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Letters,Vol.31,No.l,pp47-50,199O Great Britain

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Modification of Photochemical Photodimerisation of

V. a Central Ramamurthya,*,

Reactivity by Acenaphthylene

Zeolites: within

Cation Controlled Faujasites

D. R. Corbina,

C. V. Kumarb

and N. J. Turroc

Research and Development Department #* E. I. du Pont de Nemours and Company Experimental Station. P. 0. Box 80328. Wilmington, Delaware 19880-0328 5284 #Contribution Number: b Department c Department of Chemistry, of Chemistry, University Columbia of Connecticut, University, Storm, CT 06269

New York, NY 10027. zeolites gave the corresponding cis on the type of cation present in the excited singlet state in the case of the case of higher atomic weight into the distribution and migration

Abstract: Photolyses of accnaphthylene included in WY and trans dimcrs. The ratio of the dimers formed depends supercage. Dimerization is believed to originate from the lower atomic weight cations and from the triplet state in cation exchanged zeolites. Dimerization provides insight of molecules within the zeolite internal structures. The influence present internal on the here our of the surfaces unimolecular preliminary reactive within the of zeolites of guests results within supercage. state have within a zeolite recently of zeolite been

demonstrated molecules. 1

to exert However,

significant no such effect We the cations

photoreactivity

included

on bimolecular dimerization multiplicity that

photoreactions

frameworks

has yet been bimolecular we also

reported. reaction, show

on a study

of a photochemical framework. by careful Further, choice

of acenaphthylene,

that the

can be controlled

of the exchangeable

are present

I. . . &3 . 1
The unique subjected photobehavior of

JL&g+g
2
acenaphthylene studied (L). the molecule in various chosen extensively heavy the yields constrained

3
for investigation, media and has been of gives is

in that it has been in solution cis dimer

to one of the largest whereas

atom effects gives

on its dimerization2 both cis inside and trans

The irradiation the singlet dimers

acenaphthylene predominantly amounts.

cis (2) and the trans (2) dimers;

the triplet is presumed

in comparable supercages (of zeolite-

The photodimerisation

to occur

the spherical

Y) which possess

a diameter of ca. 13

A 3.

47

48

Photolyscs

of dry solid inclusion

complexes

of acenaphthylene

in various cation (Li. NE, K, Cis to trans dimer ratio is The relative under identical in
V~OUS

Rb, Cs snd Tl) exchanged Y zcolites gave the cis and trans dimersP dependent on the cation and on the nmbcr efficiency conditions. of dimerization Relative was calculated triplet yields of guest molecules

per supercage (<s>). complexes

by irradiating all six zcolite

and the triplet lifetimes reflectance flash photolysis

of ecenaphthylenc the accnaphthylene technique.5

included

cation exchanged

Y ,zcolites

were obtained by monitoring

triplet by its T-T

absorption at 470 nm via diffuse arc summarized Table: Cation in the Table. Dependent

Results of these studies

Photodimerizntion

of

Acenophthytene

Lncluded

in

M+Y

Type

Zeolites Zeolite Cis/Trens (s>=a.s LiY

Na Y

dimerr -&=0.25 25 22 1.6 1.1

Relative Efficiency of Dimcrizationb 0.2 0.2 a.4 1.0

Relative Triplet

Yietdc

Triplet Lifetimed

25 25 2.3 1.5 4.2 22

e e a.2 0.5 9.6 w 5.7 ps

KY Rb Y

CSY TlY

1.0

a. < S > refers to the average occupancy, i.e.. the ratio of the number of 8cenz4phthylene molecules to Relative efficiency, relative triplet yield md triplet lifetime are for the number of supercages. samples with < S > = 0.5. b. Efficiencies arc nonnalii to Rb Y and the amount of dimer formed WIS estimated by using pymne as a gc calibrant. c. Triplet yields arc normalized with respect to Tl Y; the amount of the triplet formed was estimated by measuring the intensity of T-T absorption at 470 mn. d. Triplet lifetimes were. measured from their decay half lives. e. No triplets were detected.

Absence of triplet formation in Li Y and Na Y is consistent with the solution behavior in which the intersystem crossing yield from S1 to T1 is reported to be near zero.6 This leads
US to

conclude that the dimerization in the supercages of Li Y and Na Y is from the excited singlet tite. Freferential formation of the cis dimcr also support8 this conclusion. triplet yield in K, Rb. Cs and supcrcage.7 the increasing triplet We attribute the high Tl Y to a heavy atom effect caused by the cations present within the with the expected spin-orbit coupling induced

The trends observed in the variation of the triplet yield and the triplet lifetime with mass of the cation is consistent Formation of the trans dimer. the triplet derived product, in the cages of K. Rb Further, formation of the trans dimcr is under oxygen atmosphere. when the photolysis is conducted

formation.8 quenched

and Cs Y is in agreement with the triplet generation. completely

49

A careful examination

of the rest&s

rcveqs

that the efftciency

of dimerlxetion is We believe thst the results

controlled not only by the reactive states but slso by their lifcthne. can bc undcrsmod on the basis of have any knowledge there arc supercages with double
l

modct presented in Flgurc 1. occupsncics.g

Althoughstthllstagewcdonot both double and While dlmerizstion is ceges such is distance before where in

about the distribution pattern, we believe thet even at low loading levels Dimerlzetion occurs withii of dimerixation is a sum of both.

single occupancy cages and the efftcieocy favored in the double occupsncy participation of single occupancy

cages under all conditions, cages in dimerization

in single occupsncy

possible only if moIccular migration occurs between cages.

