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Investigation into the Oxygen-Involved Electrochemiluminescence of Porphyrins and Its Regulation by Peripheral Substituents/Central Metals Guiqiang Pu, Zhaofan Yang, Yali Wu, Ze Wang, Yang Deng, Yunjing Gao, Zhen Zhang, and Xiaoquan Lu Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.8b05027 • Publication Date (Web): 14 Jan 2019 Downloaded from http://pubs.acs.org on January 19, 2019

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Analytical Chemistry

Investigation into the Oxygen-Involved Electrochemiluminescence of Porphyrins and Its Regulation by Peripheral Substituents/Central Metals Guiqiang Pu,a, b Zhaofan Yang,b Yali Wu,b Ze Wang,b Yang Deng,a YunJing Gao,b Zhen Zhang,a and Xiaoquan Lu* a, b a.

Tianjin Key Laboratory of Molecular Optoelectronic, Department of Chemistry, Tianjin University, Tianjin, 300072, P. R. China. b. Key Laboratory of Bioelectrochemistry and Environmental Analysis of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, P. R. China.

*E-mail: [email protected]; [email protected]. Tel.: +86 931 797 1276. Fax: +86 931 797 1276. ABSTRACT: We provide evidence of oxygen-involved electrochemiluminescence (ECL) of metal-free porphyrins and metalloporphyrins firstly. O2•− and OH•, that are oxygen intermediates, are indispensable for the formation of excited porphyrins, which has been proven by trapping free radical strategies. The wide differences regarding emission location and mechanism between metal-free porphyrins [including meso-tetra(4-methoxyphenyl)porphine (H2TMPP), meso-tetraphenylporphyrin (H2TPP) and meso-tetra(4-carboxyphenyl)porphine (H2TCPP)] and metalloporphyrins (MTPP) depend on whether protons are present in the center of the porphin ring. Besides, the oxygen-involved ECL of porphyrins can be controlled regularly by peripheral substituents with different polarities. Because of the stretched molecular structure and the decrease in electron density around the protons located at porphin ring; electron-withdrawing groups are more conducive to protons being attacked by O2•−, as well as the enhancement of porphyrins ECL. The ECL efficiency [ФECL, which is normalized with respect to Ru(bpy)3(PF6)2 (taking ФECL of Ru(bpy)3(PF6)2 = 1 )] is gradually improved from H2TMPP (ФECL = 0.16), H2TPP (ФECL = 2.20) to H2TCPP (ФECL = 3.83); and the ФECL = 4.21 of Zn(II)TPP is significantly higher than other MTPP [e.g. Co(II)TPP and Cu(II)TPP]. A deeper understanding regarding the improvement of porphyrins ECL efficiency and new application towards porphyrins-related devices can be achieved from this work.

Porphyrins (containing metal-free porphyrins and metalloporphyrins), which play irreplaceable role in organism such as photosynthesis and oxygen transport, are receiving constant attention because of their unique optoelectronic properties;1,2 and the delocalized π electrons endow them with outstanding performances in numerous domains.3-5 Recently, expanded porphyrins, reported by Stuyver et al., were excellent candidates for molecular switches in molecular electronic devices mainly attributed to high combination density, fast response and high energy efficiency.6 Zhang et al. reported that the conversion efficiency of solar cells could be significantly improved in the presence of zinc(II) 5,10,15,20tetraethynylporphyrin as a core and perylene diimide as end groups.7 Porphyrins and their derivatives have also been an important member in electrochemiluminescence (ECL) as typical luminophore.8-11 The ECL behavior of 5,10,15,20tetraphenylporphyrin (H2TPP) in methylene chloride was reported firstly by Bard under the condition of deoxygenation, which the radiation was derived from the collision between H2TPP radical anion (H2TPP•−) and H2TPP radical cation (H2TPP•+).8 Recently, our group, for the first time, proposed the cathode ECL phenomenon of the meso-tetra(4-

carboxyphenyl)porphine (H2TCPP)/K2S2O8.12,13 We have also constructed a novel biomimetic luminescence technology defined as interfacial electron-induced ECL (IEIECL), the pathways of charge transfer at the interface are probed conveniently using the ECL of H2TPP.14 However, the roles of oxygen intermediates (e. g. O2•−, 1O2, OH•) in the ECL process of porphyrins are still ambiguous; the impact of peripheral substitutes and central metals on the ECL of porphyrins has not been probed meticulously yet. More comprehensive understanding to oxygen-involved ECL of porphyrins is urgently desired. ECL involves the production of excited state species and ultimately light from the reaction of electrogenerated oxidants and reductants.15,16 It is the perfect product produced by the combination of chemiluminescence and electrochemistry.17-18 Conventional ECL sensors with co-reactant pathways and ECL luminescent device with annihilation mechanism have been approved in the past two decades.19-24 However, the emergence of ECL as a functional characterization technique, like UV-vis and Raman spectra, is even more exciting. For instance, Wang et al. successfully distinguished the active roles of point defects in semiconductor Cd−In−S nanoclusters by

