Estatus científico de la terminología

The preparation of novel push-pull Pcs was carried out by an unsymmetric functionalization of the diodo-functionalized Pc 12 with electron donating and anchoring/electron withdrawing groups.

We started with the synthesis of compound 30 (Scheme 2.4) that holds a carboxyethynyl group as electron-withdrawing group and a dimethylaminophenylethynyl moiety as electron-donor. It is worth mentioning that carboxyethynyl had been proved in our group as the optimal anchoring unit for Pc photosensitizers, since it provides directionality and fast electron transfer to the TIO2 in the device.¹⁰¹ On the other hand, the dimethylaminophenylethynyl group had been previously used in Pors^131,132 and can be easily linked to the Pc through a reliable Sonogashira coupling. Starting from 12, 27 was obtained in good yield (83%) by a Sonogashira reaction with propargylic alcohol. Then, 28 was obtained through another Sonogashira coupling between 27 and 4-ethynyl-N,N-dimethylaniline also in good yield (88%). The oxidation of 28 to 30 was carried out following a two-step procedure widely used for the oxidation of primary alcohol to carboxylic acids.¹⁰¹ The first step involved the treatment with IBX, leading to 29 in nearly quantitative yields, but, unfortunately, the last oxidation reaction with sulfamic acid and NaClO2 afforded a mixture of compounds that were identified by MS-spectrometry as derivatives of 30 with different contents of chlorine atoms. This chlorination is probably occurring at the highly activated dimethylamino ring (Scheme 2.4).

Scheme 2.4. Synthesis of 30. Conditions: a) propargylic alcohol, Pd(PPh3)4, CuI, Et3N, THF, 83%; b) 4-ethynyl-N,N-dimethylaniline, Pd(PPh3)4, CuI, Et3N, THF, 88%; c) IBX,

THF, DMSO; d) Sulfamic acid, NaClO2, THF; e) IBX, THF, DMSO and then N-hydroxysuccinimide, THF, DMSO, 90%.

In view of this result, a one – step oxidation of the hydroxymethylethynyl derivate 18 to 30 was tried (Scheme 2.4), following the conditions described by Mazitsche et al,¹³³ which consist in the oxidation of a primary alcohol group to a carboxylic acid in the presence of IBX and certain O-nucleophiles at ambient temperature.

In fact, the reaction of 28 with IBX afforded the aldehyde 29, which in situ reacts with N-hydroxysuccinimide to give compound 30 in high yield. It is worth mentioning that changing the reaction sequence, that is, coupling first the 4-ethynyl-N,N-dimethylaniline to Pc 12, followed by Sonogashira reaction with propargyl alcohol and subsequent oxidation, gave rise to lower overall yields.

Next we focused on the preparation of Pcs endowed with a N-linked diphenylamino unit, similarly to the case of record Por sensitizers.⁵⁶ The direct linkage of the N atom to the Pc core is expected to increase the electron donating effect of the amino group over the Pc. Amination reactions can be performed by either Buchwald – Hartwig amination protocols or by Ullmann conditions. As amination reactions over iodo derivatives usually takes place using high excess of the amine, we proceed first with the amination of Pc 27 (i.e., having only one iodine atom available for the coupling) with bis(4-hexylphenyl)amine (31), which was synthetized using a modified version of the procedure reported in literature.¹³⁴ Using conditions that had been previously described for the amination of Pcs,¹³⁵ namely Pd2(dba)3 as the catalyst, BINAP as ligand and Cs2CO3 as the base in dry toluene at 120°C (Scheme 2.5), did not afford the desired amination and, in fact, only deiodinated products were obtained. On the other hand, we decided to try an Ullmann coupling to carry out the linkage of the

diphenylamino derivative, since this procedure has been recently applied with success to introduce good electron-donating groups such as carbazoles, phenoxazines or phenothiazines in the meso positions of different Por substrates in good yield.¹³⁶ We performed this Cu(I) – catalyzed reaction on Pc 27 and Pc 32, the latter holding a formyl – ethynyl group obtained by IBX oxidation of 27.

