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By Th. Forster [*I
Dedicated to Professor H. Bredereck on the occasion of his 65th birthday
Excimers are molecular associates that exist only in excited electronic states. They are therefore detectable only in emission spectra, and particularly in fluorescence spectra. Despite their short lifetimes, they are responsible for many photophysical and phofochemical effects.
The concentration quenching of fluorescence is a phenomenon that has been known for a long time. It was discovered only recently, on the other hand, that instead of quenching, many fluorescent organic compounds exhibit a change in the fluorescence spectrum, i. e. a new component becomes evident in such a spectrum with increasing concentration. Since n o corresponding change is observed in the absorption spectrum, the new fluorescence component must be ascribed to an associate formed only after absorption of light in the electronically excited state 111. The term “excimers” has become widely accepted for associates of this type [zl. The fluorescent properties of crystals of many organic compounds and of macromolecular substances are due to excimers, as are the properties of some liquid scintillator systems. Excimers have also been detected as intermediates in many photochemical reactions, and it may be assumed that they are also involved in analogous radiochemical processes. An attempt will be made in this article to present a brief survey of existing knowledge in this field c31.
formation of excimers is still most easily demonstrated for pyrene.
Spectra of (oxygen-free) solutions of this compound at various concentrations in n-heptane at room temperature are shown in Figure 1. The structured spectrum observed at concentrations of 5 x 10-5 M and less is the fluorescence spectrum
% 110~crn-’i +
Fluorescence spectra of pyrene in n-heptane.
t = 20 “C, c (mole/l): 5 x 10-5 (a), 1.8 x 10-4 (b), 3.1 Y 1 0 - 4 (c), 7 . 0 x 1O-O (d).
2. Excimer Formation of Pyrene in Solution
The role of the association of excited molecules as the cause of a change in the fluorescence spectrum with concentration was first recognized by us in the case of pyrene and some of its derivativesr41; and the
[ * ] Prof. Dr. Th. Forster
Institut fur physikalische Chemie der Universitat 7 Stuttgart I , Wiederholdstr. 15 (Germany) [l] Th. Forster and K . Kasper, Z . physik. Chem. N.F. I , 215
(1954). 121 B. Stevens and E. Hutton, Nature (London) 186, 1045 (1960).
The term “excimer” should refer generally to electronically excited molecules whose physical and chemical properties differ appreciably from those of the same molecules in the ground state. However, the name has become commonly used for excited molecular associates, particularly dimers. [3J Cf. R. M . Hochstrasser, Annu. Rev. physic. Chem. 17, 466
(1966).  Th. Forster and K . Kasper, 2. Elektrochem., Ber. Bunsenges. physik. Chem. 59, 976 (1955).
of monomeric pyrene, which extends from the U V to the violet region of the visible spectrum. An additional unstructured Component appears at higher concentrations in the blue region, i.e. at longer wavelengths, and this component ultimately becomes the only one present. If, as in this example, the spectra are recorded for the same absorption of the exciting light, all the curves intersect at a single point. Such a n “isoemissive” or “isostilbic” point (51 of a n emission spectrum occurs if the spectrum consists of contributions due to only two components. I t corresponds to the isosbestic point of a n absorption spectrum, though the latter remains unchanged in the present case over the entire concentration range in which the fluorescence change occurs. Because of this validity of the Beer-Lambert law, as well as other observations, the blue fluorescence component is attributed to a n associate that exists only in the excited electronic state, i.e. to a n excimer. The absorption and fluorescence spectra of oxygen-free pyrene solutions remain unchanged o n prolonged irradiation, and no stable photoproduct can be detected .
The mechanism of excimer formation can be deduced from the quantitative course of the fluorescence
[SJ From ~ T ~ A P E L V shine. : I am grateful to Dr. H . E. A. Krarner, Stuttgart, for this suggestion.
Angew. Chem. internut. Edit.
VoI. 8 (1969) / No. 5
5 . physik. Munro. The curves given in Figure 3 for pyrene in cyclohexane at a concentration slightly above the half-value concentration confirm the expected time characteristics. This is obvious from the temperature dependences of the two fluorescence components. Vol. Z. 2. 132 (1962). This is due to the thermal dissociation of the excimers. The first confirmation of a time dependence of this type was provided by the different and concentration-dependent quenching of the two fluorescence components by oxygen [4. the half-value concentration being Ch = 1. A+hv A (AA) + hv’ (AA) (a) 1 J A + A -+ : Normal (“adiabatic”) reaction processeswithout alteration --e of existing excitation. 52 (1957). the concentration dependences of the fluorescence quantum yields r] and q’ of the monomeric and excimeric components are 0 [ A m 50 100 Tlfl51--.F. B. Chem. with an average decay time 7 = l/(ks + kl + k. 3. Radiation processes. Both k a and Ch should therefore depend on the viscosity of the solvent. which are shown in Figure 4 for pyrene in liquid paraffin at a medium  K . Kasper. Time dependence of excitation ( a ) .e. SOC.10 f 05 p and thus increases in proportion to the concentration. N. 34. c = 5 x 10-3 mole/l [ 8 ] . = 1.2XlO-3 mole/]. and Munro later managed to follow the emission from both components directly on flash-excitation 181. N. Angew. Relative intensities of monomer component (a) and excimer component (b) of the fluorescence of pyrene in benzene. this leads to the following reaction scheme [4. Half-value concentration q. 2. the decay of the monomer emission is purely exponential. Doller and Th. though the strict proportionality expected from eq. H. : According to reaction scheme (a). a Stern-Volmer equation (1) for the monomer component and a corresponding inverse relation (1’) for the excimer component. The slopes of the curves correspond to a bimolecular mechanism for the formation of the excimer by combination of an electronically excited molecule A* (in the lowest excited singlet state) with an unexcited molecule A (in the singlet ground state). The ratio of the quantum yields becomes The association reaction that takes place during the brief excitation of the monomer has to be very fast. The half-value concentrations measured in various inert solvents (aliphatic and aromatic hydrocarbons. : Radiationless (“diabatic”) deactivation processes. follows a complicated bi-exponential course passing through a maximum.F. The excimer emission.c). Z . on the other hand. Birks. Forster. and the dissociation of the excimer to be discussed later. 575 (1963). respectively. the radiationless deactivation of the excited monomer and of the excimer.  E. D .’ Fig. and I. i. Edit. Dyson. [ 8 ] J. alcohols) d o in fact increase with increasing viscosity. Their concentration dependences agree with equations (1) and (l’). Dyson. (London) A 275. physik. qmax and q k a x are the maximum quantum yields of the two components for very low and very high concentrations. 8 (1969)1 No. Together with the processes of fluorescence emission. Chem.) 150 200 Fig. Proc. I = 20°C. (4) is not observed. internat. Roy.2 x 10-3 molejl. which has not yet been taken into account. monomer component (b). The concentration dependence of the intensities of the two fluorescence components for equal absorption is shown in Figure 2 for pyrene in benzene. the quantities occurring in equations ignored ( k d = O (1) to (2) are 0 10 10-3 10-2 55il c Imoteill - 10. The relative quantum yields are identical with the relative intensities in Fig. Provided that the dissociation of the excimers can be ) . Chem. 12. and excimer component (c) of pyrene in cyclohexane. J. such as is also found in the formally analogous case of secondary products of a radioactive decay series.63: For k d = 0. Birks. change.71. and hence diffusion-controlled. and Ch is the half-value concentration which is common to both relations.
