Open access peer-reviewed chapter

Fullerene as Spin Converter

Written By

Elif Okutan

Submitted: 07 December 2017 Reviewed: 26 January 2018 Published: 06 April 2018

DOI: 10.5772/intechopen.74541

From the Edited Volume

Fullerenes and Relative Materials - Properties and Applications

Edited by Natalia V. Kamanina

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It has now been more than 30 years since buckminsterfullerene became a real thing. An exclusive field of study called fullerene chemistry arises and is discovered to be unique in many respects. In a very short time, a great deal of effort has been devoted on the fullerene chemistry and properties of fullerene derivatives. The fields of fullerene and light-induced processes considerably overlapped, and now numerous wonderful examples are on exhibition. The large number of these systems has been designed to take advantage of the electron-accepting property of fullerene and broadcasts the fullerenes as universal spin converter advertising its perfect intersystem crossing (ISC) quantum yield where a spin converter can be identified as a chromophore that undergoes efficient ISC with a low first excited state (S1), but does not necessarily strongly harvest visible light. Thus, donor-acceptor systems in the field of light-induced processes within multicomponent fullerene arrays have been proposed as models for optical limiters, owing to the singlet oxygen production efficiency of C60 and the C60 derivatives in the field of medicinal chemistry.


  • fullerene
  • spin converter
  • light harvesting
  • singlet oxygen
  • triplet-triplet annihilation

1. Introduction

Transformation of known and the creation of new are always intrigued to synthetic chemists. Not long ago, elemental carbon was not even a figurant as starting material. This position promoted fiercely after the family of carbon allotropes enlarged by the welcoming new members to the core family “graphite and diamond.” Unlike to graphite and diamond, fullerenes are spherical molecules with solid-state structure and are soluble in various solvents that opened a new era for chemical manipulation of carbon-based materials [1].

Few discoveries like this are captured the attention of scientist and the general public alike as much as the discovery of these architecturally esthetic molecules. But the popularity of fullerenes in science is not merely due to esthetics. Years of intense research activity showed that C60 is a powerful building block to be used in materials science and medicinal chemistry [2, 3]. What put fullerenes in the heart of nanotechnology today is the association of several extreme properties, such as outstanding mechanical, thermal, electronic, and electrical properties, coupled with chemical robustness, which have spurred a broad range of applications that provides new research possibilities for scientists, particularly in terms of electron-acceptor proficiency, both in the solid state and in solution [4]. An entirely new discipline called as “fullerene chemistry” emerged [5, 6, 7].


2. Optical studies of fullerene

Fullerene structure facilitates ingrained synthetic methodologies that catalyzing the production of a wide variety of novel derivatives often encompasses many fields outside the traditional scope [8, 9]. One of the most exciting properties of fullerene chemistry is related to their excited-state properties [10, 11]. The most abundant representative of the family C60 can be identified via its strong absorptions between 190 and 410 nm (allowed 1T1u1Ag) as well as by some pale but significant transitions in the 410 and 620 nm (orbital forbidden singlet-singlet) region which is responsible for the purple color of C60 and the red color of C70 [12, 13].

The fullerenes, in particular C60, exhibit a variety of remarkable photophysical properties, making them very attractive building blocks for the construction of photosynthetic antenna and reaction center models that result from their large pi electron system that cater dense manifolds of low-lying electronically excited states [14, 15, 16, 17]. As it is given below, most photochemical and photophysical applications of fullerenes are likely be mediated by lowest of these energetic states which present triplet spin multiplicity (Figure 1).

Figure 1.

The Jablonski diagram: schematic depiction of the energy levels of typical compound (adapted from [18, 19]).

The fullerenes can also be identified as useful optical limiters since the triplet-triplet absorptivities are higher than the ground-state absorptions [20, 21]. The singlet excited state (1.99 eV) of C60 efficiently decays to the lower lying triplet excited state (1.57 eV) via intersystem crossing [17]. The triplet quantum yields are very high. The triplet excited states are responsive to diverse processes for deactivation, such as ground-state quenching, triplet-triplet annihilation via molecular oxygen leading to 1O2, and electron transfer to donor molecules [17]. The long-lived triplet states due to the ISC process of excited singlet states gave rise to a substantial interest for their prosperous applications, such as singlet oxygen generation for [22, 23, 24, 25, 26], enhancing photoinduced electric conductivity via formation of charge-separated state caused by the excited triplet state of fullerene [27, 28, 29] and in the applications of photovoltaics, photocatalysis, photoinduced charge separation, and molecular probes (Figure 2) [30, 31, 32, 33, 34, 35, 36].

Figure 2.

Main decay channels that control the lifetime of triplet C60 in solution [37]. (reprinted by permission of ACS Publications).

In this account, we discuss some of the main achievements in this rapidly developing field and, in particular, the triplet photosensitizer (PS) phenomena associated with the excited triplet state of fullerenes that later used as catalysts in photochemical reactions. Triplet PSs as the name derived from the compounds, used to transfer energy to other, are used for not only energy transfer but also for photovoltaic reactions such as photodynamic therapy (PDT), photoinduced hydrogen production from water, and triplet-triplet annihilation (TTA) upconversion systems. The photosensitizing properties of some relevant classes of functionalized fullerene-based materials are surveyed.