One can assume that the extent of depends upon the migratory On this bssis it is

withm the excited state lifetime and the effect of cation. siting oo diffusivity.9 expected that shon being deactivated. the reactive state hu efficiencies line with lifetime will disfavor This model would predict the dimcrlsetion efficiency e short lifetime.

the excited state reaching another molecule

to be low in cews

Indeed, these predictions are realized.

OfigiU8teS

The efficiencies

Li Y and Ne Y UC low since the dlmerlxation the decreasing triplet lifetime.

from short lived (- 1 ns) slnglcts;

in Rb, Cs snd Tl Y show a decreasing trend (in spite of iocrcaslng triplet yield) in

Flgurc While dominant formation of cis diier involves is triplet. The dccrcssc in trans diier

in Ll md Ne Y 1s expected since the rcactioo state in this C8sC

singlets. its fotmation in Tl Y wss not anticipated because the mective

yield in the series Rb, Cs and Tl Y is also unforeseen. (trlplct reaction) one would expect the ratio of cis to These results, in of dimerlzatioa. control oo the stcreochcmistry

Further, based on the solution bchsvior our opinion,

trans dimer to be in the range of 0.52 whereas in sll of our csscs it is shove 1. reflect, et least partially, the cavity While the cis form is compact

~cngth-7A.

width-8A)

and will fit within e supercage. the trsns Therefore. it is more likely prcacnt in singly formed. On

dimcr is LOOlong (length-14 Ai. width-& occupied cages meet another molecule

to fit with ln e single cage.

that doubly occupied cages glvc rise to cis isomer while when excited molecules

in adjacent cages trans dimer is preferentially

the basis of the model presented in previous paragraphs. one would predict short reactive state

50

lifetimes Y). triplet

to favor reaction lifetime. Higher

in doubly occupied yields

cages and the formation in triplet reaction solution

of cis isomer within the

(Li. Na and Tl in structures from

The decrease

in trans dimer in going from Rb to Cs Y is simply a reflection of the cis dimer might to solution occupied clearly modify to

of the decrease internal are not results as organic of zeolite

of zeolites subjected doubly

compared

then be due to the fact that acenaphthylenes and dimerization of zeolites behavior of

to a uniform and singly Present results

environment cages.

as in homogeneous

attest to the vast and untapped the photochemical triplet laboratory.1B References and reactions to effect

potential

microenvironments molecules. under active

photophysical within

The use of cations investigation

the internal

structure

is

in our

1. Turro, N. J. Molecular 2. For a review Tetrahedron

Tetrahedron

1987, 43. 1589.

Ramamurthy. Press,

V.

in

Inclusion

Phenomena

and Plenum

Recognition,

(Ed) Atwood,

J. L.; Plenum

in press. of Organic Photochemistry; media see: Ramamurthy, V.

see: Cowan, D. 0.; Drisko. R. L.; Elements For a review in organized

Press New York, 1976; pp 435443. 1986. 42, 5753. Sieves

3. Zeolite Molecular Zeolite Molecular 4. General 4848. method

Structure,

Chemistry

and Use, Breck, D. W.; John Wiley, 1988. irradiation procedure and extraction of residual Therefore, experiments

1974.; of products 1988, I1 0. may products demonstated occured solvent

Sieves,

Dyer, A.; John Wiley, of complex,

of preparation were prepared Product HCl (which

have already been reported: Complexes with be left in the cages. were extracted the stabilty within X-type

Corbin, D. R.; Eaton, D. F.; Ramamurtby. in trimethylpentane dissolves under the zeolite) and a small and ether. dimers

V. J. Am. Chem. Sot. amount cages. Control

are too large to exit the zeolite acid extraction conditions.

of reactants zeolites.

and produts

No dimerization

5. Turro. N. J.; Gould, I. R.; Zimmt. M. B.; Cheng. C. C. Chem. Phys. Lett. 1985. 119, 484. 6. Samanta, A.; Fessenden, 7. For press. the effect olefms see: Ramsmurthy, R. W. J. Phys. Chem.. 1989, 93. 5823. cations on the photophysical behavior of included in press. levels (es>= 0.05) aromatics and in V.; t&par, J. V.; Corbin, D. R.; Eaton, D. F., J. Photochem. V.; Corbin. D. R. cages Coord. Chem. Rev., even under very low occupancy Photobiol., of heavy

Caspar, J. V.; Ramamutthy, of pyrene Sieves

8. Pre-aggregation

in zeolite Structure,

has been reported recently: 9. Zeolite Molecular 681.682. lO.VR Force Faculty (Received Research

Liu, X.; Iu, K. K.; Thomas. J. K. J. Phys. Chem. 1989, 93. 4120. Chemistry and Use, Breck, D. W.; John Wiley, for valuable Science technical assistance. the Of&e 1974. pp. Zeolites 1989. 9, 267. NJT thanks Air of Naval Foundation.

Karger. J.; Ruthven, D. M. and DC thank A. Pittman. of Scientific Research.

and P. Hollins the National

Office

and IBM Corporation Development in Award.

for financial

support.

CVK thanks

Merck Sharp & Dome for a

USA 19 September

1989)