Nature (London) 194. and A . At lower temperatures Ch becomes diffusioncontrolled.peryleneC191. Optika i Spektroskopija 4. 1083 (1961). 442 (1962). values between 10 and 71 kcal/mole have been found in various solvents [ 6 . Figure 5 shows the temperature dependence of the half-value concentrations of pyrene in various inert solvents 191. Birks. Yu.F. 36. 31. 8 (1969) / No. SOC. The opposing intensity variations of the two components above and below 80°C are due to the fact that the formation of the excimer predominates at low temperatures.  J.  E. in this range the excimer dissociation equilibrium is established. D . 329 (1951). 2. Fig.  Th. Mokeeva.171. (4)is replaced by the more general expression for the half-value concentration: If dissociation predominates (kd 9 kl + ki). J. Seidef.F. benz[a]anthracene[18 191. Sveshnikov. 5 . Physics 34. B. and B. Sveshnikov. ff. When it is taken into account. 58 (1965). 4. naphthalene [16.(London). internat. it seemed that the ability to form excimers was confined to this hydrocarbon and a few of its derivatives such as 3-chloropyrene and the related benzo[b]pyrene. Christophorou. These temperature functions can be used to find the kinetic and thermodynamic parameters of excimer formation. B. A . A 274. 9 1969). A. the half-value concentration n o longer depends on k a . Birks and L. 0. and increases with solvent viscosity. J.5-diphenyloxazole and attributed to excimers 1141. benzene 1151. 0: quantum yield of the monomer component. alone. N. A weak excimer component was also found for some 9-alkylanthracenes 1131. Birks and L. Bandow. Roy. 631 (1958). Christophorou. In the high temperature range (left). c = 5 x 10-3 mole/l 161. B. Lumb. 1121 N. B. 193 (1955). it is then determined by the excimer dissociationequilibrium. G . 45. but (as later by other authors"*]) had been attributed to ground state association. Z . Austral. Temperature dependence of the fluorescence of pyrene in liquid paraffin. Chem. physik. Vol. some of the excited monomers pass through the excimer stage. though not for anthracene itself. B. Chem. 010 0 ' 1 I 100 t I"CI 200 300 Fig. 552 (1963). 2. the entropy of dissociation of the excimer (based on unit concentrations) is found to be about 20 cal/deg. 3. Weinreb. I l l ] F. where it has been assigned the rate constant k d . Acta pathol.concentration 161. 586 (1962). Since 1962. Optika i Spektroskopija I 2 . Proc. 274 (1962). physik. This process is indicated in scheme (a).  J . Another one was detected by Berlmun for 2. but eq. m: of the excimer component. Chem. Norden. changes in fluorescence spectra with concentration have also been observed (though only at lower temperatures or considerably higher concentrations than in the case of pyrene) for many aromatic compounds. Bedman. 289 (1964). Chem. S . Speed and B. for which ____ [8a] R . Tischenko. Chem. The most interesting quantity is the enthalpy of dissociation of the excimer. G . Cherkasov. Ya. 325 (1962). Roy.  T . microbiol. DdUer and Th. equations (1) to (3') remain unchanged. Forster and H . 5 335 .mole. Ch increases with rising temperature and is practically independent of the nature of the solvent. scand. As dissociation equilibrium is approached the difference in the time dependences of the two components disappears L8al. Fbrster.  G. Selinger. V . If dissociation is appreciable. SOC. physik. 196. Ivanova. N. These values indicate strong bonding and a rigid configuration for the excimer of pyrene. and I.g. but on the ratio k d / k a . Angew. B. Berg and G. I [lo] J. chem. Edit. 22. P. G . while its dissociation with reformation of the excited monomer predominates at high temperatures. Proc. d With the aid of the fluorescence decay time. whose fluorescence changehad already been observed by Bandow [Ill. Munro. M. Excimer Formation of other Aromatic Compounds Following the discovery of excimer formation for pyrene (1954). Optics and Spectroscopy I 2 . so that the decay of the monomeric component is no longer exponential. Berlman and A .  I. 313 (1962). (London) A 280. Molecular Physics 5 .anthanthrenerlgl. e.  I . Temperature dependence of the half-value concentration for the change in the fluorescence spectrum of pyrene with concentration [91. and is independent of the viscosity of the solvent.
20 25 30 The conditions for the occurrence of excimer fluorescence in the cases discovered later show that such excimers are less tightly bound. Fluorescence spectra of naphthalene in toluene at various temperatures and concentrations 1161. Faraday SOC.  J. Bazilevskaya and A . Dickinson. Amer. 551 (1965).60. and thus exceeds the dissociation energy of the pyrene excimer.30. Birks and L . 825 (1966). Edit.(London) A 291.  J. SOC. Proc. B. i. Despite the difference in the dissociation energies. reduce these values further. Nishimura.Birks and Christophorou [221 have collected data on excimer formation of many aromatic compounds. J.  J. Fasman. 77 (1965). but undergoes transformation into the stable dianthracene (cf. Christophorou. Figure 7 shows the potential-energy diagram. 5 . M . C . benz[a]anthracene . J . which corresponds to an energy difference of 17 kcal/mole. I. Austral. Proc. 401 (1963). 83 (1965). B. SOC. SOC. (London) A 277. K . Amer. Figure 6 shows the fluorescence spectra of naphthalene in toluene 1161. 30. and that excimer dissociation occurs even below room temperature. Birks and L. S. Birks and R . B. Anthracene itself does not give a fluorescence change. 7. 19. Selinger. Optika i Spektroskopija 18. B. alkyl substituents. molecular Spectroscopy 23. the differences between the fluorescence maxima of the monomer and the excimer are almost as large in these cases as for pyrene. internat. Proc. SOC. Aladekomo and J . Section 11). Accordingly. about 6000 cm-1. 7. [26a] N . Potential energy diagram for the formation of the excimer. chem. Trans. J. 1 Vol.  M . 336 Angew. B. S. Chem. B. chem. 270 (1964). Forster. J. D .  J. SOC. 1201 J. The time characteristics of fluorescence have been studied for naphthalene [321. Optics and Spectroscopy 18. Birks and J. B. Stevens and M . Stevens and T. S. 367 (1965). 1311 B. Barnes. Birks. Birks. Proc. D . 1515 (1964). D . As an example.bl. (London) A 284. Molecular Physics 9. Ban. Christophorou. Domination of excimer fluorescence similar to that found in moderately concentrated pyrene solutions is observed only for a few liquid methylnaphthalenes [27-*91.and a large number of derivatives Q0-261.311. Lumb. [26b] J. Acta 20. 1321 N. Birks. The excimer component is barely visible at room temperature even at very high concentrations. 4687 (1965). Roy. SOC. Roy. m". and T. L. 58. e. 556. Pure appl. Proc. 571 (1964). This explains not only the diffuse character of excimer fluorescence. but exhibits concentration quenching. Roy. 73 (1963). 145 (1965).  B. on the other hand. are similar in magnitude to that of the pyrene excimer (w20 cal/deg-mole). and even more so than those of other aromatic excimers. Acta 19. 1281 B. (London) A 283. 6. Chem. Chem.e. Lumb and D . Dyson. Cherkasov. Spectrochim. L. Weyl.I Fig.g. G . J. D . Mataga. Roy. A .  S . Tomura. R = distance between the molecular planes. which should sterically hinder excimer formation. Braga. A. 5-6 kcal/mole for benzene 1231 and for naphthalene [24. which does not however emit.  Th.(London) A 277. G. after Stevens and BanE301. King. but also the failure of all attempts to find a corresponding component in the absorption spectrum without additional fixation of the excimer components. Spectrochim. SOC. t _-__--A+A R VO 16698. 15 (1964). According to this diagram the ground state of the excimer is unstable. 20 25 3 11~~crn-'1+ 30 Fig. 570 (1966).87. Roy. Lehrer and G.11 v. Aladekomo. 5492 (1963). 8 (1969) 1 No. 5. B. and H. including substituted anthracenes [26a. this is also due to the formation of an excimer. for a sandwich configuration of the excimer resulting from the mutual approach of the two components with their molecular planes parallel.  J. and M . The dissociation entropies. 365 (1967). and emerges only at low temperatures. the dissociation enthalpies are low.
