NANO LETTERS

Dynamic Stacked Molecular Assemblies Emit from Green to Red Colors

Wei Wang, Jason J. Han, Li-Qiong Wang, Lin-Song Li, Wendy J. Shaw, and Alexander D. Q. Li*,
Department of Chemistry and Center for Materials Research, Washington State UniVersity, Pullman, Washington 99164, and Pacific Northwest National Laboratory, Richland, Washington 99352
Received December 31, 2002; Revised Manuscript Received February 13, 2003

2003 Vol. 3, No. 4 455-458

ABSTRACT
We present a dynamic molecular self-assembly system, driven mostly by molecular orbital interactions. The formation of such selforganized dynamic systems is characterized with absorption, fluorescence, and NMR spectroscopies as well as dynamic light scattering. Our results demonstrate that proper design of molecules can promote self-organization in solution. As a result, we observed distinct red, orange, yellow, and green photoluminescence from different initial concentrations while exciting the system at the same wavelength.

The formation of molecular self-assemblies is driven mostly by weak intermolecular interactions. In particular, selforganization of perylene tetracarboxylic diimide has attracted recent interest because it can be conveniently prepared and forms ordered structures in liquid crystals1,2 and thin films.3 Even tuning the emission color using polystyrene films doped with coronene-3,4,9,10-bis(dicarboximide) was realized.4 In the perylene tetracarboxylic diimide structure, the weak interactions directing the self-organization process come from hydrophobic effects and/or - molecular orbital overlaps. Considering recent examples that such self-organization can happen in organic solvents,5-8 we attribute the self-organization driving force of perylene stacking in organic solvents mainly to the - molecular orbital overlaps, because hydrophobic effects are largely eliminated in organic solvents. Built upon previous successes on molecular self-organization,9,10 we report that optical emission color can be tuned from a dynamic - stacked molecular assembly in solution. Consequently, pure green, yellow, orange, and red photoluminescence was observed by driving the size regime of a perylene-derivative molecular assembly from single molecules to nanocrystalline assemblies. Although much of current understanding of self-assembly comes from the examination of static systems, the greatest challenges, and opportunities, lie in studying dynamic systems. In this report, we present a dynamic self-organization phenomenon driven by - molecular orbital overlaps.
* Corresponding author. Washington State University. Pacific Northwest National Laboratory. 10.1021/nl025976j CCC: $25.00 Published on Web 03/21/2003 2003 American Chemical Society

Scheme 1 a

Conditions: (a) CH3C6H4SO2Cl/TEA, 33%, RT; (b) NaN3/ CH3CN, 89%, RT; (c) PPh3, H2O/THF 86% RT; (d) perylene tetracarboxylic dianhydride/TEA, 86%, 150 C/DMSO. (e) BzCl/ Py, 31.5%, 0 C.

The general strategy for synthesizing a monomer capable of self-organization is shown in Scheme 1. The self-organized structure is shown as in a cofacial configuration for clarity reasons only because crystal structures and calculations have shown that perylene derivatives typically adopt herringbone packing or slipped cofacial configuration.11 First we synthesized the monotosylation product of tetraethylene glycol (2), which was subsequently converted to an azido compound (3). Reduction of the azide product yielded 2-(2-(2-(2-amino ethoxy)ethoxy)ethoxy) ethanol (4).12 Reaction between compound 4 with perylene tetracarboxylic dianhydride yielded the desired self-assembling block, bis-N,N-(2-(2-(2-(2hydroxyethoxy)ethoxy)ethoxy)ethyl) perylene tetracarboxylic

Figure 2. (a) Upfield shift of the aromatic protons at low temperatures indicates (b) larger self-association constant K at low temperatures. Figure 1. (a) Observed (circles) and theoretical (solid line, eq 2) chemical shifts for 5b aromatic protons Ha and Hb. (b) Theoretical prediction of various oligomers [Aj] of 5 as a function of initial concentration, [Ao].