However, both reactions failed to give the desired coupling with amine 31 (Scheme 2.5). During the development of the experimental work, optimized conditions for the Buchwald – Hartwig coupling of diphenylamino derivatives and bromoporphyrins were found in the group. In our case, application of these conditions, namely Pd2(dba)3, ^tBu3P and ^tBuONa in refluxing toluene, was the key to obtain Pc derivatives containing diphenylamino units. First, as the reaction is carried out with excess of the amine, we decided to prove the amination with Pc 27. However, as in previous attempts, the reaction did not work. MS analysis confirmed that, under these conditions, losses of iodine and hydroxymethyl residues were taking place in the reaction (Scheme 2.5).

Scheme 2.5. Functionalization using Buchwald – Hartwig or Ullmann methodologies.

Conditions: i) 27, amine 31, Pd2(dba)3, BINAP, Cs2CO3, dry toluene at 120°C; ii) 27 or 32, amine 31, CuI, N-phenyl benzohydrazide, Cs2CO3, dry DMSO at 120°C; iii) 27,

amine 31, Pd2(dba)3, ^tBu3P, ^tBuONa, dry toluene at 120°C.

Finally, we decided to carry out the amination reaction over Pc 12 following the same reaction conditions, but with less excess of amine 31. In this case, a mixture of products was obtained, from which, the di-coupled product 34, the fully deiodinated Pc 36, and the desired product 33 combined with the mono deiodinated derivative 35 were separated (Scheme 2.6). Unfortunately, a complete separation of 33 from 35 was not achieved. As previously mentioned, deiodinated Pc derivatives had been observed in previous Buchwald – Hartwig

amination reactions, and also as secondary products in other Pd – catalyzed conversions at high temperatures. In order to decrease the amount of deiodinated Pcs and facilitate the isolation of Pc 33, we performed the amination of 12 at lower temperature, i.e., at 100ºC, but it did not yield the target compound.

Hence, it was necessary to set the following reactions with a mixture of Pcs 33 and 35, relying on the lack of reactivity of the deiodinated derivative 35 under the applied conditions.

Scheme 2.6. Mixture of products obtained from the Buchwald coupling of 12.

With Pc 30 in our hands, we proceeded to prepare two different push–pull Pcs holding different acceptor/anchoring groups (Scheme 2.7). The first one (Pc 39) was obtained through a Sonogashira coupling between 33 and propargylic alcohol in the same conditions already mentioned for the synthesis of 27. This reaction proceeded in good yield, and compound 37 could be easily separated from the deiodinated Pc 35. The oxidation of 37 with IBX in order to obtain 38 proceeded in quasi-quantitative yield. Finally, the last oxidation of the formyl group to carboxylic acid by NaClO2 in presence of sulfamic acid (Scheme 2.7) gave the target compound 39 in 58% yield. Interestingly, in this case, the formation of products that contain chlorine atoms was not observed, probably due to the lower activation of the diphenylamino rings for the electrophilic substitution with chlorine in comparison with the N,N-dimethylaminophenyl ring of product 30.

Last, the second Pc synthetized starting from 33 was obtained by the incorporation of the benzothiadiazole (BTD) unit 43 as a -conjugated linker in

between the anchoring group and the chromophore. The BTD unit had been already successfully used with Pors¹³⁷ to obtain high PCEs in DSSCs because of its high electron acceptor effect. Its synthesis is shown in Scheme 2.8. Starting from 4-iodo-methylbenzoate, the organotin aryl compound 40 was formed, which was subsequently reacted with commercial dibromobenzothiadiazole in order to obtain compound 41. After that, a simple Sonogashira coupling was carried out to obtain the desired compound 42 having a trimethylsilylacetylene group.