P . physik. on the other hand. Roy. should be obtainable from the pressure dependence of the effect. which must contain a t least two molecules of the aromatic compound if the excirner is to be formed. Optika i Spektroskopija 18. Optics and Spectroscopy 18. Weller. internat.on the other hand. Selinger. J . 977 (1965) Larger molecules in which two or more aromatic residues are flexibly linked to each other by aliphatic carbon atoms should be capable of forming intramolecular excimers. 38 (1964). Forsfer.and triphenylalkanes whose phenyl groups are joined b y aliphatic chains containing exactly three carbon atoms. iNo. Physics 42. has a similar value with cetyldimethylbenzylammonium chloride as the detergent [37J. probably owing to an activation barrier to the formation of the excirner. occurring on formation of the excimer from the monomers. 8 (1969) . Hirayama. Chem. 886 (1965). (London) A 291. for naphthalene and other compounds where the dissociation equilibrium is established. Estimation of the micelle size o n this basis leads to values similar to those found by the usual metbods. N. Forster and B. Intramolecular Excimers 22 26 30 Fig. 3163 (1965). In the former case. Similarly. J . The intensity ratios of the monomer and excimer components. N. and their fluorescence spectra should contain a n excimer component that is independent of concentration. or its negative. In such solutions of aromatic hydrocarbons.6-dirnethylnaphthalenein n-heptane at various pressures. Proc. I. vary at much lower pressures. 190. Braun and Th.  Th. the change in the fluorescence spectra with concentration is controlled by the equilibrium of excimer formation. On the other hand. the extent of excimer formation should be governed. 8).0 AL361. A . Seidel and B. Bunsenges. give fluorescence spectra containing both monomer and excimer components at room temperature ‘391.  F. Forster. This deviation is due to the size of the micelles. King. Fig. Shirokov. physik. excimer dissociation attains complete equilibrium. I391 M . H . this is the case with di. the distance between the two molecular planes in the excimer can be estimated from the volume contraction to be about 3. chem. Further Investigations on Excimers i n Solution In the equilibrium case. 8. 1091 (1966). Angew. the excimer component increases with pressure [361 (cf. pyrene in the same system has a half-value concentration of 2. Bazilevskaya. and A. S. Their absorption spectra are normal and resemble those of ethylbenzene or of diphenylalkanes with shorter or longer connecting methylene chains that are incapable of excimer formation because of steric or statistical factors. for pyrene below room temperature. Seidel. the intensity ratios of the two Components in these cases depend on the solvent. they solve in the lipid phase. Austral. Fluorescence spectrum of 1. but not on the concentration. 2. This contraction is considerable if compared to twice the molar volume of naphthalene in the crystalline state (224 cm3/mole). chem. ~ 1331 J . polystyrene shows only the monomer component. Solutions of polystyrene and of polyvinylnaphthalene. 244 (1966). A .6 x 10-2 mole/l. c = 0. Physics 43. K . Birks and T . 39. 18. Naturforsch. 70. [351 H. S. e . Chem. I361 H . I 3 4 1 Th. the excimer component is found to decrease. Haebig. E d i t .or equilibrium-controlled [34. T . but by its local concentration in the lipid phase. The pressure dependences of naphthalene-excimer formation in a series of different solvents gave almost identical values of 16 cm3/mole for the volume contraction. Aromatic hydrocarbons can be solubilized in water by suitable detergents. Rice. P. Limareva. It is in fact found that 2-methylnaphthalene. the volume contraction. Ber. In the case of naphthalene. which is greater by a factor of 20 than that in a comparable homogeneous solution. but appreciable variations occur only at pressures above 10 kbar.F.351. According to Hirayama [381. which has a well defined rnicelle structure under suitable conditions. but this is merely due t o the pressure-induced increase in solvent viscosity. and S t . whose fluorescence change in homogeneous solutions corresponds to a half-value concentration of about 1 mole/l. Vala. Chern. J Vol. Chem. and V . SOC.and derivatives of these compounds [331. the volume expansion connected with dissociation. 5 337 . The fluorescence spectra of two such compounds are shown in Figure 9. not by the overall concentration of the aromatic compound in the solution. 4. 354 (1965). in which the aryl groups are again linked by aliphatic chains of three carbon atoms. 5. At 77 OK. A . J. B. The direction of this variation depends on whether excimer formation is diffusion. A . 265 (1963). 0. Cherkasov. If a sandwich structure is assumed. f = 20 “ C . The fluorescence properties of aromatic compounds in solution depend on pressure even in the absence of any molecular association. Selinger.32 mole/l 1301. the dissociation enthalpy of the excimer can be found from the temperature dependence of this equilibrium. Z . 202 (1965). L. g . C . Leiber. and the same purely exponential decay is observed for both components. J.