Even in the early reports on excited states of fullerene prepared via light excitation, researchers were concerned with the persistence of long-lived excited and low triplet states. A number of researches addressed the decay kinetics of fullerenes (C60 and C70), and the unimolecular triplet state lifetimes are found to be significantly longer than recognized [22, 38, 39, 40, 41, 42, 43, 44, 45]. In the bimolecular triplet state processes, there are various deactivation mechanisms including oxygen quenching, triplet-triplet annihilation, triplet energy exchange, and self-quenching. The deactivation of organic triplet states by dissolved oxygen is reported by numerous researchers, and oxygen quenching constants for C60 and C70 are recorded in room temperature [22, 23] and were persistent with previous results [37]. Triplet-triplet annihilation occurs between two clashing triplet states considering the deactivation of one molecule, while exposure of the other in a highly excited state that will quickly convert to first singlet excited state (S1) (Figure 2). The reported kTT values are 5.4 x 109 M−1 s−1 and 5.5 x 109 M−1 s−1 in room temperature which should considered to be high and kept in mind to eliminate contributions from this channel while measuring excited state kinetics such as studying with low concentration [37, 46]. In another scenario triplet energy may flow between two species in solution [46]. If one species T1 state is significantly lower than the other, the second specimen will collect the energy and behave as a triplet quencher. On another scenario, the two T1 states might be separated by several kTT. In this case, reverse energy transfer may also be occurred, and results showed that reversible energy transfer between triplet states C60 and C70 is a fast and efficient process [47]. Also, even though no mechanism was proposed for self-quenching mechanisms, the ground-state concentration dependence refers to the encounter of a molecule on T1 state with ground-state molecule. Studies showed that fullerene displays strong self-quenching over organic triplet states [48, 49].

Fullerene exhibits unique C–C single and double bonds. The deficiency of high-energy C–H and O–H vibrations makes these materials very interesting in photonics. The usual materials such as polymers have absorption in the near infrared because of the overtones of the abovementioned vibrations. No such absorption is observed in fullerenes while exhibiting narrow electronic bands and resonances [50, 51]. Fullerene’s large number of conjugated double bonds lead to large nonlinear polarizabilities. The third-order optical polarizability, γ, is always symmetry allowed, while the second-order polarizability, β, is reported to be zero for C60 and C70 since they have centrosymmetric structures [51]. By preparing charge-transfer complexes (fullerene as electron acceptor), the center of symmetry is interrupted, and second-order optical nonlinearity is induced [52]. Specifically, the optical limiting in fullerene based on the reverse saturable absorption which takes place when the excited state absorption cross section is bigger than that of the ground state. This effect was reported for C60 and for C70 under 532 nm and 1064 nm excitations where optical limiting performance of C60 is bigger than C70 since the latter exhibits a higher linear state absorption coefficient [53].

The design of new structures with high first hyperpolarizability (β) can be made via two state models in which β is expressed with the dipole moment difference, the transition dipole moment, and the energy difference between the key charge-transfer excited state and the ground electronic state [54]. The charge-transfer complexes can be characterized by the absorption cross section for an excited state of the organic moiety, which is significantly greater than that for the ground state [53]. Thus, these nanomaterials offer the optical limiting phenomena, particularly in the IR range. Fullerene-induced sensitization also favors bathochromic shift in the absorption spectra of related structures and activate transition in the near- and middle-IR range [55]. During the charge transfer, an additional electric field gradient is reported to be formed as substitute from the intramolecular donor to fullerene rather than to the intramolecular acceptor. Consequently, the nanomaterial offers high-frequency Kerr effect and exhibits high value of nonlinear refraction and nonlinear third-order permeability [56, 57]. In general, photoinduced electron transfer in donor-acceptor dyads in solution is reported to be related to free energy change for charge separation ΔGCS, which depends on the energies for oxidation, reduction, and excitation and also to the Coulomb interaction and solvation of the radical ions [58]. The rate for electron transfer is obtained from the charge transfer and the electronic coupling of donor and acceptor in the excited state barrier. Also, energy transfer processes dipole-dipole (Förster) and exchange (Dexter) mechanisms are generally used to explain the deactivation of the initial photoexcited state.

Afterward, fullerene chemistry allowed researchers to open a new door to link fullerenes to photoactive species, and the work to date suggests that the first excited state can be populated by singlet-singlet energy transfer from attached dye and in the appropriate conditions can be quenched by triplet energy acceptors. Thus, fullerenes hold a significant promise, and the study on these materials will be a scientific endeavor [37, 43, 59, 60, 61, 62, 63, 64, 65, 66, 67].

On the account of simple organic molecules, the triplet manifold is rarely reached by direct stimulation of the organic molecule, unless advertised spin-orbit coupling effect is populated by a heavy atom [68, 69]. The triplet manifold may be reached via indirect secondary routes such as intersystem crossing from the first excited state (S1) and charge separation and recombination between radical ions [70, 71, 72, 73]. This kind of recombination may require orbital contact via flexible link or by a rigid spacer [74, 75, 76, 77, 78, 79]. Ziessel et al. described results of photophysical properties of a closely spaced molecular dyad comprising terminal BODIPY dye and a fullerene. They investigated the driving force for light-induced electron abstraction by the S1 state of C60 from BODIPY unit and displayed the dependence to solvent polarity. In nonpolar solvents, fast excitation energy transfer was declared, while electron transfer became laborious. Polar solvents play a critical role switching on light-induced electron transfer [68].

Artificial photosynthetic systems to mimic natural systems for global energy demand are important not only to understand nature but also for environmental issues. Various synthetic models were designed and constructed based on tetrapyrroles as energy harvesting antennae due to their structural resemblance to natural chlorophylls [80, 81, 82, 83]. Owing to fullerene’s facile reduction and low reorganization energy, fullerene lessened the use of 2D electron donor-acceptor systems such as quinone and methyl viologen and was successfully demonstrated in studies as “antenna-reaction center.” Maligaspe et al. developed supramolecular triads to mimic these issued antenna-reaction center systems designing boron dipyrrin (BODIPY) entities as antenna that linked to zinc porphyrin (P) as electron donor and then coordinate to fullerene as electron acceptor (Figure 3) [84]. Similarly, BODIPY-ZnPc-fullerene system, where BODIPY unit located on peripheral position on Pc was designed, demonstrates a sequence of energy and electron transfer reactions upon photoexcitation [85]. An interesting example of distyryl-BODIPY-fullerene donor-acceptor system was also reported by Liu et al [86].