Further deprotection with TBAF afforded compound 43 (Scheme 2.8). This product was used to functionalize 33 by another Sonogashira reaction, followed by a rapid and quantitative hydrolysis of the ester group to afford the final push-pull Pc 45 (Scheme 2.7).

Scheme 2.7. Synthesis of Pcs 39 and 45. Conditions: i) Propargylic alcohol, Pd(PPh3)4, CuI, Et3N, THF to obtain 37, 75%; ii) IBX, DMSO to obtain 38, 77%; iii) Sulfamic acid, NaClO2, THF to obtain 39, 58%; i’) Benzothiadiazole 43, Pd(PPh3)4, CuI, Et3N, THF to

obtain 44, 64%; ii’) NaOH 20%, MeOH/THF to obtain 45, 62%.

Scheme 2.8. Synthesis of benzothiadiazole 43. Conditions: a) Pd(PPh3)4, toluene, reflux, 73%; b) CsF, PdCl2, CuI, ^tBu3P, DMF, 45ºC, 17%; c) PdCl2(PPh3)2, CuI, THF,

Et3N, 50ºC, 20%; d) TBAF, THF, r.t.

The structure of Pc 30, 39 and 45 was unequivocally confirmed by MALDI-TOF mass spectrometry, UV−vis, IR and NMR. UV-vis spectra demonstrate the lack of aggregation of these products in THF solution (Figure 2.19). A bathochromic shift of the Q – band is observed from 30 (691 nm) to 39 (704 nm) and 45 (708 nm), due to an increase of the electron – releasing effect of the N – donor group, and also to an increase of the electron – withdrawing effect of the acceptor/anchoring group. The Q band of Pcs 39 and 45 is notably wider, yielding improved light-harvesting capabilities in the red region. The larger extinction coefficient of the Q band of Pc 45 (i.e., 4.94 vs 4.58 and 4.48 for 30 and 39, respectively) is also remarkable, and similar to that previously observed in Pors containing the BTD unit.⁵⁶ In the 500 – 600 nm region of the spectra of Pcs 39 and 45, a weak and constant absorption is observed, which is absent in the spectrum of 30 and is probably as a result of an electron-donating effect from the diphenylamino group to the Pc core. Noteworthy, a band at 448 nm is present also in the spectrum of 45 associated to the BTD unit.⁵⁶

Figure 2.19. UV-vis spectra of 30 ( ^__ 8 M), 39 ( ^__ 10 M) and 45 ( ^__ 7 M) in THF.

A complete assignment of all the signals in the ¹H-NMR spectra is not realizable because of the complexity of the systems, but characteristic peaks of the diphenylamino rings for Pcs 29 and 45, and of the dimethylamino ring for Pc 30 are discernible. Figure 2.20 shows, as representative example, the ¹H-NMR of Pc 39 in THF-d8, in which it is possible to discriminate the principal different groups of protons.

Figure 2.20. ¹H-NMR spectrum of 39 in THF-d8. 0

0,1 0,2 0,3 0,4

300 350 400 450 500 550 600 650 700 750 800

Absorbance (a. u.)

Wavelength (nm)

alkyl chains

Pc diphenylamine

Steady-state fluorescence spectra of compounds 30, 39 and 45 were also recorded by exciting at the heights of the corresponding Q bands (Figure 2.21).

Notably, the emissions of compounds 39 and 45 are notably quenched as a consequence of the strong electron donation from the directly linked dimethylamino group.

a)

b) c)

Figure 2.21. Absortion (solid lines) and fluorescence spectra (dashed line) of Pcs a) 30 (excitation wavelength, 685 nm), b) 39 (excitation wavelength, 700 nm), and c) 45

(excitation wavelength, 702 nm) in THF.