 J . Kazzar. and perylene (a-form). Offenand R . Physics 28. 6. J. as is shown by the absorption spectra of type B crystals.and [6. Jones and M . in whose lattices adjacent molecules have an arrangement similar to that in the excimer. which act as traps and capture the initially delocalized excitation energy. 439 (1962). J. though their absorption spectra are monomolecular 1401. Physics 37. benz[u]anthracene 1501. Excimer fluorescence occurs only in crystals of the B type. J. this fluorescence shifts to still longer wavelengths as the pressure is increased. which disappears only after a relatively long time or on annealing.  A . 2540 (1962). chem. Camerman and J. Nakashima and H. Acta 18. chem. two phenyl groups are linked by methylene chains in the p. 556 (1966). 338 Angew. Thus here too the excimer configuration is achieved only after light absorption. Ron and A. with further approach of two molecules that were already adjacent. 3759 (1965). internat. J. This has been observed for crystals of naphthalene 147-491. in which the molecules are either arranged in pairs. M. In the case of pyrene [521 and a-perylene crystals 1531. and naphthacene 1511. W. 8 (1969) / No. as in pyrene. Offen and R . Birks. F. G .4-dioxane (---) 1381. Schnepp. Many observations suggest that the excimer fluorescence is emitted preferentially by lattice defects.2]-Paracyclophane exhibits pure excimer fluorescence. and T. Wolf. King. According to Stevens 1451 a general relationship exists between fluorescence and the crystal structure of aromatic compounds. all these compounds have normal absorption spectra. [SO] H .41. while those of [4. Proc.4096 (1965). SOC. W. 9. Roy. W. Sci. Offen. Schnepp. 18. favor structures of a B type. Ferguson. Schnaithmann and H. Fluorescence s p e c t r a of 1. and T . 5 .636 (1965). chem. Chem. Yarnane. For crystals that give excimer emission only at high pressures. [2. Trotter.19 (1966). Spectrochim. chem. Ron and A. Physics 44. the distance between the two phenyl groups is appreciably shorter than that of closest approach between freely mobile groups. Excimer Fluorescence in Crystals and Stable Aggregates The fluorescence of crystalline pyrene is blue and structureless. ovalene. F.53 A“441. In this connection. Physics 43. 1481 P. J. though the red shift in relation to the monomer emission is not always as large as in solution. Eisinger. J. 1237 (1963). an A type. 1441 A. ZDa. and other “elongated” molecules favor structures of 1401 J. W.a Fig. J . Physics 44. A. In addition to their excimer fluorescence. phenanthrene 1491. SOC.  A. Jones and M. Nicol. “Disk-shaped molecules”. chem. as in perylene @-form). Naturforsch. this arrangement is by no means the same. The observation that a-perylene no longer exhibits excimer fluorescence at very low temperatures1461 could be explained by a freezing of this configuration change. which exhibit excimer fluorescence even at normal pressure. Physics 48. Nucleic acids and synthetic di. E d i t . 4817 (1968). This fluorescence is also due to excimers. which is attributed to surface defects 1541. In this case it appears that even in the unexcited state. anthracene 148-501. Z . chem. benzo[g. chem. in which adjacent molecules are oriented almost perpendicular to one another. 3584 (1968). R.3-triphenylpentane (b) i n cyclohexane ( --) a n d 1.421. microcrystals of pyrene exhibit a weak monomer component.Japan 36. (London) A 291.  J. Nevertheless. B. so that after return to normal pressure the spectrum still has an excimer component. J. chem. Eliason. the molecules are arranged in parallel pairs with a n interplanar distance of 3. 16 (1965). anthracene. Physics43. ilperylene. 765 (1958).  R. Physics 48. Acad. Acta crystallogr.3-d1phenylpropane (a) a n d 1. the fluorescence change is frequently irreversible. and its maximum (4600 A) hardly differs from that of the long-wave component in solution (4760-4780 A). nat. The structureless band is generally interpreted as excimer fluorescence.4]-paracyclophane (in solution at room temperature) shows only the excimer component. Physics 48. Ferguson [431 recalled attention to the fact that in the crystal lattice of pyrene. which (apart from a slight Davydov splitting) are very similar to the solution spectra. C . Offen. Naphthalene. and may be regarded as monomer spectra. chem. chem. phenanthrene. J. [Sl] T. and benzo[b]pyrene (monoclinic form). 1451 B. In paracyclophanes. but its absorption spectrum is also different from those of its homologs. coronene.6]-paracyclophanes contain practically no excimer component. Bull. The degree of reversibility seems to depend both on the size of the crystal and on the irradiation at 1461 J . R .  P . or stacked in columns in the crystal lattice. on the other hand. 699 (1966). Schulman. Nicol.  H. USA 55. T. The fluorescence spectra of such crystals are not very different from those of dilute solutions. The fluorescence spectrum of [4. chrysene 1501. A. 5440 (1968). A . A. / Vol. GuPron.5]. 1015 (1966). Beardslee. Proc. 1531 H .h.3. Stevens. Tanaka.and polynucleotides also exhibit excimer fluorescence. The monomer fluorescence exhibited by many crystalline aromatic compounds in agreement with their lattice type changes at high pressures (10 to 50 kbar) into a structureless band at a longer wavelength.p’ position [39.
Munroe.3533 (1963). physik. 385 (1967). A . according to which excimer and singlet excited monomer are formed via an intermediate higher excited excimer state. 13 (1967).-H. They can also be formed via two monomers in metastable triplet states I551 H. 162 (1964). Mataga.high pressure An extreme case of a disordered lattice exists in solids having amorphous structures. that in prompt fluorescence.-H. Spectrochim. H . the excimer component of pyrene in solution persists over several milliseconds[21. and so takes place only over short distances. This process involves electron exchange between the two molecules. Pohl. Kortiim. 339 . Physics 44. 3546 (1966). which would not be sufficient alone. B. Razi Naqvi. 54. A. and E . A . I . 1741 C. though not necessarily so short as the distance for excimer formation by process (b). chem. P. the first resulting in monomer fluorescence and the second in excimer fluorescence[621. This biphotonic nature of the process led to its interpretation by the reaction scheme (b). Different dimers are obtained by controlled heating and by photolysis of dianthracene. process (b’) and the monomer component predominate in delayed fluorescence. Spectrochim. A. 5 At low temperatures and correspondingly high solvent viscosities. The first indication of process (b) came from the observation by Stevens and Hutton that on flash excitation. 353. B. H . Perkampus and L. Ferguson. Parker and C . 561 (1968). Y. e. Z. [ 5 8 ] E. but with the excimer component predominant because of incomplete equilibration. 40. C. 39. Physics 43. but are similar to those of the crystals. The controlled heating method yields sandwich dimers of pyrene [571 and perylene [593. but not exactly the same as. whereas the molecular planes in the other dimer are inclined at about 55’ t o each other. Physics 67. Torihashi. The dimers of anthracene itself are particularly interesting. 1641 P.  T. An excimer formed in accordance with Scheme (b) should be evident in the spectrum of “delayed fluorescence”. an emission that has the same spectrum as fluorescence. Azumi and S . 241 (1967). H. Stevens. 1591 J . 331 (1963). Physics 45. Physics Letters 1 . Birks. and B. L66-681. Parker.  C. Jarnagin. The sandwich dimer and the 55 O-dimer also differ very markedly K (r 200 and w 10 ns in their fluorescence decay times at 77 O respectively) (631. Chem. 3554 (1966). anthracene gives only monomer fluorescence both in solution and in the crystalline state. A. The ratio of the two components varies with temperature and concentration in a manner similar to. Physics 39. Ferguson.  