以氟硼吡咯染料(Bodipy)做为光吸收天线,富勒烯作为分子内自旋转换单元,分别利用前者的强吸光以及后者的高效系间窜越的优点,制备了吸收波长灵活可调、无重原子、具有强可见光吸收能力、长寿命三重激发态(92.1 μs)的二元(Dyad)、三元化合物(Triad)做为有机三重态光敏剂;其中Triad具有宽谱带可见光吸收能力,提高了光敏剂参与的分子间能量转移或电子转移过程的效率.与传统的Ru(Ⅱ)配合物等三重态光敏剂相比,光催化硫醚氧化的反应时间大大缩短.通过吉布斯自由能的计算、活性氧物种的捕获实验、电子顺磁共振等方法,证明了在光催化氧化硫醚的反应过程中,同时存在超氧负离子自由基和单线态氧两个活性物种,从而加快了光催化氧化反应速率.该研究结果将对新型有机三重态光敏剂的分子结构设计以及在光催化有机合成反应中的应用起到一定的促进作用.
参考文献
| [1] | Jun Xuan;Wen-Jing Xiao .Visible-Light Photoredox Catalysis[J].Angewandte Chemie,2012(28):6828-6838. |
| [2] | Narayanam J M R;Stephenson C R J .Visible light photoredox catalysis:applications in organic synthesis[J].Chemical Society Reviews,2011,40(01):102-113. |
| [3] | Shi L;Xia W .Photoredox functionalization of C-H bonds adjacent to a nitrogen atom[J].Chemical Society Reviews,2012,41(23):7687-7697. |
| [4] | Xi, Y.;Yi, H.;Lei, A. .Synthetic applications of photoredox catalysis with visible light[J].Organic & biomolecular chemistry,2013(15):2387-2403. |
| [5] | Prier, C.K.;Rankic, D.A.;MacMillan, D.W.C. .Visible light photoredox catalysis with transition metal complexes: Applications in organic synthesis[J].Chemical Reviews,2013(7):5322-5363. |
| [6] | Tucker, J.W.;Stephenson, C.R.J. .Shining light on photoredox catalysis: Theory and synthetic applications[J].The Journal of Organic Chemistry,2012(4):1617-1622. |
| [7] | Lalevée, J.;Peter, M.;Dumur, F.;Gigmes, D.;Blanchard, N.;Tehfe, M.-A.;Morlet-Savary, F.;Fouassier, J.P. .Subtle ligand effects in oxidative photocatalysis with iridium complexes: Application to photopolymerization[J].Chemistry: A European journal,2011(52):15027-15031. |
| [8] | Jiangtao Xu;Kenward Jung;Amir Atme;Sivaprakash Shanmugam;Cyrille Boyer .A Robust and Versatile Photoinduced Living Polymerization of Conjugated and Unconjugated Monomers and Its Oxygen Tolerance[J].Journal of the American Chemical Society,2014(14):5508-5519. |
| [9] | Lalevée J;Tehfe M A;Dumur F;Gigmes D,Blanchard N,Morlet-Savary F,Fouassier J P .Iridium photocatalysts in free radical photopolymerization under visible lights[J].ACS Macro Letters,2012,1(02):286-290. |
| [10] | Ke, M.-R.;Yeung, S.-L.;Fong, W.-P.;Ng, D.K.P.;Lo, P.-C. .A phthalocyanine-peptide conjugate with high in vitro photodynamic activity and enhanced in vivo tumor-retention property[J].Chemistry: A European journal,2012(14):4225-4233. |
| [11] | Anu Naik;Riccardo Rubbiani;Gilles Gasse .Visible-Light-Induced Annihilation of Tumor Cells with Platinum-Porphyrin Conjugates[J].Angewandte Chemie,2014(27):6938-6941. |
| [12] | Gorman, A;Killoran, J;O'Shea, C;Kenna, T;Gallagher, WM;O'Shea, DF .In vitro demonstration of the heavy-atom effect for photodynamic therapy[J].Journal of the American Chemical Society,2004(34):10619-10631. |
| [13] | Lincoln, R.;Kohler, L.;Monro, S.;Yin, H.;Stephenson, M.;Zong, R.;Chouai, A.;Dorsey, C.;Hennigar, R.;Thummel, R.P.;McFarland, S.A. .Exploitation of long-lived 3IL excited states for metal-organic photodynamic therapy: Verification in a metastatic melanoma model[J].Journal of the American Chemical Society,2013(45):17161-17175. |
| [14] | Singh-Rachford T N;Castellano F N .Photon upconversion based on sensitized triplet-triplet annihilation[J].Coordination Chemistry Reviews,2010,254(21):2560-2257. |
| [15] | Zhao J;Ji S;Guo H .Triplet-triplet annihilation based upconversion:from triplet sensitizers and triplet acceptors to upconversion quantum yields[J].RSCAdvances,2011,1(06):937-950. |
| [16] | Jianzhang Zhao;Wanhua Wu;Jifu Sun .Triplet photosensitizers: from molecular design to applications[J].Chemical Society Reviews,2013(12):5323-5351. |
| [17] | Hammarstr(o)m L;Johansson O .Expanded bite angles in tridentate ligands.Improving the photophysical properties in bistridentate RuⅡ polypyridine complexes[J].Coordination Chemistry Reviews,2010,254(21):2546-2559. |
| [18] | Zhao J;Ji S;WuW;WuW,GuoH,Sun J,Sun H,Liu Y,Li Q,Huang L .Transition metal complexes with strong absorption of visible light and long-lived triplet excited states:from molecular design to applications[J].RSCAdvances,2012,2(05):1712-1728. |
| [19] | Whittle C E;Weinstein J A;George M W;Schanze K S .Photophysics of diimine platinum(Ⅱ) bis-acetylide complexes[J].Inorganic Chemistry,2001,40(16):4053-4062. |
