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Substituent and Solvent Effects on the Hyperporphyrin Spectra of Diprotonated Tetraphenylporphyrins†

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Substituent and Solvent Effects on the Hyperporphyrin Spectra of Diprotonated Tetraphenylporphyrins† 3486 J. Phys. Chem. A 2003, 107, 3486-3496 Substituent and Solvent Effects on the Hyperporphyrin Spectra of Diprotonated Tetraphenylporphyrins† James R. Weinkauf, Sharon W. Cooper, Aaron Schweiger, and Carl C. Wamser* Department of Chemistry, Portland State UniVersity, Portland, Oregon 97207-0751 ReceiVed: September 11, 2002; In Final Form: NoVember 13, 2002 UV-visible spectra have been studied for a series of p-substituted tetraphenylporphyrins (TPPs) titrated with strong acid in various solvents. Substituent effects on the Soret and Q(I) absorption peaks and the fluorescence emission peaks have been treated by Hammett correlations. In general, there are only small effects with electron-withdrawing substituents, but electron-donating substituents lead to lower energy transitions, with especially strong effects observed in the case of the diprotonated porphyrins with good electron-donating substituents (hyperporphyrin effects). The hyperporphyrin effects are attributed to the crossing of a π molecular orbital on the substituted phenyl group above the usual porphyrin π highest occupied molecular orbital. For the neutral TPPs, this crossing is estimated to occur with a substituent as electron-donating as p-methoxy, and for the diprotonated TPPs, the crossing occurs at approximately unsubstituted TPP. Distinctive solvent effects on the spectra and the Hammett correlations are observed. Introduction protonated TPP8 shows a nonplanar (saddle) form, in which the four N-H bonds adopt positions alternately above and below Porphyrins have a wonderful repertoire of optical and the mean porphyrin plane; this twisting allows the phenyl rings electronic properties that allow them to play a variety of roles, to become more coplanar with the mean molecular plane. Thus, in nature and in technical applications.1 The spectroscopy of it has been of some interest to determine the extent to which porphyrins has received detailed treatment because of its peripheral substituents can interact with the central porphyrin relevance to functionality as well as its fascinating variety.2 In positions, where the charges are nominally located. the ultraviolet-visible region, the characteristic spectrum includes the intense Soret band around 400 nm and a series of Systematic effects of para substituents on the properties of TPPs have been studied electrochemically9,10 and spectroscopi- bands (Q bands) through the visible range. Different patterns 11-13 of peripheral substitutions, π conjugations, or central metal cally. In general, electron-donating substituents lead to red incorporations lead to well-characterized spectral patterns.2 shifts for both the Soret (B) and Q bands, maintaining - 13 Specialized spectral features also appear based on interactions approximately a constant B Q splitting. The magnitude of between porphyrin units, such as H and J aggregates3 or the energy shifts can be correlated with Hammett substituent constants, either a mix of resonance and inductive components12 interactions with other molecules based on charge, π stacking, + 13 9,10 4,5 or σ values. Substituent effects on the redox potentials H-bonding, or hydrophobic effects. The Gouterman four 12 orbital model suffices to explain most of the fundamental and pKa values also correlate with Hammett substituent features of porphyrin and metalloporphyrin electronic spectra,2 constants. but there are increasingly common examples of unusual spectral Nevertheless, several studies of TPPs substituted with highly features that require additional interpretation. electron-donating groups have shown unusual spectroscopic Acid-base behavior of porphyrins has also been well-studied. effects. Studies with para-hydroxy TPP derivatives have il- The tetrapyrrole skeleton allows for loss of two N-H protons lustrated numerous spectral and structural features, complicated to form a dianion in strong base or gain of two protons to form by accompanying redox processes leading to paramagnetic 14-16 a dication in acid. Each case leads to an increase in symmetry species and quinonelike structures. Para-amino TPP deriva- and corresponding changes in the spectra, which are often tives have long been known to have unusual spectral properties, distinctive in their colors (e.g., purple tetraphenylporphyrins in particular broader, lower energy bands for both the Soret and 17,18 (TPPs) change to green in acid). Moreover, peripheral substit- the visible regions. Protonation of these amino-substituted uents may confer additional acidic or basic properties, a tactic derivatives leads to further red shifts and unusual red bands. often used to control water solubility.4 For example, tetrakis(p-dimethylaminophenyl)porphyrin (TD- The basic structure of the porphyrin framework can be MAPP) can be titrated with acid to show protonated derivatives + + 19 described as a planar aromatic system, but steric effects around from 2to 6. The diprotonated form shows an unusually the periphery, in particular meso substituents that interact with intense red band, described as a hyperporphyrin. A similar band 6 has been observed in long chain dialkylamino-substituted â pyrrole positions, often lead to nonplanar forms of porphyrins. 