Figure 3.

Optimized structures of BODIPY-ZnPc-C60 triads [85]. (Reprinted by permission of RSC).

Upconversion systems are used in photovoltaics, photocatalysis, nonlinear optics, and luminescent molecular probes [87]. To facilitate upconversion one or two methods are deployed for such as rare-earth materials or two-photon absorption fluorescent dyes [88, 89]. These conventional upconversion methods come with the disadvantages of weak absorption, low upconversion quantum yield, or requirement of consistent high-power density excitation source. New upconversion method based on triplet photosensitizer and triplet accelerator become popular where triplet photosensitizers are responsible for light harvesting and enhancement of triplet excited state by intersystem crossing (ISC) [90]. The previously reported triplet photosensitizers are usually transition-metal complexes, such as PtII/PdII porphyrin complexes, IrIII/RuII complexes, or heavy-atom derivatives of organic fluorophores since ISC is facilitated by the heavy atom spin-orbital coupling effect [91, 92, 93]. Designing these systems via chemical derivatization of a known heavy atom-free organic triplet photosensitizer is not a decisive way to prepare new organic triplet photosensitizers because even simple derivatization of the chromophore may diminish ISC [25, 26]. Heavy atom-free organic triplet photosensitizers with absorption in visible range are highly desired and remained rare for TTA upconversion system (Figure 4) [36, 87, 94]. An intramolecular spin converter is used to overcome the aforementioned challenges. Both C60 and C70 were also used to construct heavy atom-free triplet photosensitizer, both red-to-green and green-to-blue upconversions [36, 95, 96].

Figure 4.

Structure of the C60-based dyads as organic triplet sensitizers for triplet-triplet annihilation upconversions [36] (Reprinted by permission of ACS).

Lim et al. also reported a supramolecular tetrad bearing covalently linked ferrocene-zinc porphyrin-BODIPY system coordinated to fullerene that proposed as photosynthetic antenna reaction center mimicked by performing systematic spectral, computational, and electrochemical studies to evaluate the role of each entity in the photochemical reactions [97].

Even the early studies on evaluation of using fullerene derivatives to generate singlet oxygen. Even if there was little quantitative data at that time displayed the singlet oxygen generation by dissolving C60 in polyvinylpyrrolidone (mutagenic for Salmonella strains TA102, TA104, and YG3003) in the presence of rat liver microsomes followed by the irradiation with visible light [98]. Singlet oxygen efficiency dependence on the kind and number of addends was also studied during the early period of fullerene chemistry. The results suggested that efficiency easy independent from the kind of addends but decreased with an increasing number of the substituent [99]. A strong correlation was also reported by Prat et al. between triplet properties and the topology of the fullerene core [100]. Since fullerene chemistry evolved during that time, several fullerene derivatives were prepared to effectively generate singlet oxygen for numerous applications [101, 102, 103, 104]. For their possible application in photodynamic therapy, a prototype macromolecule bearing a distyrylbenzene dimer as TPA unit and a [60]fullerene moiety for singlet oxygen generation endowed with a high two-photon absorption (TPA) cross section and a high singlet oxygen quantum yield were reported by Collini et al. (Figure 5) [105]. The singlet oxygen generation and photoinduced charge separation of zinc phthalocyanine-fullerene dyad bearing tetra polyethylene glycol moieties were also reported for PDT application [106].

Figure 5.

Fullerene-distyrylbenzene conjugate [105] (Reprinted by permission of RSC).

In organic synthesis, oxidation is one of the primary reactions; thus, there has been an extensive research interest devoted on the use of singlet oxygen as photocatalysis in photooxidation reactions [25, 26, 107, 108]. Huang et al. used energy funneling for the first time with C60-BODIPY triads and tetrads as dual functional photocatalysis for two different photocatalytic reactions. They produce juglone via photooxidation of naphthol and superoxide radical ion by photocatalytic aerobic oxidation of aromatic boronic acids to produce phenol. Reaction time was also reduced reasonably with this strategy [109]. Novel heavy atom-free triplet photosensitizers to generate singlet oxygen contain one and two light-harvesting antennas as well as associated with different absorption wavelengths were successfully designed and synthesized in our laboratory (Figure 6).

Figure 6.

Heavy atom-free BODIPY-fullerene triplet photosensitizers [25, 26].



The author would like to thank to Gebze Technical University.


Conflict of interest

There is no conflict of interest.