J. Birks. J. Physics 47. McRae. G . 165 (1961). At higher temperatures. Hutton. Tanaka. Parker in A . 1192 (1963). Seances Acad. Edit. Dupuy and Y.and 9. 1651 C . N. Ban. One should therefore also expect excimer fluorescence from isdated pairs of molecules having a similar configuration. Ferguson. has been proposed by Birks [70-721 and further discussed by other authors [73-751. J. Sci. Obviously. B.  E. C.  E. have also been obtained by one or other of these methods[60. J. Physics Letters 24A. Excimers from Triplet States or Free Radicals The formation of excimers is not restricted to the combination of a singlet excited monomer with an unexcited monomer (Scheme (a)). Nature (London) 198. Z. 8 (1969) 1 No. chem.  H. Ferguson. Chem. j7OJ J . 323 (1966). J . (denoted by (t) to distinguish them from singlet excited states (*)): At + At + (AA)* [ z ? A* + A] (b) To produce a singlet excimer. A.lO-disubstituted anthracenes. B.F. but a longer decay time because of the time spent in the triplet state. whose absorption and fluorescence spectra differ considerably from those of the monomeric compounds. C. 1677 (1967). which also give excimer fluorescence. J. 1299 (1963).  C . Nature (London) 200.  N. G. Cambridge University Press 1967. are added together. F. Fielding and R. Physics 45. Perkampus and L. J . such “sandwich dimers” can be produced from supercooled solutions of the aromatic compounds in vitreously solidifying solvents by controlled heating and recoolingf571. f Vol. Films of anthracene prepared in this way at -70°C exhibit excimer fluorescence. E. J. chern. McGlynn. Birks. hebd. the excitation energies of the two triplet molecules. 261. It has been deduced from fluorescence decay times that deformed anthracene crystals contain lattice defects corresponding to the 55 “-dimer f641. E. B. 4175 (1965). 479 (1967).  E. and. which changes into monomer fluorescence on crystallization ( 5 5 561. which are obtained in the case of organic substances by condensation from the vapor at low temperatures. 397 (1966). Excimer formation appears from these observations to concern parallel pairs of adjacent molecules within the crystal rather than the crystal as such. Molecular Crystals 4. Ferguson. Stevens and M . also by photolytic decomposition of the stable photodimers 1581. low-intensity component. the excited monomer (as indicated in (b)) is regenerated by dissociation of the excimer. Chandross and J . The concurrent processes (b) and (b’) are considered together in the Parker-Stevens mechanism of delayed fluorescence. Parker and Hatchard later found that this is due to a separate. 397 (1963). The singlet excited monomer may also be formed directly by an energy transfer process between the two separate triplet molecules [691: At At + A* L A (b’) 7. Physics Letters 1. 2677 (1966). Parker. in the case of anthracene and some of its derivatives. Nature (London) 190. chem. A .  J . Tanaka. Physics 45. slowly decaying. Zahlan: The Triplet State. chem. J. these sandwich dimers too emit only after further approach of their components. Chandross and J . internat. Angew. Moore.  K . chem. According to Ferguson.  J . Perkampus and K . and Y. G . Physics 43. Sandwich dimers of 9. physik.F. Chem. and I . Ota. Chandross. Rousset. Hatchard. 306 (1965). which is superimposed on the normal fluorescence. R. In agreement with its crystal type (A). A different mechanism. The monomer component also appears with that of the excimer in delayed fluorescence. and is proportional to the square of the excitation intensity. J. Acta 22. p. A. Acta 22. i . N.  J . 3075 (1965). chem. Pohl. chern. Chem. Chandross. It can be concluded from the absorption spectra that only the latter has a sandwich configuration. J. ibid.  F.611. chem. 173 (1968). Chern.
Obyknovennaya and A. Angew. R. Chem. S . Joyce. S. 87. Physics 36. Ezumi. 46 (1968). Cherkasov. Wiley. F. Aromatic compounds having very similar constitutions.  R. chem. More favorable conditions for the formation of unsymmetrical excimers are provided by molecules having very different ionization potentials and electron affinities. Optika i Spektroskopija 21. 1921 H. The formation of unsymmetrical excimers between molecules of aromatic compounds having essentially different excitation energies is less obvious. the emission of less strongly bound excimers is confined to a narrow temperature range. SOC. chem. 22 (1968). obviously. Bunsenges. Marmor Spruch: Luminescence of Organic and Inorganic Materials. where they give rise to broad structureless absorption bands in addition to those of the components. 5 . 34. Besides these stable complexes. 8. 752 (1967). as has been observed e. / Vol. 1062 (1964). Physics 45. Mataga and K .185-871.lO-diphenylanthracene can also be detected in delayed fluorescence. Cherkasov. The mixed excimer of anthracene and 9. Ezumi. M. Nature (London) 186. L . I. Optics and Spectroscopy 6.931.Leonhard and A. With radical-anions and radical-cations produced by alternating current electrolysis under potentiostatic conditions.  I. 1967. 347 (1966). Chandross. Weller. the terms heteropoluv exci I.or Pacetylanthracenes. Christophorou. Amer. In delayed as well as in prompt fluorescence. For example.g. Mixed excimers of this type e. Japan 40. SOC. Cherkasov. should produce unsymmetrical as well as symmetrical excimers in mixed solutions. 989 (1963). and K . Okada. Molecular Physics 10. Weller. 172 (1967). 23 (1966). Nature (London) 203. A non-fluorescent or weakly fluorescent component can thus quench the fluorescence of the other.1138. A.  T. The combination of formation and rapid dissociation of mixed excimers represents a mechanism for the transfer of excitation energy from one component to the other. ionization potentials.  C. in which the approach of the triplet molecule is sufficiently fast. or electron affinities is important t o the problem of the bonding mechanism in excimers. Acta 19. Mataga.lO-dialkylanthracenes [80. McGiynn. Okada. Cherkasov.lOdialkylanthracenes by 9-bromo. Bull. T. Optika i Spektroskopija 6. Pairs of this type tend to form electron donoracceptor complexes [91J (EDA or charge-transfer complexes) in the solid state or even in solution. A. E. S .  N . Excimers should be formed not only by electron exchange between two molecules in triplet states but also by electron transfer between a radical-anion and a radical-cation (both in their unexcited states): A. Investigations on solid solutions of perylene in pyrene 1891 and on mixed solutions of both compounds in a liquid solvent 1901 have revealed changes in the fluorescence spectra.Excimer components have also been found in the delayed fluorescence of solutions of naphthalene [761.  E. P. Obyknovennaya and A . though participation of other processes cannot be ruled out 1791. Vember and A . J . The existence and stability of unsymmetrical excimers whose components differ in their excitation energies. they should also be capable of forming excimers. A .  N. Chem. Bard. Hochstrasser. Commun. internat. Ezumi. 148 (1959). New York and London 1962. A. J.  B. but the dissociation of the excimer is not yet too pronounced. others have been discovered that exist only in the fluorescing excited state. Obyknovennaya. 188 (1966). 1355 (1967). Sprin G.g. but n o typical excimer bands have been found. physik. 6284 (1968). Optika i Spektroskopija 22.f A+ + (AA)* (4 have been detected by specific excitation of one component or by measurement of the total excimer fluorescence as a function of composition. A subsequent quantitative investigation of the concentration dependence of the two components for 9. 