| [20] | Hissler M;Connick W B;Geiger D K;McGarrah J E,Lipa D,Lachicotte R J,Eisenberg R .Platinum diimine bis (acetyhde) complexes:synthesis,characterization,and luminescence properties[J].Inorganic Chemistry,2000,39(03):447-457. |
| [21] | Yuanhang Pan;Choon Wee Kee;Li Chen .Dehydrogenative coupling reactions catalysed by Rose Bengal using visible light irradiation[J].Green chemistry,2011(10):2682-2685. |
| [22] | Yuanhang Pan;Shuai Wang;Choon Wee Kee .Graphene oxide and Rose Bengal: oxidative C-H functionalisation of tertiary amines using visible light[J].Green chemistry,2011(12):3341-3344. |
| [23] | Ulrich G;Ziessel R;Harriman A .The chemistry of fluorescent hodipy dyes:versatility unsurpassed[J].Angewandte Chemie International Edition,2008,47(07):1184-1201. |
| [24] | Ziessel, R.;Harriman, A. .Artificial light-harvesting antennae: Electronic energy transfer by way of molecular funnels[J].Chemical communications,2011(2):611-631. |
| [25] | Lu H;Mack J;Yang Y;Shen Z .Struetural modification strategies for the rational design of red/NIR region BODIPYs[J].Chemical Society Reviews,2014,43(13):4778-4823. |
| [26] | Aurore Loudet;Kevin Burgess .BODIPY Dyes and Their Derivatives:Syntheses and Spectroscopic Properties[J].Chemical Reviews,2007(11):4891-4932. |
| [27] | Takatoshi Yogo;Yasuteru Urano;Yukiko Ishitsuka;Fumio Maniwa;Tetsuo Nagano .Highly Efficient and Photostable Photosensitizer Based on BODIPY Chromophore[J].Journal of the American Chemical Society,2005(35):12162-12163. |
| [28] | Anyanee Kamkaew;Siang Hui Lim;Hong Boon Lee .BODIPY dyes in photodynamic therapy[J].Chemical Society Reviews,2013(1):77-88. |
| [29] | Huang, L.;Yu, X.;Wu, W.;Zhao, J. .Styryl Bodipy-C _(60) dyads as efficient heavy-atom-free organic triplet photosensitizers[J].Organic letters,2012(10):2594-2597. |
| [30] | Ziessel, Raymond;Allen, Ben D.;Rewinska, Dorota B.;Harriman, Anthony .Selective Triplet-State Formation during Charge Recombination in a Fullerene/Bodipy Molecular Dyad (Bodipy = Borondipyrromethene)[J].Chemistry: A European journal,2009(30):7382-7393. |
| [31] | Ling Huang;Xiaoneng Cui;Bruno Therrien;Jianzhang Zhao .Energy-Funneling-Based Broadband Visible-Light-Absorbing Bodipy–C_(60) Triads and Tetrads as Dual Functional Heavy-Atom-Free Organic Triplet Photosensitizers for Photocatalytic Organic Reactions[J].Chemistry: A European journal,2013(51):17472-17482. |
| [32] | David A. Nicewicz;David W. C. MacMillan .Merging Photoredox Catalysis with Organocatalysis: The Direct Asymmetric Alkylation of Aldehydes[J].Science,2008(5898):77-80. |
| [33] | Yoko Yamakoshi;Naoki Umezawa;Akemi Ryu;Kumi Arakane;Naoki Miyata;Yukihiro Goda;Toshiki Masumizu;Tetsuo Nagano .Active Oxygen Species Generated from Photoexcited Fullerene (C_(60)) as Potential Medicines: O_2~(-·) versus ~1O_2[J].Journal of the American Chemical Society,2003(42):12803-12809. |
| [34] | Xiangyong Gu;Xiang Li;Yahong Chai .A simple metal-free catalytic sulfoxidation under visible light and air[J].Green chemistry,2013(2):357-361. |
| [35] | Pengfei Zhang;Yong Wang;Haoran Li .Metal-free oxidation of sulfides by carbon nitride with visible light illumination at room temperature[J].Green chemistry,2012(7):1904-1908. |
| [36] | Dad'ová J;Svobodová E;Sikorski M;K6nig B,Cibulka R .Photooxidation of sulfides to sulfoxides mediated by tetra O acetylriboflavin and visible light[J].ChemCatChem,2012,4(05):620-623. |
| [37] | Baciocchi E;Giacco T D;Elisei F;Gerini M F,Guerra M,Lapi A,Liberali P .Electron transfer and singlet oxygen mechanisms in the photooxygenation of dibutyl sulfide and thioanisole in MeCN sensitized by N-methylquinolinium tetrafluoborate and 9,10-dicyanoanthracene.The probable involvement of a thiadioxirane imermediate in electron transfer photooxygenations[J].Journal of the American Chemical Society,2003,125(52):16444-16454. |
| [38] | Bonesi SM;Manet I;Freccero M;Fagnoni M;Albini A .Photosensitized oxidation of sulfides: Discriminating between the singlet-oxygen mechanism and electron transfer involving superoxide anion or molecular oxygen[J].Chemistry: A European journal,2006(18):4844-4857. |
| [39] | Liu, Q.;Li, Y.-N.;Zhang, H.-H.;Chen, B.;Tung, C.-H.;Wu, L.-Z. .Reactivity and mechanistic insight into visible-light-induced aerobic cross-dehydrogenative coupling reaction by organophotocatalysts[J].Chemistry: A European journal,2012(2):620-627. |
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