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Scheme 1. Oxygen-involved ECL of metal-free porphyrins and metalloporphyrins, along with the structures of investigated porphyrins.

ECL technology.25 Xu et al. also employed ECL microscopy to image the electrocatalysis of a novel bimetallic gold−platinum Janus nanoparticle.26 Furthermore, the effect of peripheral substitutes on luminophore can be distinguished using ECL.2729 Hence more meticulous and unique perspective information can be presented for materials with the help of ECL. In the present work, we describe the oxygen-involved ECL of various porphyrins for the first time (shown in Scheme 1). The participation of oxygen contributes to a remarkable improvement in ECL strength and stability through a new approach, which is completely different from the annihilation mechanism of the collision between cation and anion radical of porphyrins.8 Hydroxyl radicals (OH•) and superoxide anion radicals (O2•-), the intermediates of O2, are indispensable for the anode ECL of metal-free porphyrins and cathode ECL of metalloporphyrins, respectively; and it has been confirmed by trapping free radical strategies. The location and mechanism of ECL radiation are completely transformed after the porphyrin centre is occupied by metal ions; the intrinsic interaction was subsequently investigated. In addition, peripheral substituents with different polarities can directly regulate the ECL behavior of porphyrins on account of the molecular spatial structure and electron density distribution. The ECL spectrum was measured finally to illustrate the correctness of the mechanisms. This study shows that the protons located at porphin ring, molecular spatial structure, and the distribution of delocalized π electrons have a regular impact on the oxygeninvolved ECL of porphyrins.

EXPERIMENTAL SECTION Reagents. Meso-tetra(4-methoxyphenyl)porphine (H2TMPP), meso-tetraphenylporphyrin (H2TPP), mesotetra(4-carboxyphenyl)porphine (H2TCPP), zinc(II) mesotetraphenylporphyrin [Zn(II)TPP] were synthesized according to the literature; and 1H NMR (500 MHz) characterization of the as-synthesized porphyrins can be found in Supporting Information.8 Copper(II) mesotetraphenylporphine [Cu(II)TPP, 99%], cobalt(II) mesotetraphenylporphine [Co(II)TPP, 99%], iron(III) mesotetraphenylporphine chloride [Fe(III)TPP, 99%] and tris(2,2′-bipyridine)ruthenium(II) hexafluorophosphate [Ru(bpy)3(PF6)2, +99.8%] were obtained from Aladdin Industrial Corporation (Shanghai, China). Tetra-nbutylammonium hexafluorophosphate [(TBA)PF6, 99%] obtained from Aladdin Industrial Corporation (Shanghai,

China) was recrystallized three times from absolute ethanol and dried for 48 hours under vacuum at 60 °C. Anhydrous 1, 2, -dichloromethane (DCM, +99.9%, H2OIH2TPP>IH2TMPP) further illustrates the correctness of the aforementioned mechanism. The ECL efficiency (ФECL, which is the standard for judging the performance of luminophore) of the porphyrins can be obtained by means of the following formula.47-49 ФECL = Ф0ECL (IQf0/I0Qf)

(9)

Ф0

Where the value of the ECL of the 1.00 mM standard Ru(bpy)3(PF6)2 is artificially defined as 1.00. Values of Qf0 and Qf are the amount of transferred electrons in the process of ECL reaction toward Ru(bpy)3(PF6)2 and porphyrins, respectively. I0 and I represent the ECL intensity of Ru(bpy)3(PF6)2 under the deoxygenated conditions and porphyrins under the ambient conditions, respectively. Subsequently, the ФECL of the three metal-free porphyrins were all obtained, which gradually increased from H2TMPP (ФECL = 0.16), H2TPP (ФECL = 2.20) to H2TCP (ФECL = 3.83) (shown in table S2). The above results further demonstrate that electron-withdrawing groups substitution is more conducive to the enhancement of oxygen-involved ECL of porphyrins.

