J. Am. Chem. SOC.1994,116, 1345-1351
1345
Organic Guests within Zeolites: Xenon as a Photophysical Probet V. Ramamurthy Contribution from Central Research and Development, Experimental Station, The DuPont Company,* Wilmington, Delaware 19880-0328 Received October 22, 1993. Revised Manuscript Received December 10, I993@
Abstract: Location and motion of aromatic guest molecules within Na X and Na Y zeolites have been probed with
xenon. Xenon perturbs the photophysical properties of the excited singlet state of aromatic guest molecules through the external heavy atom effect. Naphthalene, phenanthrene, and pyrene have been used as guests, and they are nonuniformly distributed within zeolites, as indicated by their multiexponential decay of excited singlet states. Of the many locations in which the guest molecules are speculated to be present, only one has photophysical properties which are influenced by the presence of xenon. Diffusion coefficients estimated by the photophysical method presented here compare favorably with the numbers obtained by other conventional methods.
Type111 (X)
Introduction
During the past few years xenon has been an efficientadsorbate for probing the pore structure and guest location and measuring the rates of intracrystalline self-diffusion within zeolites.’ In these studies the sensitivity of the nuclear shielding of the spin 1/2 129Xe to the environment (and therefore the chemical shift of Xe in NMR spectra) is utilized.2 One of the less appreciated, but well-established, properties of xenon is its heavy atom characteristics which offer an efficient spin-orbit-coupling quenching mechanism to the excited guest molecules with which it comes into contact.3 This property of xenon has been utilized by us to probe the distribution and motion of molecules within zeolites. Photophysical characteristics (emission and excitedstate lifetime) of zeolite-included aromatic guest molecules (pyrene, phenanthrene, and naphthalene) are perturbed, as a result of the “external heavy atom effect”, by coadsorbed xenon molecules. Information concerning distribution (nonhomogen e ~ u s )and ~ location of guest molecules within zeolites comes from a remarkable feature observed in the quenching process, “selectivity”. Diffusion of molecules on surfaces of zeolites is measured via conventional adsorption techniques or through modern NMR techniques.5 The experimentally simple photophysical quenching technique which has been utilized in this study t Dedicated to Professor J. K. Thomas on the occasion of his 60th birthday. t Contribution No. 6733. Abstract published in Advance ACS Abstracts, February 1, 1994. (1) (a) Chen,Q. J.; Fraissard, J. J. Phys. Chem. 1992,96,1814. (b) Ryoo, R.; Cho, S.J.; Pak, C.; Kim, J. G.; Ihm, S.K.; Lee, J. Y. J. Am. Chem. SOC. 1992,114,76. (c) Liu, S. B.; Ma, L. J.; Lin, M. W.; Wu, J. F.; Chen, T. L. J.Phys. Chem. 1992.96.8 120. (d) Heink, W.; Karger, J.; Pleifer, H.;Stallmach, F. J. Am. Chem. SOC.1990,112,2175. (e) Karger, J.; Pleifer, H.; Stallmach, F.; Spindler, H. Zeolites 1990,10, 288. (f) de Menorval, L. C.; Raftery, D.; Liu, S.B.; Takegoshi, K.; Ryoo, R.; Pines, A. J. Phys. Chem. 1990, 94, 27. (g) Ripmeester, J. A.; Ratcliffe, C. I. J. Phys. Chem. 1990, 94, 7652. (h)
Ryoo, R.; Liu, S. B.; de Menorval, L. C.; Takegoshi, K.; Chmelka, B.; Trecoske, M.; Pines, A. J. Phys. Chem. 1987, 91, 6575. (2) (a) Ito, T.; Fraissard, J. J. Chem. Phys. 1982; 76,5225. (b) Ripmeester, J. A. J. Am. Chem. SOC.1982,104,289. (3) (a) Robinson, G. W. J. Mol. Spectrosc. 1961,6,58. (b) Horrocks, A. R.; Kearvell, A.; Tickle, K. Wilkinson, F. Trans. Faraday SOC.1966, 62, 3393. (c) Horrocks, A. R.; Wilkinson, F. Proc. R . SOC.London. A. 1968,306, 257. (d) Carroll, F. A.; Quina, F. H. J. Am. Chem. SOC.1976,98,1. (e) Scully, F.; Nylund, T.; Palensky, F.; Morrison, H. J. Am. Chem. SOC.1978, 100, 7352. (f) Morrison, H.; Miller, A. Tetrahedron 1981,37,3405. (g) Morgan, M. A.; Pimental, G. C. J. Phys. Chem. 1989, 93, 3056. (4) (a) Weiss, R. G.; Ramamurthy, V.; Hammond, G. S . Acc. Chem. Res. 1993, 26, 530. (b) Ramamurthy, V.; Weiss, R. G.; Hammond, G. S. Adv. Photochem. 1993,18,67. ( 5 ) Karger, J.; Ruthven, D. M. Diffusion in Zeolites; John Wiley & Sons: New York, 1992.