  1. 1. Kroto HW, Heath JR, O’Brien SC, Curl RF, Smalley RE. C60: Buckminsterfullerene. Nature. 1985;318:162-163. DOI: 10.1038/318162a0
  2. 2. Prato M. [60] fullerene chemistry for materials science applications. Journal of Materials Chemistry. 1997;7:1097-1109. DOI: 10.1039/A700080D
  3. 3. Da Ros T, Prato M. Medicinal chemistry with fullerenes and fullerene derivatives. Chemical Communications. 1999:663-669. DOI: 10.1039/A809495K
  4. 4. Fagan PJ, Calabrese JC, Malone B. Metal complexes of buckminsterfullerene (C60). Accounts of Chemical Research. 1992;25:134-142. DOI: 10.1021/ar00015a006
  5. 5. Hirsch A, editor. Fullerenes and Related Structures. Topics in Current Chemistry. 1st ed. Berlin: Springer; 1999. DOI: 10.1007/3-540-68117-5
  6. 6. Taylor R. Lecture Notes on Fullerene Chemistry. 1st ed. London: Imperial College Press; 1999
  7. 7. Diederich F, Thilgen C. Covalent fullerene chemistry. Science. 1996;271:317-323. DOI: 10.1126/science.271.5247.317
  8. 8. Lopez AM, Mateo-Alonso A, Prato M. Materials chemistry of fullerene C60 derivatives. Journal of Materials Chemistry. 2011;21:1305-1318. DOI: 10.1039/C0JM02386H
  9. 9. Yadav BC, Kumar R. Structure, properties and applications of fullerenes. International Journal of Nanotechnology and Applications. 2008;2:15-24
  10. 10. Foote CS. Photophysical and Photochemical Properties of Fullerenes. Topics in Current Chemistry. Vol. 169. Berlin, Heidelberg: Springer; 1994. pp. 347-363. DOI: 10.1007/3-540-57565-0_80
  11. 11. Sun YP. Molecular and supramolecular photochemistry. In: Organic Photo Chemistry. New York: CRC Press; 1997. pp. 325-390
  12. 12. Palit DK, Sapre AV, Mittal JP, Rao CNR. Photophysical properties of the fullerenes, C60 and C70. Chemical Physics Letters. 1992;195:1-6. DOI: 10.1016/0009-2614(92)85900-U
  13. 13. Ajie H, Alvarez MM, Anz SJ, Beck RD, Diederich F, Fostiropoulos Huffman KDR, Krätschmer W, Rubin Y, Shriver KE, Sensharma D, Whetten RL. The Journal of Physical Chemistry. 1990;94:8630-8633. DOI: 10.1021/j100387a004
  14. 14. Imahori H, Sakata Y. Donor-linked fullerenes: Photoinduced electron transfer and its potential application. Advanced Materials. 1997;9:537-546. DOI: 10.1002/adma.19970090704
  15. 15. Imahori H, Sakata Y. Fullerenes as novel acceptors in photosynthetic electron transfer. European Journal of Organic Chemistry. 1999;10:2445-2457. DOI: 10.1002/(SICI)1099-0690(199910)1999:10<2445::AID-EJOC2445>3.0.CO;2-G
  16. 16. Guldi DM. Fullerene–porphyrin architectures; photosynthetic antenna and reaction center models. Chemical Society Reviews. 2002;31:22-36. DOI: 10.1039/B106962B
  17. 17. Guldi DM, Kamat PV. Fullerenes, Chemistry, Physics and Technology. New York: Wiley; 2000. 225p. DOI: 10.1002/aoc.173
  18. 18. Medvedev ES, Osherov VI. Radiationless Transition in Polyatomic Molecules. Moscow: Springer-Verlag Berlin Heidelberg; 1983
  19. 19. Couris S, Koudoumas E, Ruth AA, Leach S. Concentration and wavelength dependence of the effective third-order susceptibility and optical limiting of C60 in toluene solution. Journal of Physics B: Atomic, Molecular and Optical Physics. 1995;8:4537-4554. DOI: 10.1088/0953-4075/28/20/015
  20. 20. Sun YP, Riggs JE, Liu B. Optical limiting properties of [60]fullerene derivatives. Chemistry of Materials. 1997;9:1268-1272. DOI: 10.1021/cm960650v
  21. 21. Wray JE, Liu KC, Chen CH, Garret WR, Payne MG, Goedert R, Templeton D. Optical power limiting of fullerenes. Applied Physics Letters. 1994;64:2785-2787. DOI: 10.1063/1.111470
  22. 22. Arbogast JW, Darmanyan AP, Foote CS, Diederich FN, Whetten RL, Rubin Y, Alvarez MM, Anz SJ. Photophysical properties of sixty atom carbon molecule (C60). Journal of Physical Chemistry. 1991;95:11-12. DOI: 10.1021/j100154a006
  23. 23. Arbogast JW, Foote CS. Photophysical properties of C70. Journal of American chemical Society. 1991;113:8886-8889. DOI: 10.1021/ja00023a041
  24. 24. Tanigaki K, Ebbesen TW, Kuroshima S. Picosecond and nanosecond studies of the excited state properties of C70. Chemical Physics Letters. 1991;185:189-192. DOI: 10.1016/S0009-2614(91)85045-X
  25. 25. Ünlü H, Okutan E. Novel distyryl BODIPY–fullerene dyads: Preparation, characterization and photosensitized singlet oxygen generation efficiency. New Journal of Chemistry. 2017;41:10424-10431. DOI: 10.1039/C7NJ02010D
  26. 26. Ünlü H, Okutan E. Preparation of BODIPY- fullerene and monostyryl BODIPY-fullerene dyads as heavy atom free singlet oxygen generators. Dyes and Pigments. 2017;142:340-349. DOI: 10.1016/j.dyepig.2017.03.055
  27. 27. Wang Y. Photoconductivity of fullerene-doped polymers. Nature. 1992;356:585-587. DOI: 10.1038/356585a0
  28. 28. Smilowitz L, Sarıçiftçi NS, Wu R, Gettinger C, Heeger AJ, Wudl F. Photoexcitation spectroscopy of conducting-polymer-C60 composites: Photoinduced electron transfer. Physical Review B: Condensed Matter and Materials Physics. 1993;47:13835-13842. DOI: 10.1103/PhysRevB.47.13835
