溶剂对四苯基卟啉氯化锰飞秒瞬态吸收光谱的影响

doi:10.6023/A23010017

化学学报 ›› 2023, Vol. 81 ›› Issue (4): 345-350.DOI: 10.6023/A23010017 上一篇下一篇

研究论文

溶剂对四苯基卟啉氯化锰飞秒瞬态吸收光谱的影响

李万红^a, 于明月^a, 王丽丽^b, 朱德煌^c, 彭素红^a^,^*(), 王惠^b, 刘海洋^d

a 宜春学院化学与生物工程学院宜春 336000
b 中山大学光电材料与技术国家重点实验室广州 510275
c 武夷学院生态与资源工程学院绿色与化工技术福建省高等学校重点实验室南平 354300
d 华南理工大学化学系广州 510641

投稿日期:2023-01-27 发布日期:2023-04-06
基金资助:
国家自然科学基金(21671068); 宜春学院2018地方发展研究中心项目(DF2018021); 江西省教育厅科学技术项目(GJJ2201723); 江西省教育厅科学技术项目(GJJ2201724); 江西省卫生健康委科技计划项目(202212701); 绿色化工技术福建省高校重点实验室开放基金(WYKF-GCT2022-1)

Sovlent Influence on the Femtosecond Transient Absorption Spectra of Tetraphenylporphyrin Manganese(III) Chloride

Wanhong Li^a, Mingyue Yu^a, Lili Wang^b, Dehuang Zhu^c, Suhong Peng^a^,^*(), Hui Wang^b, Haiyang Liu^d

a College of Chemsitry and Bioengineering, Yichun University, Yichun 336000, China
b State Key Laboratory of Optoelectronics Materials and Technologies, Sun Yat-sen University, Guangzhou 510275, China
c Key Laboratory of Green Chemical Technology of Fujian Province University, College of Ecology and Resources Engieneering, Wuyi University, Nanping 354300, China
d Department of Chemistry, South China University of Technology, Guangzhou 510641, China

Received:2023-01-27 Published:2023-04-06
Contact: * E-mail: shpeng1987@163.com
Supported by:
National Natural Science Foundation of China(21671068); 2018 local Development Research Center Project of Yichun Univeristy(DF2018021); Science and Technology Research Project of Education Comission of Jiangxi Province(GJJ2201723); Science and Technology Research Project of Education Comission of Jiangxi Province(GJJ2201724); Science and Technology Research Project of Health Commission of Jiangxi Province(202212701); Open Fund of Key Laboratory of Green Chemical Technology of Fujian Province University(WYKF-GCT2022-1)

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摘要/Abstract

采用稳态和飞秒瞬态吸收光谱技术研究了四苯基卟啉氯化锰Mn^III(TPP)Cl在甲苯(TOL)、二氯甲烷(DCM)、乙腈(ACN)和N,N-二甲基甲酰胺(DMF)四种溶剂中的光物理性质. 结果表明随溶剂极性的增加, 其紫外-可见吸收光谱的B带与Q带与飞秒瞬态对应的漂白信号均发生蓝移. 随着Mn^III(TPP)Cl二氯甲烷溶液浓度的增加, ⁵S₂态寿命无明显变化, ⁵S₁态和⁵T₁态寿命依次变短. 在四种溶剂中, 非极性溶剂甲苯中的⁵S₂态寿命最长而⁵S₁和⁵T₁态寿命最短, 这与⁵S₂→⁵S₁能差最大, ⁵S₁→⁵S₀能差最小对应. 从弱极性DCM到极性更大的DMF时, ⁵S₁和⁵T₁态寿命依次缩短. 从非极性TOL到极性ACN时⁵S₂态寿命依次缩短. 在极性溶剂DMF中, 锰卟啉的⁵S₂态寿命更长. 这主要是配位溶剂DMF中的氮原子与锰卟啉⁵S₂激发态进行配位, 从而使五配位的锰卟啉变成六配位的锰卟啉, 结果使锰卟啉的激发态寿命延长. 锰卟啉在DMF中具有更长的⁵S₂态寿命是溶剂的配位作用与极性作用共同影响的结果且配位作用为主.