Figure 6. Oxygen-involved ECL spectrum of the H2TMPP(red trace), H2TPP(black trace), H2TCPP(green trace) and Zn(II)TPP(blue trace) in DCM:DMF (v:v = 3:1) under the ambient conditions. The concentrations of all porphyrins are 0.50 mM. The inset shows the ECL spectrum of H2TMPP.

Oxygen-involved ECL of metalloporphyrins. The introduction of various metal ions into the porphyrin ring permits a series of physiological functions to porphyrins, such as chlorophyll with magnesium ions and heme with iron ions.33, 50 Meaningful difference exists in optical and electrochemical properties of metalloporphyrins compared to its protoporphyrin. However, changes in oxygen-involved ECL of porphyrins after the addition of metal ions have hardly been explored. Hence in the

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current work, Zn(II)TPP was chosen to illustrate the above puzzle. As shown by the blue trace in Figure 7a, O2 was first reduced at -0.85 V vs Fc+/Fc when scanning toward the negative direction, followed by the production of ZnTPP•− derived from ZnTPP (at -1.46 V vs Fc+/Fc). Simultaneously, intense ECL (~7400.a.u.) was produced (red trace in Figure 7a), which is a completely different result compared to anode ECL of H2TPP. More efficient affinity of Zn(II)TPP to O2 leads to a stronger ECL signal compared metal-free porphyrins. The ФECL of Zn(II)TPP, ФECL=4.21, is also superior to other porphyrins. It is worth noting that a new ECL radiation peak (at 700 nm) is generated in addition to the radiant peak of Zn(II)TPP located at 603 and 652 nm (blue trace in Figure 6). This indicates that another substance is also excited during the scanning process. Stable and continuous ECL always existed under the condition of applying constant voltage (at -1.80 V vs Fc+/Fc) shown in Figure 7b, which indicates that the oxygen-involved ECL of Zn(II)TPP is a completely steady state. The anode ECL of Zn(II)TPP cannot appear when the scan is in the positive direction, and the optimizations for scanning potential and stability testing are also explored in Supporting Information and are shown in Figure S9 and Figure S10. Obviously, the pathway to produce excited Zn(II)TPP [Zn(II)TPP*] is altered due to the addition of zinc ion.

Figure 7. (a) Oxygen-involved ECL (red trace) and CV (blue trace) of the 0.50 mM Zn(II)TPP in DCM:DMF (v:v = 3:1) under the ambient conditions; R(O2), R(D), R(D•−) represent the reduction potential of O2, Zn(II)TPP and Zn(II)TPP•−, respectively; scan rate: 0.10 V·s-1. (b) Oxygen-involved ECL of the 0.50 mM Zn(II)TPP under the condition of applying constant voltage (-1.80 V). (c) Spatial molecular structure of H2TPP and Zn(II)TPP.

Figure 8. Oxygen-involved ECL (a) and absorption spectra (b) from 0.50 mM Zn(II)TPP (red trace), 0.50 mM Zn(II)TPP+0.05 mM TEOA (blue trace), 0.50 mM Zn(II)TPP+0.05 mM Quinone (green trace) and 0.50 mM deoxygenated Zn(II)TPP (black


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trace). Inset: Fluorescent photos of 0.50 mM Zn(II)TPP (I), 0.50 mM Zn(II)TPP+0.05 mM TEOA (II), 0.50 mM Zn(II)TPP +0.05 mM Quinone (III) and 0.50 mM deoxygenated Zn(II)TPP (IV) (left); as well as enlargement of 530-630 nm region (right).

Trapping free radical strategies were also used to explore intermediate produced by O2 reduction and the cathode ECL mechanism of Zn(II)TPP. As shown in Figure 8, The ECL of Zn(II)TPP could not be quenched by the addition of TEOA (blue trace); but it almost disappeared after adding Quinone (green trace) or deoxygenated treatment (black trace). Furthermore, the Zn(II)TPP is not denatured by the radical trappers because of the constancy of the UV-vis spectra and the FL characteristics before and after injecting radical trappers. This indicates that only O2•− exists in the process of Zn(II)TPP* production. Therefore, it can be concluded that the oxygen-involved ECL mechanism of Zn(II)TPP is as shown in eqs 10 - 16. Cathode scanning: O2 + e = O2•−