  29. 29. Komamine S, Fujitsuka M, Ito O, Itaya A. Photoinduced electron transfer between C60 and carbazole dimer compounds in a polar solvent. Journal of Photochemistry and Photobiology A: Chemistry. 2000;135:111-117. DOI: 10.1016/S1010-6030(00)00290-2
  30. 30. Singh Rachford TN, Castellano FN. Photon upconversion based on sensitized triplet-triplet annihilation. Coordination Chemistry Reviews. 2010;254:2560-2573. DOI: 10.1016/j.ccr.2010.01.003
  31. 31. Zhao J, Ji S, Guo H. Triplet-triplet annihilation based upconversion: From triplet sensitizers and triplet acceptors to upconversion quantum yields. RSC Advanced. 2011;1:937-950. DOI: 10.1039/C1RA00469G
  32. 32. Khnayzer RS, Blumhoff J, Harrington JA, Haefele A, Deng F, Castellano FN. Upconversion-powered photoelectrochemistry. Chemical Communications. 2012;48:209-211. DOI: 10.1039/C1CC16015J
  33. 33. Ceroni P. Energy up-conversion by low-power excitation: New applications of an old concept. Chemistry A European Journal. 2011;17:9560-9564. DOI: 10.1002/chem.201101102
  34. 34. Baluschev S, Miteva T, Yakutkin V, Nelles G, Yasuda A, Wegner G. Up-conversion fluorescence: Noncoherent excitation by sunlight. Physical Review Letters. 2006;97:143903-143905. DOI: 10.1103/PhysRevLett.97.143903
  35. 35. Chen HC, Hung CY, Wang KH, Chen HL, Fann WS, Chien FC, Chen P, Chow TJ, Hsu CP, Sun SS. White light emission from an upconverted emission with an organic triplet sensitizer. Chemical Communications. 2009:4064-4066. DOI: 10.1039/B905572J
  36. 36. Wu W, Zhao J, Sun J, Guo S. Light-harvesting fullerene dyads as organic triplet photosensitizers for triplet-triplet annihilation upconversions. The Journal of Organic Chemistry. 2012;77:5305-5312
  37. 37. Fraelich MR, Weisman RB. Triplet states of fullerene C60 and C70 in solution: Long intrinsic lifetimes and energy pooling. Journal of Physical Chemistry. 1993;97:11145-11147. DOI: 10.1021/j100145a002
  38. 38. Ebbesen TW, Tanigaki K, Kuroshima S. Excited-state properties of C60. Chemical Physics Letters. 1991;181:501-504. DOI: 10.1016/0009-2614(91)80302-E
  39. 39. Biczok L, Linschitz H, Walter RI. Extinction coefficients of C60 triplet and anion radical, and one-electron reduction of the triplet by aromatic donors. Chemical Physics Letters. 1992;195:339-346. DOI: 10.1016/0009-2614(92)85613-F
  40. 40. Kajii Y, Nakagawa T, Suzuki S, Achiba Y, Obi K, Shibuya K. Transient absorption, lifetime and relaxation of C60 in the triplet state. Chemical Physics Letters. 1991;181:100-104. DOI: 10.1016/0009-2614(91)90339-B
  41. 41. Terazima M, Hirota N, Shinohara H, Saito Y. Photothermal investigation of the triplet state of carbon molecule (C60). The Journal of Physical Chemistry. 1991;95:9080-9085. DOI: 10.1021/j100176a013
  42. 42. Closs GL, Gautam P, Zhang D, Krusic PJ, Hill SA, Wasserman E. Steady-state and time-resolved direct detection EPR spectra of fullerene triplets in liquid solution and glassy matrixes: Evidence for a dynamic Jahn-teller effect in triplet C60. The Journal of Physical Chemistry. 1992;96:5228-5231. DOI: 10.1021/j100192a011
  43. 43. Dimitrijevic NM, Kamat PV. Triplet excited state behavior of fullerenes: Pulse radiolysis and laser flash photolysis of fullerenes (C60 and C70) in benzene. The Journal of Physical Chemistry. 1992;96:4811-4814. DOI: 10.1021/j100191a017
  44. 44. Palit D, Sapre AV, Mittal JP, Rao CNR. Photophysical properties of the fullerenes, C60 and C70. Chemical Physics Letters. 1992;195:1-6. DOI: 10.1016/0009-2614(92)85900-U
  45. 45. Gijzeman OLJ, Kaufman F, Porter G. Oxygen quenching of aromatic triplet states in solution. Part 1. Journal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics. 1973;69:708-720. DOI: 10.1039/F29736900708
  46. 46. Turro NJ. Modern Molecular Photochemistry. Menlopark CA: The Benjamin/Cummings Publishing Company; 1978
  47. 47. Sandros K. Transfer of triplet state energy in fluid solutions. III. Reversible energy transfer. Acta Chemica Scandinavica. 1964;18:2355-2374. DOI: 10.3891/acta.chem.scand.18-2355
  48. 48. Liddell PA, Sumida JP, Macpherson AN, Noss L, Seely GR, Clark KN, Moore AL, Moore TA, Gust D. Preparation and photophysical studies of porphyrin-C60 dyads. Photochemistry and Photobiology. 1994;60:537-541. DOI: 10.1111/j.1751-1097.1994.tb05145.x
  49. 49. Kuciauskas D, Lin S, Seety GR, Moore AL, Moore TA, Gust D, Drovetskaya T, Reed CA, Boyd PDW. Energy and Photoinduced electron transfer in Porphyrin-fullerene dyads. Journal of Physical Chemistry. 1996;100:15926-15932. DOI: 10.1021/jp9612745
  50. 50. Kafafi ZH, Lindle JR, Pong RGS, Bartoli FJ, Lingg LJ, Milliken J. Off-resonant nonlinear optical properties of C60 studied by degenerate four-wave mixing. 1992;188:492-496. DOI: 10.1016/0009-2614(92)80854-5