20 TPP has been observed in three different crystal forms, but in porphyrins in thin films. each case, the meso phenyl groups are significantly twisted from Hyperporphyrins have been defined as porphyrins that exhibit - the plane of the porphyrin.7 The X-ray structure of doubly extra bands in the UV visible, either due to specific interactions with metal orbitals or due to charge transfer interactions with 2 † Part of the special issue “George S. Hammond & Michael Kasha substituents. Molecular orbital calculations supporting the Festschrift”. charge transfer nature of hyperporphyrin bands in diprotonated 10.1021/jp022046f CCC: $25.00 © 2003 American Chemical Society Published on Web 12/20/2002 Spectra of Diprotonated Tetraphenylporphyrins J. Phys. Chem. A, Vol. 107, No. 18, 2003 3487 mL of propionic acid and brought to reflux. Pyrrole (6.2 mL, 89 mmol) was added, followed by para-methoxybenzaldehyde (8.9 mL, 73 mmol), and the solution was stirred at reflux for 45 min. The reaction mixture was allowed to cool to room temperature and then placed in an ice bath, yielding purple crystals. Thin-layer chromatography (TLC) indicated two major components, identified as TMPP and HM3PP. Several mil- ligrams of pure HM3PP were isolated by flash chromatography using toluene/chloroform solutions as eluting solvents. NMR (CDCl3): -2.75 ppm (s, 2H, NH), 4.09 ppm (s, 9H, OCH3), 7.20 ppm (d, 2H, H-ArOH), 7.28 ppm (d, 6H, H-ArOCH3), 8.07 Figure 1. Tetrasubstituted porphyrins and abbreviations. TPP, X ) ppm (d, 2H, H-ArOH), 8.14 ppm (d, 6H, H-ArOCH ), 8.86 ppm ) ) ) ) 3 H; TTP, X CH3; THPP, X OH; TMPP, X OCH3; TAPP, X (broad singlet, 8H, pyrroles). ICR-MS: M + 1 ) 721.25 (calcd NH ; TDMAPP, X ) N(CH ) ; TNPP, X ) NO ; TCPP, X ) COOH; 2 3 2 2 721.297). TCMPP, X ) CO2CH3. Mixed substituent porphyrins: HnMmPP, X ) OH or OCH3;H1M3PP, H2M2PP, H3M1PP. DMAnPP, X ) Hor H2M2PP and H3MPP. Although the above preparation yielded N(CH3)2; DMA1PP, DMA2PP, DMA3PP. traces of other porphyrins, improved yields of the other substituted derivatives were obtained by using a different ratio TAPP have recently been presented.21 We have collected UV- of the two benzaldehydes. The above procedure was modified visible absorption and fluorescence spectroscopy data on a series by using para-hydroxybenzaldehyde (2.5 g, 20 mmol), para- of substituted TPPs (Figure 1) to categorize the effects of methoxybenzaldehyde (4.5 mL, 37 mmol), and pyrrole (5.5 mL, substituents on the spectra. We have also investigated the role 80 mmol). The reaction mixture did not yield crystals but a of solvent effects on the spectra. thick tar, which was treated with toluene and filtered. The toluene solution was evaporated, and the solid residue was Experimental Section chromatographed several times on silica gel using chloroform eluent and then 1-5% MeOH in chloroform. The cis and trans Materials. Solvents and reagents were typically the highest isomers of H M PP were not separated. grade commercially available and were stored under nitrogen 2 2 - with molecular sieves. Methanol (MeOH), acetonitrile (ACN), H2M2PP. NMR (CDCl3): 2.75 ppm (s, 2H, NH), 4.12 ppm and tetrahydrofuran (THF) were Sigma-Aldrich high-perfor- (s, 6H, OCH3), 7.23 ppm (d, 4H, H-ArOH), 7.30 ppm (d, 4H, mance liquid chromatography (HPLC) grade, 99.9% with no H-ArOCH3), 8.09 ppm (d, 4H, H-ArOH), 8.14 ppm (d, 4H, inhibitors. Dimethyl sulfoxide (DMSO) and dimethylformamide H-ArOCH3), 8.86 ppm (broad singlet, 8H, pyrroles). MALDI- + ) (DMF) were Aldrich spectrometric grade, 99.9 and 99.8%, MS: M 1 707.27 (calcd 707.266). - respectively. Dichloromethane (DCM) was from Mallinckrodt, H3MPP. NMR (CDCl3): 2.76 ppm (s, 2H, NH), 4.12 ppm indicating 0.0007 mequiv/g titratable acid; however, this source (s, 3H, OCH3), 7.23 ppm (d, 6H, H-ArOH), 7.31 ppm (d, 2H, of DCM did not detectably protonate the porphyrins, a common H-ArOCH3), 8.09 ppm (d, 6H, H-ArOH), 8.14 ppm (d, 2H, problem with most chlorinated solvents from most other sources. H-ArOCH3), 8.88 ppm (broad singlet, 8H, pyrroles). MALDI- Acids used for titrations were either trifluoroacetic acid (TFA) MS: M + 1 ) 693.27 (calcd 693.250). or methanesulfonic acid (MSA). TFA was from Aldrich, 99+% Spectroscopy. UV-visible absorption spectra were taken on spectrometric grade, and MSA was from J. T. Baker, 98%. a Shimadzu model 260 usinga2mmslit width. Data acquisition Water was distilled water available in the lab, boiled before was via a GPIB card and a PC using Shimadzu UV-265 software use. (version 3.1). Fluorescence spectra were taken on a Spex All of the porphyrins used were tetrasubstituted in their meso Fluorolog model 112 spectrofluorimeter using a 150 W xenon positions with para-substituted phenyl groups. The various light source and right angle detection with optically dilute symmetrically substituted porphyrins used in this study are samples (<1 µM).
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