Ec = -0.85 V vs Fc+/Fc

Zn(II)TPP + e = Zn(II)TPP•− +

Zn(II)TPP•−

e=

Zn(II)TPP2−

Ec = -1.46 V vs

Fc+/Fc

Ec = -1.72 V vs

Fc+/Fc

Zn(II)TPP + Zn(II)TPP2− = Zn(II)TPP•−

(10) (11) (12) (13)

Zn(II)TPP•− + O2•− = Zn(II)TPP* + O22− or = Zn(II)TPP2− + 1O2* 1O

2*

=

3O

2

(14)

+ hv (λ = 700 nm)

(15)

Zn(II)TPP* = Zn(II)TPP + hv (λ = 603 and 652 nm)

(16)

Unlike H2TPP, there is no proton in the porphin ring of Zn(II)TPP, and the generated O2•− cannot be further converted into H2O. Hence Zn(II)TPP* and excited singlet oxygen molecules (1O2*), derived from the interaction of Zn(II)TPP•− with cumulated O2•−, are directly produced in the cathode region and releases overlaped cathode ECL. In addition, because the occupying of zinc ion has a negligible effect on the spatial framework and electron density distribution (Figure 7c and Figure 5), the internal causes of different oxygen-involved ECL between metalloporphyrins and metal-free porphyrins is whether protons are present in the center of the porphin ring.

shown in Figure 9 and Figure S11, although they have similar absorption spectra, fluorescence spectrum, electrochemical behavior and ECL mechanism (Eqs 10 - 16) compared to Zn(II)TPP, there are significant differences regarding ECL radiation intensity. Moreover, no ECL signal is detected and its reduction process is irreversible for Fe(III)TPP(Figure S12). It can be confirmed that there is a large difference in the oxygen-involved ECL intensity for different metalloporphyrin even if their ECL mechanism are the same. The possible reason is that different metalloporphyrins have different affinity for O2•−. which is being studied more deeply in our group.

CONCLUSION In summary, we have described the oxygen-involved ECL behavior of metal-free porphyrins and metalloporphyrins firstly; the intensity of this new ECL is about one hundred times compared to reported annihilation pathway. We have explored the role of various intermediates derived from O2 in the process of excited-state porphyrin production through trapping free radical strategies. For metal-free porphyrins, the anode ECL radiation comes from the interaction between OH• and porphyrins radical anions. But for metalloporphyrins, O2•− reacts directly with porphyrins radical anions, leading to overlaped cathode ECL. The above differences mainly depend on whether protons are present in the center of the porphin ring. Besides, the oxygen-involved ECL of porphyrins can be controlled regularly by peripheral substituents with different polarities. The difficulty of attacking protons located at porphin ring by O2•− determines the strength of ECL, which can be considered from the molecular space structure and electron density distribution. A deeper understanding regarding the improvement of porphyrins ECL efficiency can be achieved from this work, and this research will open new possibilities towards porphyrin-related sensors and lightemitting devices.

ASSOCIATED CONTENT Supporting Information

NMR characterization of as-synthesized various porphyrins; additional CV curves; and ECL response curves. The Supporting Information is available free of charge on the ACS Publications website.

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]; [email protected]. Tel.: +86 931 797 1276. Fax: +86 931 797 1276. Figure 9. (a) Oxygen-involved ECL (dark cyan trace) and CV (black trace) of the 0.50 mM Co(II)TPP in DCM:DMF (v:v = 3:1) under the ambient conditions. (b) Oxygen-involved ECL (magenta trace) and CV (black trace) of the 0.50 mM Cu(II)TPP in DCM:DMF (v:v = 3:1) under the conditions of ambient conditions. R(O2), R(E), R(E•−), R(F) and R(F•−) represent the reduction potential of O2, Co(II)TPP, Co(II)TPP•−, Cu(II)TPP and Cu(II)TPP•−, respectively; scan rate: 0.10 V·s-1.

Co(II)TPP and Cu(II)TPP were subsequently explored in order to confirm the correctness of the above conclusions. As

ORCID Xiaoquan Lu: 0000-0003-2375-668X

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This work was supported by National Natural Science Foundation of China (Grant Nos. 21575115, 21327005, 21705117, 21427808); the Program for Chang Jiang Scholars and Innovative Research Team, Ministry of Education, China (Grant No. IRT-16R61) and the Program of Gansu



Provincial Higher Education Research Project (Grant No. 2017-D-01). Furthermore, we extend our thanks to Professor Guizheng Zou at Shandong University for his support.

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Investigation into the Oxygen-Involved Electrochemiluminescence of

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