  51. 51. Kajzar F, Taliani C, Zamboni R, Rossini S, Danieli R. Nonlinear optical properties of fullerenes. Synthetic Metals. 1996;77:257-263
  52. 52. Wang Y, Cheng LT. Nonlinear optical properties of fullerenes and charge-transfer complexes of fullerenes. The Journal of Physical Chemistry. 1992;96:1530-1532
  53. 53. Shulev VA, Filippov AK, Kamanina NV. Laser-induced processes in the IR range in Nanocomposites with fullerenes and carbon nanotubes. Technical Physics Letters. 2006;32:694-697. DOI: 10.1134/S1063785006080177
  54. 54. Loboda O, Zalesny R, Avramopoulos A, Luis JM, Kirtman B, Tagmatarchis N, Reis H, Papadopoulos MG. Linear and nonlinear optical properties of [60]fullerene derivatives. The Journal of Physical Chemistry. A. 2009;113:1159-1170. DOI: 10.1021/jp808234x
  55. 55. Kamanina N. Mechanisms of optical limiting in π conjugated organic system: Fullerene doped polyimide. Synthetic Metals. 2002;127:121-128. DOI: 10.1016/S0379-6779(01)00598-7
  56. 56. Kamanina NV. Properties of optical limitation of radiation in π-conjugated organic systems doped with fullerenes (the COANP-C70 system). Optics and Spektroscopy. 2001;90:931-937. DOI: 10.1134/1.1380795
  57. 57. Kamanina NV. Nonlinear optical coefficients of polyimide doped with fullerenes. Synthetic Metals. 2003;139:547-550. DOI: 10.1016/S0379-6779(03)00358-8
  58. 58. van Hal PA, Janssen RA, Lanzani G, Cerullo G, Zavelani-Rossi M, De Silvestri S. Two-step mechanism for the photoinduced intramolecular electron transfer in oligo (p-phenylene vinylene)-fullerene dyads. Physical Review B. 2001;64:075206-1-075206-7. DOI: 10.1103/PhysRevB.64.075206
  59. 59. Imahori H, Hagiwara K, Akiyama T, Taniguchi S, Okada T, Sakata Y. Synthesis and Photophysical property of Porphyrin-linked fullerene. Chemistry Letters. 1995;24:265-266. DOI: 10.1246/cl.1995.265
  60. 60. Linssen TG, Dürr K, Hanack M, Hirsch A. A green fullerene: Synthesis and electrochemistry of a Diels-Alder adduct of [60]fullerene with a Phthalocyanine. Journal of the Chemical Society, Chemical Communications. 1995;0:103-104. DOI: 10.1039/C39950000103
  61. 61. Maggini M, Dono A, Scorrano G, Prato M. Synthesis of a [60]fullerene derivative covalently linked to a ruthenium(II) tris(bipyridine) complex. Journal of the Chemical Society, Chemical Communications. 1995;0:845-846. DOI: 10.1039/C39950000845
  62. 62. Maggini M, Karlsson A, Scorrano G, Sandona G, Farina G, Prato M. Ferrocenyl fulleropyrrolidines: A cyclic voltammetry study. Journal of the Chemical Society, Chemical Communications. 1994;0:589-590. DOI: 10.1039/C39940000589
  63. 63. Drovetskaya T, Reed CA, Boyd PDW. A fullerene Porphyrin conjugate. Tetrahedron Letters. 1995;36:7971-7974. DOI: 10.1016/0040-4039(95)01719-X
  64. 64. Imahori H, Cardoso S, Tatman D, Lin S, Macpherson AN, Noss L, Seely GR, Sereno L, Chessa de Silber J, Moore TA, Moore AL, Gust D. Photoinduced electron transfer in a carotenobuckminsterfullerene dyad. Photochemistry and Photobiology. 1995;62:1009-1014. DOI: 10.1111/j.1751-1097.1995.tb02401.x
  65. 65. Williams RM, Zwier JM, Verhoeven JW. Photoinduced Intramolecular electron transfer in a bridged C60 (acceptor)-aniline (donor) system; Photophysical properties of the first “active” fullerene Diad. Journal of the American Chemical Society. 1995;117:4093-4099. DOI: 10.1021/ja00119a025
  66. 66. Imahori H, Sakata Y. Synthesis of closely spaced Porphyrin-fullerene. Chemistry Letters. 1996;25:199-200. DOI: 10.1246/cl.1996.199
  67. 67. Williams RM, Koeberg M, Lawson JM, An YZ, Rubin Y, Paddon-Row MN, Verhoeven JW. Photoinduced electron transfer to C60 across extended 3- and 11-bond hydrocarbon bridges: Creation of a long-lived charge-separated state. Journal of Organic Chemistry. 1996;61:5055-5062. DOI: 0.1021/jo960678q
  68. 68. Ziessel R, Allen BD, Rewinska DB, Harriman A. Selective triplet-state formation during charge recombination in a fullerene/Bodipy molecular dyad (Bodipy=Borondipyrromethene). Chemistry – A European Journal. 2009;15:7382-7393. DOI: 10.1002/chem.200900440
  69. 69. van Haver P, van der Auweraer M, Viaene L, De Schryver FC, Verhoeven JW, Van Ramesdonk HJ. Enhanced intersystem crossing in 3-(1-pyrenyl)propylbromide. Chemical Physics Letters. 1992;198:361-366. DOI: 10.1016/0009-2614(92)85065-I
  70. 70. Bartczak WM, Hummel A. Formation of singlet and triplet excited states on charge recombination in tracks of high-energy electrons in nonpolar liquids. A computer simulation study. Chemical Physics Letters. 1993;208:232-236. DOI: 10.1016/0009-2614(93)89067-R
  71. 71. Murakami M, Ohkubo K, Mandal P, Ganguly T, Fukuzumi S. Does bimolecular charge recombination in highly exergonic electron transfer afford the triplet excited state or the ground state of a photosensitizer? The Journal of Physical Chemistry A. 2008;112:635-642. DOI: 10.1021/jp0767718