diimide (5a).13,14 To improve solubility, we further synthesized the monobenzoylation product (5b) from 5a. As the concentration of 5a or 5b increases, we observe rapid exchange of free monomers and self-associated oligomers of 5 on the NMR time scale. This concentration-driven self-organization of 5 yields considerable upfield shift (Figure 1) of the aromatic protons, (Ha) ) 0.62 and (Hb) ) 0.88 ppm when the initial concentration [Ao] is changed from 10-5 to 10-1 M. To the first-order approximation, the strength of - stacking is expected to be the same between the jth oligomer and the (j + 1)th oligomer; therefore, the equilibrium Ki is approximately a constant K (i.e., K1 ) K2 ) K3 ) ... ) Kj ) K). Since the monomer, dimer, trimer, and other higher-order oligomers are in rapid exchange, the observed chemical shift is the mole-fraction-weighted average of various oligomers given by eq 1

obs )

i)1

[A]iKi-1 [Ao] i (1)

where [Ao] and [A] are the initial and equilibrium concentrations of free monomer, respectively, and i is the chemical shift of ith oligomer. The power series in eq 1 must converge under our experimental conditions (K[A] < 1) because the average chemical shift bs is finite and well defined. After some mathematical manipulations,15 we obtained eq 2

from which the equilibrium constant K for self-association of 5 was determined to be K ) 52 ( 5 M-1 in CHCl3. In Figure 1a, the solid lines are fits to the experimentally observed chemical shifts using K ) 52. Moreover, the distribution of various oligomers of 5 is given in Figure 1b as a function of [Ao]. In general the self-association constant KSA depends on the solvent used. Good solvents such as chloroform will solubilize compound 5 and therefore have relatively low association constants, while addition of poor solvents such as methanol will promote self-association and therefore yield large formation constants. The self-association constant KSA ) 52 M-1 indicates that the formation of self-assembled oligomers is spontaneous. To validate these results, we carried out variable temperature 1H NMR of 5b in CD2Cl2 (KSA[CD2Cl2] KSA [CCl3D]). Again, we observed a large upfield chemical shift (Figure 2a) as we lowered the temperature, indicating favorable - stacking at low temperatures. Self-association constants measured at various temperatures are plotted against inverse temperature in Figure 2b, from which we can deduce standard Gibbs free energy, G ) -2-3 kcal/mol for an addition of 5 to the self-organized oligomer. In Figure 2, chemical shifts of the sample and references were measured as a function of temperature, and the selfassociation constant KSA(T) is obtained by fitting those data at the corresponding temperature T to eq 2. The plot in Figure 2b allows us to deduce enthalpy and entropy changes according to the vant Hoff equation (eq 3). LnKSA ) H S + RT R (3)

obs ) 1 +

[A]iKi(i+1 - i) i)1

and [Ao] K[Ao] + 1

[A] )
456

(2)

For self-association of perylene tetracarboxylic diimide derivatives (5a and 5b), we obtained S ) - 17.5 ( 0.7 cal/molK and H ) - 7.41 ( 0.19 kcal/mol. These results indicate that self-organization of perylene derivatives is driven by the exothermic enthalpy change while the system must overcome the unfavorable entropy contribution to achieve an ordered state. Whether the system undergoes selforganization will depend on which contribution dominates
Nano Lett., Vol. 3, No. 4, 2003

Figure 3. UV-vis spectra of compound 5a in CHCl3 at various concentrations, 31 mM (solid), 7.7 mM (dots), 0.48 mM (long dash, dot), 0.12 mM (dash). Spectra at all concentrations were normalized to unity because we are interested in showing the peak shapes. To record spectra at high concentrations, ultrathin quartz cells were used to reduce absorbance values within the instrumental detection limit (Amax ) 2.7). Actual absorbances are 1.72 (31 mM; l 0.16 mm), 1.76 (7.7 mM; l ) 0.65 mm), 1.49 (0.48; l ) 1 cm), and 0.42 (0.12 mM; l ) 1 cm). Vibronic features coupled to the -* transition corresponding to 0 f 0, 0 f 1, 0 f 2, and 0 f 3 are resolved.