关键词: 四苯基卟啉氯化锰, 卟啉, 锰, 瞬态吸收光谱

The photophysical properties of tetraphenylporphyrin manganese(III) chloride Mn^III(TPP)Cl in four solvents of toluene (TOL), dichloromethane (DCM), acetonitrile (ACN) and N,N-dimethylformamide (DMF) were investigated through the steady-state and the femtosecond transient absorption spectroscopy. The Mn^III(TPP)Cl molecule is populated to the lifetimes of the second excited singlet state (⁵S₂) with pump pulse at 400 nm. Broad band white light continuum in the visible region from 420 nm to 700 nm is used in the probe. With a detail analysis of the measured transient spectra, three decay time constants τ₁, τ₂ and τ₃ corresponding to the lifetime of the second excited singlet state (⁵S₂), the lifetime of the first excited singlet state (⁵S₁) and the first excited triplet state (⁵T₁) are obtained in the four solvents. The results show that the steady-state B-band and Q-band absorption and the bleaching signal of the femtosecond transient absorption exhibit blue-shift. With the increase of the concentration of Mn^III(TPP)Cl in DCM, the lifetimes of the second excited singlet state (⁵S₂) had no significant change. And the lifetimes of the first excited singlet state (⁵S₁) and the first excited triplet state (⁵T₁) shortened. In these four solvents, its ⁵S₂ lifetime in nonpolar solvent TOL was the longest and the ⁵S₁ lifetime, ⁵T₁lifetime were the shortest. This is in accord with the largest ⁵S₂→⁵S₁ energy gap and the least ⁵S₁→⁵S₀ energy gap in TOL. From weak polar solvent DCM to the more polar solvent DMF, the ⁵S₁ lifetime and ⁵T₁lifetime shortened. With the solvent polarity increasing from nonpolar solvent TOL to the more polar solvent ACN, the ⁵S₂ lifetime shortened. While its ⁵S₂ lifetime becomes longer in polar solvent DMF. This is mainly caused by the axial ligation of nitrogen atom of coordinating solvent DMF with ⁵S₂of Mn^III(TPP)Cl. The structure of Mn^III(TPP)Cl changed from five-coordinate to six-coordinate. As a result, the longer ⁵S₂ lifetime in DMF should be due to the combined influence of the polarity of solvent and the axial ligation and the latter plays the main part.

Key words: tetraphenylporphyrin manganese(III) chloride, porphyrin, manganese, transient absorption spectroscopy

引用此文

李万红, 于明月, 王丽丽, 朱德煌, 彭素红, 王惠, 刘海洋. 溶剂对四苯基卟啉氯化锰飞秒瞬态吸收光谱的影响[J]. 化学学报, 2023, 81(4): 345-350.

Wanhong Li, Mingyue Yu, Lili Wang, Dehuang Zhu, Suhong Peng, Hui Wang, Haiyang Liu. Sovlent Influence on the Femtosecond Transient Absorption Spectra of Tetraphenylporphyrin Manganese(III) Chloride[J]. Acta Chimica Sinica, 2023, 81(4): 345-350.

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图/表 5

图1. MnIII(TPP)Cl在TOL(灰色)、DCM(黑色)、ACN(绿色)和DMF(红色)中的紫外-可见吸收光谱

Figure 1. UV-Vis absorption spectra of MnIII(TPP)Cl in TOL (Gray), DCM (black), ACN (green) and DMF (red)

Solvent	ε^[13]	B-band (λ_max/nm)
TOL	2.34	477	530	585	621
DCM	9.08	477	529	583	618
ACN	37.5	472	526	572	609
DMF	37.6	467	525	566	602

表1. MnIII(TPP)Cl在TOL, DCM, ACN和DMF中的紫外-可见吸收光谱数据

Table 1. UV-Vis absorption spectral data of MnIII(TPP)Cl in TOL, DCM, ACN and DMF

图2. MnIII(TPP)Cl在TOL (a), DCM (b), ACN (c)和DMF (d)在不同延迟时刻的飞秒瞬态吸收光谱. 相应的稳态吸收光谱(黑色点线)作对照

Figure 2. Femtosecond transient absorption spectra of MnIII(TPP)Cl in TOL (a), DCM (b), ACN (c) and DMF (d) monitored at different time delays. The corresponding steady-state absorption spectra (black dotted lines) are shown as comparisons

图3. MnIII(TPP)Cl (20 μmol/L)在DCM中采用SVD-GLF分析的飞秒瞬态吸收光谱(a)和动力学曲线(b)及特征波长处的动力学曲线(c)(蓝色点线, 稳态光谱; A1, A2和A3, 多指数拟合的振幅数据; 实验曲线, 灰色; 拟合曲线, 红色)

Figure 3. Femtosecond transient absorption spectra (a) and kinetic profiles (b) of MnIII(TPP)Cl (20 μmol/L) in DCM obtained from the SVD-GLF analysis and its kinetic profiles monitored at representative wavelengths (c) (blue dotted lines, the corresponding steady-state absorption spectra; A1, A2 and A3, multiexponential fitting results of the amplitudes; empirical curve, gray; fitted curve, red)

Solvent	Concentration	τ₁/ps	τ₂/ps	τ₃/ps
TOL	20 μmol/L	0.35	1.75	17.00
DCM	20 μmol/L	0.32	3.25	33.70
DCM	40 μmol/L	0.33	2.82	20.57
DCM	50 μmol/L	0.35	2.80	17.60
ACN	20 μmol/L	0.18	2.13	26.74
DMF	20 μmol/L	0.35	1.89	26.32