593 (1968). Edit. Chem.  H .  N . 3131 (1964). and phenanthrene [773. 232 (1959). the fluorescence of pyrene (acceptor) in dilute benzene solution is replaced by a structureless component at a longer wavelength on addition of dimethylaniline (donor) [92.  N . and in other systems of the same kind  C . chem. Longworth. The formation enthalpies of mixed excimers have also been determined [84J. P. B. 201 (1966).lO-dimethylanthracene in dimethylformamide confirmed reaction scheme (a). M . Optics and Spectroscopy 21. Unsymmetrical Excimers Just as dissimilar molecules can form stable associates and complexes. 317 (1967). chem. 8 (1969) / No. Kawaoka and D . A . S. and differing e. Faulkner and A . J. Beens and A. between anthracene and 9-alkyl. I . between pyrene and l-methylpyrene [823331. Physics 41. Berlin 1961. in the case of 9. and A. Vember. E. only in the position of the alkyl substituents. Obyknovennaya. E. Optics and Spectroscopy 20. Visco. Weller in H. Molecular Physics 10.  T. Neznaiko. Optika i Spektroskopija 24. and R. it is formed from the triplet states of the two partners in accordance with (b) 1881. SOC. Briegleb: Elektronen-Donator-Akzeptor-Komplexe. Optics and Spectroscopy 24. Parker. and T . E. 67. Since this phenomenon is analogous to excimer formation [94-961. J . Parker and G. Birks and L . K. Neznaiko. E. chem. Longworth. F. J.  C. Acta physica polon.  N. J . 147 (1966). Amer.g. S . D .811. H. Azumiand S. W.  K . 203 (1966). A. benz[u]anthracene 1711. Optika i Spektroskopija 20. 90. Kearns. M. 791 (1963). 1821 J. J. 3259 (1965). Optics and Spectroscopy 22. Cherkasov. chem. Short. Leonhard and A. Kallmann and G. Chandross. Ber. K .or 9. 410 (1967). 1098 (1962). Mataga. Trans.2618 (1967). The excimer emission then appears as chemiluminescence. and A . Selinger. 45 (1966). and Visco [781 obtained chemiluminescence spectra with monomer and excimer components as well from several aromatic hydrocarbons. Faraday SOC. 63. 33 (1962).  T. though their structureless fluorescence spectra would be difficult to identify. Parker and T . G . Optika i Spektroskopija 22. ger. Spectrochim. benzo[b]pyrene [661. Optics and Spectroscopy 22.
J. 4717 (1968). chem. J. the properties of which are similar to those of the excimer component in the fluorescence spectrum. Chem. Diffuse regions in the lowtemperature phosphorescence spectra of some halogenobenzenes in the crystalline state [lo61 and in solution in organic glasses [lo71 have been interpreted in this way. B.961. 1183 (1967). Mataga. as is to be expected in view of the polar nature of hetero-excimers [g4. Greater stability is then to be expected if the state of the excimer is derived. The hitherto clearest evidence of the existence of triplet excimers has been found in alcoholic solutions of naphthalene. S . For the same donor. chem. Phys. Japan 39. Chem. F. Rettschnik. who interpreted it as a charge-transfer state. physik. K . Chem. Triplet Excimers We therefore assumed at first that the stability of the pyrene excimer was due to excitation (or exciton) resonance between the two configurations in formula (e)[11. A. Forster. 72. E d i t . M . SOC.35) [109. 766 (1963). chem. Z . Mataga. [loo] H . chem. 5 341 . Ware and H. Mataga. [loll M . Weller. J. 11051 H . Rehm. Hoijtink. 95 (1967). University of Amsterdam 1969. Nonspecific solvent effects may lead to spectral effects similar to those of the formation of hetero-excimers but should be interpreted differently 11011. chem. Lim and S . N. J. Matsui. W . Dissertation. SOC. K .1111. J .Japan 39. chem. and A . 48. Chakrabarti. Hochstrasser. Birks. Physics Letters 1. Physics 47. H . J . A second hypothesis for the state of the excimer was proposed by Ferguson[431.140 (1968). [lo71 E. which is only slightly higher (86 kcal/mole) and also has a very high oscillator strength (f = 0.1101. chern. Knibbe. and A . Nevertheless. Physics Letters I . H . Chem. Hetero-excimers have been found with numerous aromatic hydrocarbons as acceptors and several aromatic amines as donors in nonpolar solvents 195. Okada. chem. J. M . The excimer band shows a red shift with increasing electron affinity of the acceptor and with decreasing ionization potential of the donor. 10. H. 119 (1967). P . it is impossible to decide in favor of one of the two hypotheses. Knibbe and A. 11121 A. and A . Physics Letters 2. R . Molecular Physics 13. 609 (1968). Slifkin. P. and N . Weller. Richter. Angew. Bull. T. [lo91 G. 156 (1960). Origin of the Excimer Binding Energy The electronic state of a symmetrical singlet excimer could obviously be described by a resonance hybrid with uniform distribution of the excitation energy over both components: A*A t-f AA* (e) 9.A + (AA) t (d)  N . 257 (1968). Lumry. Lim. Bunsenges. Phys. 56. Mataga. W . J. T . 2563 (1966). Okada. however. 64. Weller. physic. T. Ber. Rehm. The spectrum shifts toward the red with increasing dielectric constant of the solvent. Chem. Bull. R. a linear relation is found between the wave number of the band maximum and the electron affinity or the reduction potential of the acceptor[g*J. Walker. and N . K . not from the lowestenergy state I L b (77 kcal/mole) of the monomer. D . and A. but from the state lLa. 49. Physics 47. The fluorescence of a heterotriple complex has also been reported [loo]. Bunsenges. Chem. Bednar. J Vol. F. Physics 45. Knibbe. 2562 (1966). Elektrochem. and N . 102. Ber.F. Nature (London) 200. [lo81 J . The fluorescence effect in this case and the well-known quenching of fluorescence by non-absorbing impurities are related in the same manner as the concentration-induced fluorescence change and concentration quenching. physik. Chem. A resonance hybrid can again be formulated for a symmetrical excimer: A question of considerable theoretical interest is whether molecules in metastable triplet states form triplet exdmers with molecules in singlet ground states: A t $. 4352 (1966). 121 (1962). [I101 Th. 2589 (1968). Pure appl. C. 1184 (1967). Okada. H . Beens. 11111 M . 99 (1967). These should appear as an additional component in the phosphorescence spectrum. 1595 (1968). Physics 48. F. J. 293 (1967). The fluorescence yield and the decay time decrease simultaneously. Oohara. and G . Weller. Okada. 3455 (1966). States with even higher energies have also been considered [110al. H . 8 (1969)1 No. Rollig. T.. [lo31 H. Oohari. N. which has to be interpeted by a solvent dependence either of the electronic structure of the excimer or of its formation and decomposition kinetics [1051.  H . In most of the cases studied the acceptor was the lower excitation energy so that it becomes primarily excited under usual conditions. Langelaar. A good correlation exists between this difference and the position of the excimer emission [77. Langelaar. Yamamoto. Physics Letters I . According to this hypothesis. H . Lambooy. that of hetero-excimers exhibits an appreciable solvent dependence. Physics 45. Unlike the fluorescence of symmetrical excimers. and H.  H. for which an excimer-like component is superimposed on the monomer phosphorescence over a narrow temperature range around 180 "K [lo*]. Yamamoto. chem. Knibbe. Schafer. C . Chem. [lo21 N .1031. Beens and A. 56. D. Matsumoto. 2. A. Weller. Chem. there are also examples for the opposite case [991. [110a] J . Chandra and E. physik. Chem. Knibbe. [lo61 G. Hoytink. since the correlation with the position of the 'La state is equally good[1121. 304 (1967). Weller.mers or hetero-excimers are used [973. Castro and R . 4. Z . 11041 N . the energy of the excimer should depend on the difference between the ionization potential and the electron affinity of the monomer. internat. P . T. J. and R .