Figure 4. Rainbow-color photoluminescence of 5a in CHCl3 at various initial concentrations excited at either 369 or 429 nm (0 f 3). Similar to absorption, the emission peaks exhibit the harmonic nature of the vibrational progression: 18700 cm-1 (0 f 0), 17400 cm-1 (0 f 1), 16100 cm-1 (0 f 2), and 14800 (0 f 3). The coupled mode ) 1300-1400 cm-1 has been assigned to the out-of-phase combination of C-C and CdC stretches of the perylene periphery. Inset: photograph of fluorescent emissions at corresponding concentrations.

the situation. In dilute concentrations (<1 mM), perylene derivatives exist predominately as free monomers and no self-organization occurs as evidenced by the plateau region of NMR chemical shift in Figure 1a. When the initial concentration is high (>1 mM), intermolecular interactions increase and self-organization begins to take shape (Vide supra, Vide infra) due to favorable exothermic processes. Self-organization of compound 5 is also unambiguously manifested in the electronic absorption spectra. The HOMO to * LUMO transition of the free monomer (5) is well isolated from other allowed transitions. Furthermore, this electronic absorption has a pronounced coupling to the vibronic features corresponding to V ) 0 f V ) 0, 1, 2, and 3 transitions with an energy difference of 0.17 eV between adjacent levels (1400 cm-1; out-of-phase combination of aromatic rings), where V and V are quantum vibrational numbers of the ground and excited states, respectively. The fractional intensity of V f V, for harmonic oscillators, is proportional to the square of the FranckCondon factor V|V.16 In the free monomer, we observed normal progression of Franck-Condon factors, i.e., A0f0 > A0f1 > A0f2 > A0f3 (Figure 3). This result indicates that the ground-state vibrational eigenfunction 0 (V ) 0) in free monomer has the best overlap with the excited vibrational state 0 (V ) 0).17 As compound 5 begins to self-aggregate, we observed an increase in 0 f 1 and 0 f 2 transitions. These results indicate that the better vibronic wave function overlaps between 1|0 are established in the self-organized structures. This gradually shifts the absorption intensity from the 0 f 0 to the 0 f 1 transition as the monomer begins to assemble into higher oligomers (Figure 3). This observation is supported by the covalently bound perylene dimer, in
Nano Lett., Vol. 3, No. 4, 2003

which the intensity of the 0 f 1 optical absorption is higher than that of 0 f 0 optical absorption.18 The self-organized oligomers of 5 emit green to red colors (Figure 4). At [Ao] ) 31 mM, red photons (674 nm) are emitted, while at [Ao] ) 7.7 mM, fluorescence has an orange color (643 nm). At 0.96 mM, we observed mostly bright yellow emission (577 nm), whereas light green (535 nm) is emitted below 0.12 mM. Although it is tempting to explain this rainbow color emission using band theory as in the case of color changes in semiconductor nanocrystals,19-22 we found the absorptions (0 f V, V ) 0, 1, 2, 3) of assemblies of 5 did not significantly red-shift as the emissions did. However, the absorption bands indicate that the FranckCondon factor begins to favor more and more to the higher excited vibronic states (e.g., 0 f 1 and 0 f 2 in Figure 3) as nanostructures begin to take shape. Similarly, the reverse emission process will in turn also favor those emissions to the higher vibronic levels in the ground state. As molecular assemblies become larger, the relative absorption favors 0 f 1 and 0 f 2 transitions more and more because the Franck-Condon factor 1|0 is increasing faster relative to 0|0. Consequently, in the emission processes, the vibrational overlap integral 0|V favors radiative transitions to higher and higher ground vibronic states (V ) 0, 1, 2, 3) as the size of the self-assembled nanostructures increases. Thereby, the emission of larger assemblies shifts more and more to the red. As a result, monomers emit pure green (532 nm; V ) 0 f V ) 0 dominates), and larger oligomers emit yellow (574 nm; V ) 0 f V ) 1 dominates), orange (621 nm; V ) 0 f V ) 2 dominates), and red photons (674 nm; V ) 0 f V ) 3 dominates). The energy difference between adjacent emission peaks is 0.16 eV, slightly lower than the energy difference between the 0.17 eV interval of absorption peaks. As concentration increases, emission of higher energy photons by monomers and/or lower oligomers can be
457

compound 5 forms rapid dynamic self-assemblies driven by high concentration or/and low temperature. These results demonstrate that proper design of monomers can promote self-organization of nanoobjects in solution. As a result, we observed distinct red, orange, yellow, and green photoluminescence from a dynamic self-assembly system by adjusting the initial concentrations. Acknowledgment. We acknowledge the support of the U.S. Department of Energy (DOE) Los Alamos National Laboratory, subcontract (28893-001-01-35); DOE Office of Basic Energy Sciences, Division of Materials Science and Engineering, and the Department of Chemistry, the Center for Materials Research, and College of Sciences at WSU. Supporting Information Available: Detailed synthetic procedures of compounds 1-5; variable temperature 1H NMR spectra, and 1H NMR as a function of concentration. This material is available free of charge via the Internet at http://pubs.acs.org.
Figure 5. Unimodal dynamic light scattering results at various angles indicate the presence of -stacked self-assemblies. However, due to the dynamic nature of the self-assembling system, the distribution does not yield accurate information on aggregate sizes.