  72. 72. Lavrik NL. Analysis of the recombination probability of geminate triplet radical ion pairs at single encounter by means of magnetic field effects. The Journal of Chemical Physics. 2001;114:9492-9495. DOI: 10.1063/1.1365083
  73. 73. Tero-Kubota S. Singlet and triplet energy splitting in the radical ion pairs generated by photoinduced electron-transfer reactions. Pure and Applied Chemistry. 2001;73:519-523. DOI: 10.1351/pac200173030519
  74. 74. Nishimura T, Nakashima N, Mataga N. Intersystem crossing in anthracene-N,N-diethylaniline exciplex. Chemical Physics Letters. 1977;46:334-338. DOI: 10.1016/0009-2614(77)85275-5
  75. 75. Mataga N, Migita M, Nishimura T. Picosecond chemistry of some exciplex systems. Journal of Molecular Structure. 1978;47:199-219. DOI: 10.1016/0022-2860(78)87185-3
  76. 76. Mataga N. Picosecond laser photolysis studies upon charge separation and intersystem crossing processes in some exciplex systems. Radiation Physics and Chemistry. 1977;21:83-89. DOI: 10.1016/0146-5724(83)90133-4
  77. 77. Swinnen AM, Van der Auweraer M, De Schryver FC, Nakatani K, Okada T, Mataga N. Photophysics of the intramolecular exciplex formation in .Omega.-(1-pyrenyl)-.Alpha.-(dimethylamino)alkanes. Journal of the American Chemical Society. 1987;109:321-330. DOI: 10.1021/ja00236a005
  78. 78. Kuciauskas D, Liddell PA, Moore AL, Moore TA, Gust D. Magnetic switching of charge separation lifetimes in artificial photosynthetic reaction Centers. Journal of the American Chemical Society. 1998;120:10880-10886. DOI: 10.1021/ja981848e
  79. 79. Kobori Y, Yamauchi S, Akiyama K, Tero-Kubota S, Imahori H, Fukuzumi S, Norris JR. Primary charge-recombination in an artificial photosynthetic reaction center. PNAS. 2005;102:10017-10022. DOI: 10.1073.pnas.0504598102
  80. 80. Fukuzumi S, Guldi DM. In: Balzani V, editor. Electron Transfer in Chemistry. Vol. 2. Weinheim: Wiley-VCH; 2001. pp. 270-337
  81. 81. Umeyama T, Imahori H. Carbon nanotube-modified electrodes for solar energy conversion. Energy & Environmental Science. 2008;1:120-133. DOI: 10.1039/B805419N
  82. 82. Guldi DM. Fullerene–porphyrin architectures; photosynthetic antenna and reaction center models. Chemical Socety Review. 2002;31:22-36. DOI: 10.1039/B106962B
  83. 83. Chitta R, D’Souza F. Self-assembled tetrapyrrole–fullerene and tetrapyrrole–carbon nanotube donor-acceptor hybrids for light induced electron transfer applications. Journal of Materials Chemistry. 2008;18:1440-1471. DOI: 10.1039/B717502G
  84. 84. Maligaspe E, Kumpulainen T, Subbaiyan NK, Zandler ME, Lemmetyinen H, Tkachenko NV, D’Souza F. Electronic energy harvesting multi BODIPY-zinc porphyrin dyads accommodating fullerene as photosynthetic composite of antenna-reaction center. Physical Chemistry Chemical Physics. 2010;12:7434-7444. DOI: 10.1039/C002757J
  85. 85. Rio Y, Seitz W, Gouloumis A, Vazquez P, Sessler JL, Guldi DM, Torres T. Panchromatic Supramolecular fullerene-based donor–acceptor assembly derived from a peripherally substituted Bodipy–zinc Phthalocyanine dyad. Chemistry - A European Journal. 2010;16:1929-1940. DOI: 10.1002/chem.200902507
  86. 86. Liu JY, El-Khouly ME, Fukuzumi S, Ng DKP. Photoinduced electron transfer in a Distyryl BODIPY–fullerene dyad. Chemistry, an Asian Journal. 2011;6:174-179. DOI: 10.1002/asia.201000537
  87. 87. Huang D, Zhao J, Wu W, Yi X, Yang P, Ma J. Visible-light-harvesting Triphenylamine Ethynyl C60-BODIPY dyads as heavy-atom-free organic triplet photosensitizers for triplet-triplet annihilation Upconversion. Asian Journal of Organic Chemistry. 2012;1:264-273. DOI: 10.1002/ajoc.201200062
  88. 88. Chen CY, Chen JG, Wu SJ, Li JY, Wu CG, Ho KC. Multifunctionalized ruthenium-based super sensitizers for highly efficient dye-sensitized solar cells. Angewanthe Chemie. 2008;120:7452-7455. DOI: 10.1002/ange.200802120
  89. 89. Monguzzi A, Mezyk J, Scotognella F, Tubino R, Meinardi F. Upconversion-induced fluorescence in multicomponent systems: Steady-state excitation power threshold. Physical Review B. 2008;78:195112. DOI: 10.1103/PhysRevB.78.195112
  90. 90. Wu W, Zhao J, Guo H, Sun J, Ji S, Wang Z. Long-lived room-temperature near-IR phosphorescence of BODIPY in a visible-light-harvesting N^C^N PtII–Acetylide complex with a directly Metalated BODIPY Chromophore. Chemistry—a European Journal. 2012;18:1961-1968. DOI: 10.1002/chem.201102634
  91. 91. Singh-Rachford TN, Castellan FN. Photon upconversion based on sensitized triplet–triplet annihilation. Coordination Chemistry Reviews. 2010;254:2560-2573. DOI: 10.1016/j.ccr.2010.01.003
  92. 92. Ji S, Wu W, Wu W, Guo H, Zhao J. Ruthenium(II) Polyimine Complexes with a Long-Lived 3IL Excited State or a 3MLCT/3IL Equilibrium: Efficient Triplet Sensitizers for Low-Power Upconversion. Vol. 50. Angewandte Chemie International Edition; 2011. pp. 1626-1629. DOI: 10.1002/anie.201006192