- Type
Type I1
Figure 1. Structure of the supercages of X and Y zeolites. Cation positions are shown as Types I, 11, and 111.
to monitor the diffusion of guest molecules has not been widely recognized thus far in the area of zeolite chemistry.6 Zeolites may be regarded as open structures of silica in which aluminum has been substituted in a fraction of the tetrahedral sites.’ The frameworks thus obtained contain pores, channels, and cages. The topological structure of X- and Y-type zeolites (also known as faujasites) consists of an interconnected three dimensional network of relatively large spherical cavities termed supercages (diameter of about 13 A; Figure 1). Each supercage is connected tetrahedrally to four other supercages through 8-1( windows or pores. The interior of zeolites X and Y also contains, in addition to supercages, smaller sodalite cages. The windows to the sodalite cages are too small to allow organic molecules access. Charge-compensating cations present in the internal structure are known to occupy three different positions (Figure 1) in the zeolites X and Y. The above description of the cation location should be considered as a simplified model, since the exact location depends on a number of factors such as the presence of adsorbent molecules, temperature, framework composition, and the size and charge of the cations. Only cations present within the supercages are expected to be readily accessible to the adsorbed organic molecule. (6) For studies on silica surfaces: (a) Drake, J. M.; Levitz, P.; Turro, N. J.; Nitsche, K. S.;Cassidy, K. F.J. Phys. Chem. 1988,92,4680. (b) Turro, N. J.; Zimmt, M.B.; Gould, I. R. J. Am. Chem. SOC.1985, 107, 5826. (c) Oelkrug, D.; Uhl, S.;Wilkinson, F.; Willsher, C. J. J. Phys. Chem. 1989,93, 4551. (d) de Mayo, P. Pure Appl. Chem. 1982,54, 1623. (7) (a) Breck, D. W. Zeolite Molecular Sieues; Krieger Publishing Company: Malabar, FL, 1984. (b) Dyer, A. An Introduction to Zeolite Molecular Sieues; John Wiley and Sons: Bath, U.K., 1988. (c) van Bekkum, H., Flanigen, E. M., Jansen, J. C., Eds. Introduction to Zeolite Science and Practice; Elsevier: Amsterdam, The Netherlands, 1991. (d) Szostak, R. Molecular Sieves. Principles of Synthesis and Identification; Van Nostrand: New York. 1989.
0002-7863/94/ 1516-1345$04.50/0 0 1994 American Chemical Society
1346 J. Am. Chem. SOC.,Vol. 116, No. 4, 1994
Ramamurthy
I
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.
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100
200
300
Xenon (torr)
Figure 3. Illustrative examples of Stem-Volmer plots for the quenching of pyrene (:0.01) and phenanthrene (: 0.01) included within Na Y by xenon. The x-axis xenon pressure docs not correspond to the amount of xenon adsorbed; it only represents the pressure applied. The amountof xenon adsorbed was estimatedutilizing an adsorption isotherm.
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500
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Figure 2. Emission spectra of naphthalene and phenanthrene in Na X at 77 K under various pressures of xenon; both at a of 0.01. (a) Naphthalene: --, 0 Torr; 18 torr; -, 100 Torr; -, 200 Torr of xenon. (b) Phenanthrene: -, 0 Torr; 25 Torr; -,100Torr of xenon. In both cases the emission in the region 300-400 nm corresponds to fluorescence and that in the region 450-600 nm to phosphorescence.
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Results Steady-state and time-resolved emission characteristics of pyrene, naphthalene, and phenanthrene adsorbed within zeolites N a X and N a Y have been investigated. Emphasis is on the perturbation of the above characteristics by the gaseous quencher xenon. Complexes of the above aromatics with Na X and Na Y were prepared by the method outlined in the Experimental Section. The loading level (: number of molecules per supercage) of the aromatics was maintained in the range 0.005-0.05. This corresponded to an average local concentration of 0 . 0 1 4 1 M.* Hexane washings of the complex reduce the amount of aromatics adsorbed on the external surfaces of zeolites. At room temperature, steady-state emission spectra of the aromatics included within zeolites consisted of intense fluorescence and fairly weak phosphorescence. The emission characteristics of all three aromatics were influenced by the quencher xenon; a t room temperature fluorescence intensity decreased with the increase in the pressure of xenon. As illustrated in Figure 2 with phenanthrene and naphthalene the fluorescence quenching at 17 K was accompanied by an increase in the intensity of phosphorescence emission with the pressure of xenon. The relationship (8) Occupancy number refers to the number of molecules per supercage. Assuming the X and Y supercage volume to be 800 A3, one can convert the occupancy number to a concentration unit.* An occupancy of one atom or molecule per supercage(800 A3) corresponds to an average local concentration of 2.08 M.Knowing this conversion factor, any occupancy number can be converted to concentration units (M). The concentration represented here is only approximate and realistically may not be comparable with solution concentration. Looking at the loading levels in this term provides a better feeling for the amount of guest within a certain volume. In this calculation volume refers to the space accessible to the guest, which may vary depending on the size of the guest. (9) Ramamurthy, V. In Photochemistry in Organized and Constrained Media; Ramamurthy, V., Ed.; VCH Publishers: New York, 1991; Chapter 10, p 435.
between the intensity of fluorescence (IOIOand xenon pressure (Stern-Volmer plots) is shown in Figure 3 at one loading level of aromatics within N a Y. Similar plots were obtained at other loading levels of aromatics and within N a X. While a linear relationship is observed at low pressures (