Electrochemical characterization of 30, 39 and 45 was performed using cyclic voltammetry in 0.1M tetrabutylammonium phosphate (TBAP) CH2Cl2 solutions, using ferrocene as internal reference. Figure 2.22 shows the cyclic

processes were obtained by square wave measurements (Figure 2.22). The respective oxidation/reduction potentials, together with the HOMO/LUMO values vs the normal hydrogen electrode (NHE), are summarized in Table 2.1. HOMO and LUMO levels were estimated from peak potentials by setting the oxidative peak potential of Fc/Fc⁺ vs NHE to 0.642 V. ^139,140

Figure 2.22. Cyclic voltammograms and square-wave voltammetry of Pcs 30, 39 and 45. Potential values are registered vs Ag/AgNO3 reference electrode.

0,E+00 2,E-06 4,E-06 6,E-06 8,E-06 1,E-05

0 0,3 0,6 0,9 1,2

Current

Potential/V vs Ag/AgNO₃ Pc 30

Pc 39 Pc 45

-5E-06 -4E-06 -3E-06 -2E-06 -1E-06 0E+00 -1,5 -1,2 -0,9 -0,6 -0,3 0

Current

Potential/V vs Ag/AgNO₃

Table 2.1. First oxidation and reduction potentials and HOMO/LUMO levels for Pcs 30,

a Reversible. ^b Irreversible. ^c Quasi-reversible.

The first oxidation reactions of compounds 30, 39 and 45 were reversible or quasi-reversible processes, with values in the range 0.42–0.26V versus Fc/Fc⁺. The potential of compounds 39 and 45 are 120 and 160 mV lower than that of 30, respectively, thus evidencing the strong impact that the direct linkage of the diphenylamino group has on the HOMO of the Pc macrocycle. On the other hand, the first reduction is irreversible for all compounds and occurs at very similar potentials, between -1.40 V (for 30) and -1.45 V (for 45) versus Fc/Fc⁺. Incorporation of the BTD unit between the Pc core and the COOH group in 45 has limited influence on the electronic properties of the Pc, namely, a slight stabilization of the HOMO and LUMO levels with regard to Pc 39. Notably, the electrochemical HOMO–LUMO bandgap is consistent with the optical (E^0-0) bandgap obtained from the interception between the absorption and emission spectra (Figure 2.21).

Figure 2.23 shows an energy-level diagram for the Pc dyes, comparing their HOMO–LUMO levels with the standard potential for the CB of TiO2 vs. NHE (ECB

= –0.5 V), and for the iodide/triiodide (I^–/I3–) redox couple vs. NHE (E = 0.53 V).^141–

144 The driving forces for electron injection from the Pc excited singlet state to the CB of TiO2 (ΔGinj) and for the regeneration of the Pc radical cation by the I^–/I3–

redox couple (ΔGreg) in a conventional DSSC have been determined (Table 2.1).

Both processes are thermodynamically feasible and allow electron transfer in a solar cell.

Figure 2.23. Schematic energy-levels diagram of Pcs 30, 39 and 45.

Additionally, DFT and TDDFT calculations have been performed to get insights into the electronic structure of the synthetized dyes, which can help in the understanding of the photovoltaic results of the corresponding cells. In all three dyes, the HOMO has extended delocalization toward the donor moiety (Figure 2.24). However, the LUMO has a slight delocalization onto the acceptor group for Pcs 30 and 39 and is rather centered in the Pc core for 44, whereas the LUMO⁺¹ is completely centered in the Pc core for Pcs 30 and 45 and has a small delocalization toward the acceptor group in the case of 39 (Figure 2.24). The degree of delocalization of the LUMO and LUMO⁺¹ orbitals on the acceptor group is one of the factors considered to rationalize the photovoltaic behaviour of these molecules, as mentioned in the next section.

Figure 2.24. Contour plots for the HOMO (left), LUMO (center), and LUMO⁺¹ (right) of Pcs 30 (top), 39 (middle), and 45 (bottom) computed by using

wB97xD/6-31G(d)/CPCM(THF). Isovalue set to 0.02.

HOMO LUMO LUMO⁺¹

30

45 39

2.3.2 Photovoltaic studies of novel donor-π-acceptor substituted Pcs