  93. 93. Chen HC, Hung CY, Wang KH, Chen HL, Fann WS, Chien FC, Chen P, Chow TJ, Hsu CP, Sun SS. White-light emission from an upconverted emission with an organic triplet sensitizer. Chemical Communications. 2009;0:4064-4066. DOI: 10.1039/B905572J
  94. 94. Yang P, Wu W, Zhao J, Huang D, Yi X. Using C60-bodipy dyads that show strong absorption of visible light and long-lived triplet excited states as organic triplet photosensitizers for triplet–triplet annihilation upconversion. Jounal of Materials Chemistry. 2012;22:20273-20283. DOI: 10.1039/c2jm34353c
  95. 95. Moor K, Kim JH, Snow S, Kim JH. [C70] Fullerene-sensitized triplet–triplet annihilation upconversion. Chemical Communications. 2013;49:10829-10831. DOI: 10.1039/c3cc46598e
  96. 96. Guo S, Sun J, Ma L, You W, Yang P, Zhao J. Visible light-harvesting naphthalenediimide (NDI)-C60 dyads as heavy-atom-free organic triplet photosensitizers for triplet-triplet annihilation based upconversion. Dyes and Pigments. 2013;96:449-458. DOI: 10.1016/j.dyepig.2012.09.008
  97. 97. Lim GN, Maligaspe E, Zandler ME, D’Souza F. A Supramolecular tetrad featuring covalently linked Ferrocene–zinc Porphyrin–BODIPY coordinated to fullerene: A charge stabilizing, photosynthetic antenna–reaction Center mimic. Chemistry – A European Journal. 2014;20:17089-17099. DOI: 10.1002/chem.201404671
  98. 98. Sera N, Tokiwa H, Miyata N. Mutagenicity of the fullerene C60-generated singlet oxygen dependent formation of lipid peroxides. Carrinogenesis. 1996;17:2163-2169. DOI: 10.1093/carcin/17.10.2163
  99. 99. Hamano T, Okuda K, Mashino T, Hirobe M, Arakane K, Ryu A, Mashikoc S, Nagano T. Singlet oxygen production from fullerene derivatives: Effect of sequential functionalization of the fullerene core. Chemical Communications. 1997;0:21-22. DOI: 10.1039/A606335G
  100. 100. Prat F, Stackow R, Bernstein R, Qian W, Rubin Y, Foote CS. Triplet-state properties and singlet oxygen generation in a homologous series of functionalized fullerene derivatives. Physical Chemistry A. 1999;103:7230-7235. DOI: 10.1021/jp991237o
  101. 101. Prat F, Martí C, Nonell S, Zhang X, Foote CS, Moreno RG, Bourdelande JL, Font J. C60 fullerene-based materials as singlet oxygen O2(1Δg) photosensitizers: A time-resolved near-IR luminescence and optoacoustic study. Physical Chemistry Chemical Physics. 2001;3:1638-1643. DOI: 10.1039/B009484F
  102. 102. Bourdelande JL, Font J, Gonzalez-Moreno R. Fullerene C-60 bound to insoluble hydrophilic polymer: Synthesis, photophysical behavior, and generation of singlet oxygen in water suspensions. Helvetica Chimica Acta. 2001;84:3488-3494. DOI: 10.1002/1522-2675(20011114)84:11<3488::AID-HLCA3488>3.0.CO;2-7
  103. 103. Murata Y, Komatsu K. Photochemical reaction of the open-cage fullerene derivative with singlet oxygen. Chemistry Letters. 2001;9:896-897. DOI: 10.1246/cl.2001.896
  104. 104. McCluskey DM, Smith TN, Madasu PK, Coumbe CE, Mackey MA, Fulmer PA, Wynne JH, Stevenson S, Phillips JP. Evidence for singlet-oxygen generation and Biocidal activity in Photoresponsive metallic nitride fullerene-polymer adhesive films. ACS Applied Materials & Interfaces. 2009;1:882-887. DOI: 10.1021/am900008v
  105. 105. Collini E, Fortunati I, Scolaro S, Signorini R, Ferrante C, Bozio R, Fabbrini G, Maggini M, Rossi E, Silvestrini S. A fullerene-distyrylbenzene photosensitizer for two-photon promoted singlet oxygen production. Physical Chemistry Chemical Physics. 2010;12:4656-4666. DOI: 10.1039/b922740g
  106. 106. Gobeze HB, Tram T, Chandra BKC, Cantu RR, Karr PA, D’Souza F. Singlet oxygen generation and Photoinduced charge separation of tetra Polyethyleneglycol functionalized zinc Phthalocyanine-fullerene dyad. Chinese Journal of Chemistry. 2016;34:969-974. DOI: 10.1002/cjoc.201600403
  107. 107. Montagnon T, Tofi M, Vassilikogiannakis G. Using singlet oxygen to synthesize Polyoxygenated natural products from furans. Accounts on Chemical Research. 2008;41:1001-1011. DOI: 10.1021/ar800023v
  108. 108. Kyriakopoulos J, Papastavrou AT, Panagiotoua GD, Tzirakis MD, Triantafyllidis K, Alberti MN, Bourikas K, Kordulis C, Orfanopoulos M, Lycourghiotis A. Deposition of fullerene C60 on the surface of MCM-41 via the one-step wet impregnation method: Active catalysts for the singlet oxygen mediated photooxidation of alkenes. Journal of Molecular Catalysis A: Chemical. 2014;381:9-15. DOI: 10.1016/j.molcata.2013.09.036
  109. 109. Huang L, Cui X, Therrien B, Zhao J. Energy-Funneling-based broadband visible-light-absorbing Bodipy–C60 triads and tetrads as dual functional heavy-atom-free organic triplet photosensitizers for Photocatalytic organic reactions. Chemistry – A European Journal. 2013;19:17472-17482. DOI: 10.1002/chem.201302492

Written By

Elif Okutan

Submitted: 07 December 2017 Reviewed: 26 January 2018 Published: 06 April 2018