表2. MnIII(TPP)Cl在不同溶剂中采用SVD-GLF分析的时间常数

Table 2. Time constants for MnIII(TPP)Cl from the SVD-GLF analysis in different solvents

参考文献 20

[1]	Liu, H. Y.; Mahmood, M. H. R.; Qiu, S. X.; Chang, C. K. Coord. Chem. Rev. 2013, 257, 1306. doi: 10.1016/j.ccr.2012.12.017
[2]	Peng, S. H.; Zhou, R.; Zou, H. B. Chinese J. Org. Chem. 2019, 39, 3384. (in Chinese) doi: 10.6023/cjoc201904013
	(彭素红, 周蓉, 邹怀波, 有机化学, 2019, 39, 3384.) doi: 10.6023/cjoc201904013
[3]	Mauzerall, D. In the porphyrins handbook, Vol. 5, Ed.: Dolphin, D., Academic Press, New York, 1978, p. 29.
[4]	Weschler, C. J.; Hoffman, B. M.; Basolam F. J. Am. Chem. Soc. 1975, 97, 5278. pmid: 170324
[5]	Hoffman, B. M.; Weschler, C. J.; Basola, F. J. Am. Chem. Soc. 1976, 98, 473.
[6]	Harriman, A. J. Chem. Soc., Faraday Trans 1 1981, 77, 369.
[7]	Irvine, M. P.; Harrison, R. J.; Strahand, M. A.; Beddard, G. S. Ber. Bunsen-Ges. Phys. Chem. 1985, 89, 226. doi: 10.1002/bbpc.v89:3
[8]	Yan, X. W.; Kirmaier, C.; Holten, D. Inorg. Chem. 1986, 25, 4774. doi: 10.1021/ic00246a037
[9]	Kim, Y.; Choi, J. R.; Yoon, M.; Furube, A.; Asahi, T.; Masuhara, H. J. Phys. Chem. B 2001, 105, 8513. doi: 10.1021/jp0116757
[10]	Wang, L. L.; Peng, S. H.; Wang, H.; Ji, L. N.; Liu, H. Y. Phys. Chem. Chem. Phys. 2018, 20, 20141. doi: 10.1039/c8cp02223b pmid: 30027945
[11]	Fan, M. G.; Tong, Z. H. Molecular Photochemistry, Science Press, Beijing, 2013, p. 25. (in Chinese)
	(樊美公, 佟振合, 分子光化学, 科学出版社, 北京, 2013, p. 25.)
[12]	Wang, L. L.; Wang, H.; Chen, F.; Liang, Z. H.; Liu, C. F.; Li, Y.; Wang, W. Q.; Peng, S. H.; Wang, X.; Ying, X.; Ji, L. N.; Liu, H. Y. J. Phys. Chem. C 2017, 121, 12350. doi: 10.1021/acs.jpcc.7b00168
[13]	Hurjui, I; Ivan, L. M.; Dorohoi, D. O. Spectrochim, Acta, Part A 2013, 102, 219. doi: 10.1016/j.saa.2012.09.059 pmid: 23220660
[14]	Yu, H. Z.; Baskin, J. S.; Zewail, A. H. J. Phys. Chem. A 2002, 106, 9845. doi: 10.1021/jp0203999
[15]	Baskin, J. S.; Yu, H. Z.; Zewail, A. H. J. Phys. Chem. A 2002, 106, 9837. doi: 10.1021/jp020398g
[16]	Brӓm, O.; Consani, C.; Cannizzo, A.; Chergui, M. J. Phys. Chem. B 2011, 115, 13723. doi: 10.1021/jp207615u
[17]	Doǧan, N.; Dumanoǧulları, F. M.; Hayvalı, M.; Yılmaz, H.; Kürüm, U.; Yaglioglu, H. G.; Elmali, A. Chem. Phys. Lett. 2011, 508, 265. doi: 10.1016/j.cplett.2011.04.047
[18]	Velate, S.; Liu, X.; Steer, R. P. Chem. Phys. Lett. 2006, 427, 295. doi: 10.1016/j.cplett.2006.06.119
[19]	Alder, A. D.; Longo, F. R.; Finrelli, J. D. J. Inorg. Nucl. Chem. 1970, 32, 2443. doi: 10.1016/0022-1902(70)80535-8
[20]	Foggi, P.; Bussotti, L.; Neuwahl, F. V. R. Int. J. Photoenergy. 2001, 3, 103. doi: 10.1155/S1110662X01000125

溶剂对四苯基卟啉氯化锰飞秒瞬态吸收光谱的影响

Sovlent Influence on the Femtosecond Transient Absorption Spectra of Tetraphenylporphyrin Manganese(III) Chloride

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