The (unsensitized) photodimerization of acenaphthylene [I331 is known to involve two different mechanisms. Fritchie. J. Elektrochem. SOC. Chern. Physics 45. Paldus. P . chem. K. I. chem. I t is also very probable that the photodimerizations of naphthacene. Birks. Chem. 1856 (1964). and St. A mechanism proposed for the formation of the syn dimer proceeds via the excimer “341. E. are chemical reactions proceeding from excited electronic states. Aust. Photochemical reactions.1291 in position 9 or 10.1171. H . 28. In addition to highly symmetrical sandwich configurations (Dzh). 27. Chestnut. F.  T . and Photobiol. Japan 23. Azumi and S . Smith. Hillier. Selinger.The first quantum chemical calculations on excimers from parallel molecules of naphthalene. 21. Azumi. 0 .561 or in the presence of bulky substituents [62. the excimer undergoes transformation to the stable photodimer. 2. St. Physics 48. Hartmann. J. Acad. 11231 B. 342 Angew. 120 (1950). several of them based o n orbitals extending over both components of the excimer [112. 363 (1 964). A . Physics 42. and H . e.and charge resonance are taken into account. Excimers as Intermediates in Photochemical Reactions and Photophysical Processes Depending on the particular case. P . A . A . Srinivasan. and particularly in genetics. Quantum chemical calculations have been carried out for the excimers of anthracene and perylene as well as for those of naphthalene and pyrene [114. Bunsenges. Armstrong. 318 (1959).1151. and Photobiol. Forster. Res. The photodimerization of thymine is of interest in biology. the treatment of which includes the paracyclophanes. J. Physics 41.6 A were obtained in every case. chem. 2131 (1968). T . Commun. Sci. N . 2. 3886 (1966). instead of emitting. 23 (1966). one of which leads to the syn dimer and the other to the anti. chem. chem. The potential surface of the ground state of the benzene excimer has also been used for the calculation of the spectral distribution of its emission [1241. J. and particularly the equilibrium distance between the planes of the two excimer compounds. Lamola. pyrene. this transformation is suppressed. 56. Optika i Spektroskopija 6. simpler and less conventional semiempirical methods have also been used. Armstrong. 279 (1967). J. Kongnenberg. P . J. SOC. Bull. N . W .  T. 11281 Th. McGlynn. A . Schenck. W.0 and 3. C .  A . A .  J . R.  M . McGlynn. 548 (1967). Bently. Lamola and J. 2311 (1966). Chem. B. Biochem. Lamola. and J. [1341 J. Rice. 51.  J. H. etc. Excimers are also assumed to participate in this process 11353 1361. Quantum chemical calculations of the actual energy states. 11181 J . Wilairat and B. chem. 619 (1968). Bowen and D . Livingston and Kei Sin Wei. SOC. 11. Paldus. and S . less symmetrical ones have also been discussed [116. either the neutral or the ionic configurations may predominate. and particularly of the distance between the two molecules within the excimer. have been carried out only for a few examples. J.  A . McGlynn. This reaction. nat. T . Cherkasov and T. 5 . T. Optics and Spectroscopy 6. 716 (1952). Similar calculations for the benzene excimer. J. 11171 T . 415 (1963). Chem. V . Vol. benzene [1221 and naphthalene [123J. Aladekomo. H. Glass. A . P. The latter itself.Japan 40.  P . 46 (1968). have also been carried out for configurations of lower symmetry[11*-12ol. J. Most of these calculations give only the excitation energy of the excimer as a function of its geometrical configuration. M . B. McGlynn. Simmons. A . 3839 (1964). 2667 (1963). Chem. Dissertation. 11191 J . I. Physics 41.  M . chem. Photochem.1291. were performed by Konijnenberg [*I31 and by Murrell and Tanaka 11141 by the semi-empirical PPP method. J.e. 3146 (1967).1211. Proc. 71. Z. H. Suzuki. Freie Universitat Amsterdam 1963. chem. Physics 44. Azumi. can only be deduced from the agreement of calculated and experimental values for the position of the excimer band. 8 (1969) No. chem. Russell. Photochem. Trans. 541. J. chem. W . Arumi and H . Sterns and B. At lower temperatures 155. since it is involved in the inactivation of deoxyribonucleic acid by UV irradiation. G. later to be identified as the excimer 1126. Besides the PPP method. USA 59. Rice. 503 (1959). Austral. Excimers occur as intermediates in photochemical dimerizations in which an excited and an unexcited molecule form a stable dimer whose components are linked by principal valences. The formulation (8) can likewise be applied to unsymmetrical and hetero-excimers. Vala Jr.  T . Drickamer. Eisinger and A . J. Chem. Ber. Czechoslov. The best-known example is the photodimerization of anthracene with formation of dianthracene. B. These calculations showed that with acceptable values of the parameters involved. Collect. Ber. J. Photochern. Bull. 21. apart from trivial exceptions. 1127 (1965). the photochemical reaction is the reason for the concentration quenching of fluorescence at room temperature. i.. Very probably.  D . which proceeds from the excited singlet state state [125. Hillier. A . Azumi. 28.  M . and Photobiol. Molecular Physics 7. 558 (1967). Koutecki. biophysic. internat. chem. Edit. Azumi and H . Commun. czechoslov.g. J. and S . physik.1281. Commun.475  E. Murrell and J . so that excimer fluorescence occurs.1261. pentacene [ I 3 0 4 and 2-alkoxynaphthalenes 1131 1321 occur via excimers. Selinger. the position of the excimer band can be reproduced only if both excitation. 1829. and H . and G . Bull. Values between 3. 7. Vember. 442 (1966). J. and J . Birks and J . chem. 100. J. Physics 42. This corresponds to a combination of (e) and (f) and to a more general formulation of the excimer state as a resonance hybrid: by simplified semi-empirical methods. 1675 (1965). chem. 599 (1962). B. [l131 E.. Eisinger.  J . Collect.  L . the potential surfaces of the excimer and its unstable ground state. 17291 J . Japan 39. Austral. was assumed t o occur via an electronically excited associate [127. 733 (1968). Jortner. S. physic. Faraday SOC.  R . 1931 (1968). (1955). and S. B. Physics 44. Appleyard. Hartmann. M .493 (1963). Tanner. and Rosalin Pope. Tanaka.
