Chain Length Effect on the Structure and Photoelectrochemical Properties of Self-Assembled Monolayers of Porphyrins on Gold Electrodes

Abstract

Disulfides, with a systematic series of alkyl spacers containing porphyrins at both terminals, were prepared to investigate the effect of the spacer length on the structure and photoelectrochemical properties of self-assembled monolayers (SAMs) of the porphyrins on a gold electrode. The structure of the SAMs was studied using ultraviolet (UV)−visible absorption spectroscopy in transmission mode, cyclic voltammetry, UV−visible ellipsometry, and fluorescence spectroscopy. These measurements showed that as the length of the spacers increases, the SAMs tend to form highly ordered structures on the gold electrodes. In addition, the structures of the monolayers vary depending on the even and odd number of the methylene spacers (n). From these measurements a porphyrin dimer model is proposed in that the two porphyrins take J-aggregate-like partially stacked structures in the monolayers. Photoelectrochemical studies were carried out in argon-saturated Na2SO4 aqueous solution containing methyl viologen as an electron carrier using the modified gold working electrode, a platinum wire counter electrode, and a Ag/AgCl reference electrode. The quantum yield increases in a zigzag fashion with an increase in the spacer length up to n = 6 and then starts decreasing slightly as the chain lengths become longer. A plausible explanation for the photocurrent trend comes from the following points: (i) there are two competitive deactivation pathways for the excited singlet state of the porphyrin dimer, i.e., the quenching by the electrode via energy transfer and by the electron carrier via electron transfer, (ii) the porphyrin aggregation enhances the rate of nonradiative pathway in the excited state, and (iii) the electron transfer rate from the gold electrode to the resulting porphyrin cation radical decreases with an increase of the spacer lengths. These results will provide basic information for the construction of molecular assembly with photoactive function on surface.

Tetraferrocenylporphyrins as active components of self-assembled monolayers on gold surface

“…This difference is probably due to a decrease of the dielectric constant in the diffuse monolayer when compared to that of the bulk solution. 16 Interestingly, a significant shift in the half-wave potential was found switching from 1 (E 1/2 = +0.145 V vs. FcH/FcH + ) to 2 (E 1/2 = +0.185 V vs. FcH/FcH + ) due to the introduction of 1-butanethiol. As for ZnTFcP-containing monolayers ( Fig.…”

“…Meso-arylporphyrins are well-known sensitizers for photocurrent generation and several papers have reported their properties. 16,18 Imahori and Fukuzumi 18 showed that an electron transfer can occur from an electron donor (TEOA = triethanolamine) and the singlet excited state of such porphyrins. Although electrochemical experiments were carried out in a different solvent/electrolyte system, we took into account the oxidation potential measured for 2, i.e.…”

Controlled rotary motion of light-driven molecular motors assembled on a gold film

“…Energy transfer from chromophores to nearby metal particles and films has been observed. [47][48][49][50][51][52] For example, we showed that in a gold break junction reversibility of single molecule isomerization was blocked.…”

Design of fluorescent materials for chemical sensing

“…However, SAM-based fluorescent sensors development has encountered difficulties due to an efficient fluorescent quenching by the metal surfaces. 202,203 Only few reports have been published on the detection of fluorescence from selfassembled monolayers on gold. Motesharei and Myles reported in 1998 the preparation of layers of a fluorescent isophthalic acid adsorbate on gold.…”