMO+1<br>HOMO→LUMO+2</td></tr><tr><td>334 (3.72)</td><td>0.3406</td><td>HOMO-2→LUMO+1</td></tr><tr><td>529 (2.34)<br>436 (2.84)<br>407 (3.05)</td><td>0.0000<br>1.4466<br>0.0794</td><td>HOMO→LUMO<br>HOMO-1→LUMO<br>HOMO-2→LUMO<br>HOMO-1→LUMO+1</td></tr><tr><td rowspan="5">242b</td><td>495 (2.50)<br>482 (2.57)</td><td>0.0000<br>1.4500</td><td>HOMO→LUMO<br>HOMO-1→LUMO</td></tr><tr><td>448 (2.77)<br>381 (3.26)<br>377 (3.29)</td><td>0.1747<br>0.3942<br>0.0753</td><td>HOMO-2→LUMO<br>HOMO-2→LUMO+1<br>HOMO-1→LUMO+1</td></tr><tr><td>450 (2.80)<br>440 (3.10)</td><td>0.0000<br>0.0000</td><td>HOMO→LUMO<br>HOMO-1→LUMO</td></tr><tr><td>448 (2.77)<br>381 (3.26)<br>377 (3.29)</td><td>0.1747<br>0.3942<br>0.0753</td><td>HOMO-2→LUMO<br>HOMO-2→LUMO+1<br>HOMO-1→LUMO+1</td></tr></tbody></table>

<figure><img src="image_193.png" /><figcaption>Annex 4. Excited-state dynamics of 241a (A) and 241b (B) in neat film with detection in two emission bands.</figcaption></figure>

<figure><img src="image_194.png" /></figure>
<table><caption>Annex 5. Relevant computed data for complexes 245.</caption><thead><tr><th></th><th>245a</th><th>245b</th><th>245c</th><th>245d</th><th>245e</th></tr><tr><th>Compound</th><th>CN</th><th>OMe</th><th>NPh<sub>2</sub></th><th>OMe</th><th>OMe</th></tr></thead><tbody><tr><td>HOMO-LUMO gap (eV)</td><td>4.15</td><td>4.19</td><td>3.80</td><td>3.28</td><td>4.23</td></tr><tr><td>Pt-Cl (Å)</td><td>2.454</td><td>2.440</td><td>2.454</td><td>2.453</td><td>2.454</td></tr><tr><td>[Wiberg bond indice]</td><td>[0.301]</td><td>[0.312]</td><td>[0.301]</td><td>[0.303]</td><td>[0.302]</td></tr><tr><td>Pt-N(py) (Å)</td><td>2.020</td><td>2.020</td><td>2.019</td><td>2.019</td><td>2.021</td></tr><tr><td>[Wiberg bond indice]</td><td>[0.396]</td><td>[0.399]</td><td>[0.398]</td><td>[0.398]</td><td>[0.395]</td></tr><tr><td>Pt-N(ppy) (Å)</td><td>2.016</td><td>2.019</td><td>2.017</td><td>2.017</td><td>2.016</td></tr><tr><td>[Wiberg bond indice]</td><td>[0.411]</td><td>[0.408]</td><td>[0.411]</td><td>[0.410]</td><td>[0.412]</td></tr><tr><td>Pt-C(ppy) (Å)</td><td>1.978</td><td>1.971</td><td>1.981</td><td>1.978</td><td>1.977</td></tr><tr><td>[Wiberg bond indice]</td><td>[0.689]</td><td>[0.696]</td><td>[0.679]</td><td>[0.687]</td><td>[0.686]</td></tr><tr><td>Py/Pt(ppy) torsion angle (°)</td><td>66</td><td>67</td><td>65</td><td>65</td><td>65</td></tr><tr><td>NAO charges</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Pt</td><td>0.63</td><td>0.65</td><td>0.63</td><td>0.64</td><td>0.63</td></tr><tr><td>Cl</td><td>-0.69</td><td>-0.68</td><td>-0.69</td><td>-0.69</td><td>-0.69</td></tr><tr><td>N(py)</td><td>-0.52</td><td>-0.52</td><td>-0.52</td><td>-0.52</td><td>-0.52</td></tr><tr><td>N(ppy)</td><td>-0.54</td><td>-0.54</td><td>-0.54</td><td>-0.54</td><td>-0.55</td></tr><tr><td>C(ppy)</td><td>-0.19</td><td>-0.17</td><td>-0.22</td><td>-0.20</td><td>-0.17</td></tr></tbody></table>
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**Titre** : Matériaux luminescents hétérocycliques organiques et organométalliques: vers des applications OLEDs

**Mots clés** : diode électroluminescente organique (OLED), chromophore push-pull, pyrimidine, platine, luminescence

**Résumé** : Depuis 1987, date à laquelle la première diode électroluminescente organique (OLED) a été préparée par C. W. Tang et S. V. Slyke (Eastman Kodak company), il y a eu un grand intérêt pour le développement de dispositifs d'éclairage à base de matériaux organiques. Dans ce manuscrit, des luminophores organiques et organométalliques portant un hétérocycle pyrimidine en tant que groupement attracteur d'électrons sont discutés. Trois séries avec des caractéristiques structurelles différentes ont été préparées: (i) Une série de 2,4-di (arylvinyl)- et de 2,4,6-tri(arylvinyl)pyrimidines avec des groupes électro-donneurs périphériques identiques ou différents, (ii) Une série de 4-arylvinyl- et de 4,6-di(arylvinyl)pyrimidines portant un groupement phénylacridine torsadé en position

2 du cycle pyrimidine (iii) Des complexes de platine (II) cyclométalé à base de 2-phénylpyrimidine. Les propriétés de photoluminescence de tous les dérivés finaux ont été mesurées. Des relations structure-photoluminescence au sein de chaque série ont été tirées de ces résultats et discutées en détail. Des phénomènes de luminescence intéressants, tels que l'émission accordable par protonation, l'émission induite par l'agrégation, l'émission duale, l'émission à l'état solide ou l'émission de lumière blanche, ont été observés pour certains de ces dérivés.

**Title** : Organic and organometallic heterocyclic luminescent materials: towards OLED applications

**Keywords** : organic light-emitting diode (OLED), push-pull chromophore, pyrimidine, platinum, luminescence

**Abstract** : Since 1987, when the first organic light-emitting diode (OLED) was prepared by C. W. Tang and S. V. Slyke (Eastman Kodak company), there has been a great interest in the development of lighting devices based on organic materials. In this dissertation, organic and organometallic luminophores bearing pyrimidine heterocycle as electron-withdrawing moiety are discussed. Three series with different structural features were prepared: (i) 2,4-di(arylvinyl)- and 2,4,6-tri(arylvinyl)-pyrimidines with identical or different peripheral electron-donating groups, (ii) 4-arylvinyl- and 4,6-di(arylvinyl)pyrimidines with twisted phenylacridan structure in position 2 of pyrimidine ring and (iii) 2 phenylpyrimidine

cyclometalated platinum (II) complexes. Photoluminescence properties of all final derivatives were measured. Structure-photoluminescence relationships within each series were drawn from these results and thoroughly discussed. Interesting luminescence phenomena, such as tuneable emission by protonation, aggregation-induced emission, dual emission, solid-state emission or white light emission, were observed for certain derivatives across the series.