E. Voltz. d) I. 1026 (1968). processes such as A*+A which are evidently analogous to the Grotthus proton transfer process. Chem.Chem. Pesaro. followed by coupling of the C  a) R . 217. Lumb. K. A. Sci. Felner. The concept of corrin synthesis used in our previous work [41 requires the construction of two bicyclic intermediates ( 1 ) and (2) containing the AID. This could occur as a radiationless process between separated molecules [1371. Faraday SOC. Roy. 1. Haifa 1968. Fischli.I6-hydrogen transfer leading to an antarafacial ( n + ~ ) . and H. I1391 J . Federat. L . R. b) A . Amata.  P. 253. 79. Chem. 1830 (1966). Meyer. Edit. B. Organic Synthesis). Miljkovic. The key step is a light-induced I. One of the important contributions to the synthetic aspects of the field has recently come from A . D . Wehrli. Eschenmoser. Res. Wagner. 3rd Edit. (London) A 288.1391. Gschwend.-1ng. Crowfoot Hodgkin. must also be considered [1403 1 4 1 1 . D. Boos. Universitatsstrasse 6 (Switzerland) [l] a) D . Muller. W. 364 (1969) + (AA)* A+A* (h) [I371 R . R. b) A . Chem. Welch Foundation Conf. SOC.2. Eschenmoser. induced the development of a new type of corrin synthesis. Accounts chem.-1ng. E d i t . c) A .An important photophysical process is the intermolecular transfer of electronic excitation energy. internat. K. F. SCances Acad. L . 1883 (1967). Dr. Nr. internat. the continuing investigations in the Harvard and ETH (Zurich) laboratories towards a synthesis of vitamin B12 have produced results of a methodological 121 and theoretical 131 nature which. Dr. Pesaro. 141 a) E. P. 490 (1964). and A .-Chem. have Dr. Biochem. c) A . [*I Vol. Coche. and R. A . Smith: Vitamin B12. Chimia 19. Their function depends on the transfer of excitation energy initially produced in the solvent to the solute. Special Publ. A . Jones and M . Angew. P. C. Dip1. 21. since excimers are rapidly and reversibly formed in toluene and other common solvents 1138. Golding. Thanks are due to the Fonds der Chemischen Industrie and the Deutsche Forschungsgemeinschaft for their generous support of the work in this field carried out in the author’s institute. Keese. Edit. Schrauzer. generally toluene. Chemistry in Britain 1967. Schefofd. Conferenze. P. Micol. Physics 48. F. L . Chem. Trans. Wehrli. Woodward: Aromaticity. 97 (1968). In addition. Chem. Dr. Ann. Carter and L . London 1968. which plays an important part in the function of the widely used liquid scintillators. 1473 (1963). 2. Chem. Academia dei Lincei. internat. (XII. 81. Winnacker. Chem. Braga. Keese.  R . 864 (1967). ETH. Angew. A New Type of Corrin Synthesis By Yasuji Yamada. ETH. Corso Estivo di Chimica (1967). Eschenmoser. with a dissolved substance that fluoresces at longer wavelengths. M . Bormann. and A. Birks. R. J. 566 (1965). Methuen. Physics 46. Chem. Bertele.(London) 1967. Eschenmoser. B. Angew. 1964. Physics 49. C . Excimers also appear to be involved in the transfer of electronic excitation from host to guest molecules in crystals under high pressure 11431. G . XI. Miiller. XI. Angew. 306 (1965). Dunitz. E. H . D . These consist of an aromatic solvent. hebd. SOC. and Prof.. N. A . SOC. 6. Internat. P. Pesaro. ScheF fold. on chemical Res. Gschwend. B.g.  C. Loliger. G. 5457 (1968). D . 5 343 . J. Christophorou. W. J. Proc. Received: January 16.  P .7. ETH. Eschenmoser. and A . D . 1969 [A 698 IE] German version: Angew. Robert A.12-heptamethyltrans-corrin perchlorate (20). Gribi.  J.and B/Cmoieties respectively. Laustriat. I . EschenmoserI*l Work towards a synthesis of vitamin 3 1 2 has inspired a new type of corrin synthesis. Dip1. This is exemplified by the synthesis of (&)palladium(Ix)-l5-cyano -1. K . Woodward. Angew. Johnson and his collaborators [lc] through their synthesis of corrinoid complexes from tetrapyrrolic precursors. 76. R. The construction of the seco-corrinoid ligand system i s achieved by coupling monocyclic ring precursors in their enamide or enamine form through the methods of sulfide-contraction via oxidative coupling and of iminoester-enamine condensation. Proc. B. chem. The structural and functional uniqueness of vitamin B12 and Bl2-coenzymes continues to stimulate chemical research on corrins in a number of laboratories [I]. 333 (1968).2. 405 (1966). in press.-1ng. London 1965. Yasuji Yamada. However. P. J. chem. G. 863 (1967). H . Proc. Felner. Birks and J. Bertele. Loliger. Proc. in press. and J. Pesaro.c y c l o isomerization of a seco-corrinoid metal complex. 8 (1969) J No. Golding. 326. 85 (1968). Felner. Eschenmoser Organisch-chemisches Laboratorium der Eidgenossischen Technischen Hochschule CH-8006 Zurich. Ludwig and C . and A. Yguerabide. F. 35/I. chem. M..(London) A 303. c) M. Pure and appl.5-diphenyloxazole (PPO). D. among other things. d) G . Conference on Coordination Chemistry. IUPAC Symposium on Natural Products. B. This may be a useful principle in the search for new scintillator systems [14*1. chem. 592. in press. b) F. 393 (1964). Roy.7. J. 257.62. H .  J . M. Rev. Physics 49..1 Z. e. Johnson. Eschenmoser. Miljkovic. E. Wick. I . Pure and appl. in press. Elsinger. Dip1. 3. Conte. M. E.-Chem. B. Chem.
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