References
(1) Cormier, R. A.; Gregg, B. A. Chem. Mater. 1998, 10, 1309. (2) Liu, S. G.; Sui, G. D.; Cormier, R. A.; Leblanc, R. M.; Gregg, B. A. J. Phys. Chem. B 2002, 106, 1307. (3) Thalacker, C.; Wurthner F. AdV. Funct. Mater. 2002, 12, 209. (4) Rohr, U.; Schlichting, P.; Bohm, A.; Gross, M.; Meerholz, K.; Brauche, C.; Mullen, K. Angew. Chem., Int. Ed. 1998, 37, 1434. (5) Oh, K.; Jeong, K. S.; Moore, J. S. Nature 2001, 414, 889. (6) Bert, V.; Huc, I.; Khoury, R. G.; Krische, M. J.; Lehn, J.-M. Nature 2000, 407, 720. (7) Zubarev, E. R.; Pralle, M. U.; Sone, E. D.; Stupp, S. I. J. Am. Chem. Soc. 2001, 123, 4105. (8) Orr, G. W.; Barbour, L. J.; Atwood, J. L. Science 1999, 285, 1049. (9) Lahiri, S.; Thompson, J. L.; Moore, J. S. J. Am. Chem. Soc. 2000, 122, 11315. (10) Prince, R. B.; Barnes, S. A.; Moore, J. S. J. Am. Chem. Soc. 2000, 122, 2758. (11) Pope, M.; Swenberg, C. E. Electronic processes in organic crystals; Oxford University Press: New York, 1982. (12) Frisch, B.; Boeckler, C.; Schuber, F. Bioconjugate Chem. 1996, 7, 180. (13) Langhals, H.; Jaschke, H.; Ring, U.; von Unold, P. Angew. Chem., Int. Ed. 1999, 38, 201. (14) Cubberley, M. S.; Iverson, B. L. J. Am. Chem. Soc. 2001, 123, 7560. (15) Since the chemical shift difference between two adjacent larger oligomers (i > 4) is negligible, only the first four terms are included in the calculations. To determine the chemical shift difference between lower oligomers, we have synthesized covalently bound dimer, trimer, tetramer, pentamer, and hexamer and experimentally determined 2 - 1 ) 0.315, 3 - 2 ) 0.215, 4 - 3 ) 0.125, 5 - 4 ) 0.05, and 6 - 5 ) 0.04 for Ha. (16) Hennessy, M. H.; Soos, Z. G.; Pascal, R. A., Jr.; Girlando, A. Chem. Phys. 1999, 245, 199. (17) Ruhoff, P. T.; Ratner, M. A. Int. J. Quantum Chem. 2000, 77(1), 383. (18) Langhals, H.; Ismael, R. Eur. J. Org. Chem. 1998, 9, 1915. (19) Li, L. S.; Hu, J. T.; Yang, W. D.; Alivisatos, A. P. Nano Lett. 2001, 1, 349. (20) Chan, W. C. W.; Nie, S. M. Science 1998, 281(5385), 2016. (21) Cao, Y. W.; Jin, R. C.; Mirkin, C. A. J. Am. Chem. Soc. 2001, 123, 7961. (22) Peng, Z. A.; Peng, X. G. J. Am. Chem. Soc. 2001, 123(1), 183.

reabsorbed or quenched. Therefore, longer wavelength emission becomes more prominent. For example, the yellow curve at [Ao] ) 0.24 mM in Figure 4 can be regarded as the green curve at [Ao] ) 7.5 M with some of the 0 f 0 emission being reabsorbed. The long wavelength emission resembles an excimer emission. However, self-organization apparently occurred before photo-excitation as demonstrated by NMR results. Therefore, these emissions were not from excimers. Excitation of stacks of perylenetetracarboxylic diimide could generate both molecular (Frenkel) and charge transfer (CT) states coupled to a molecular vibration.16 The exciton model can neither explain only one set of well-resolved vibronic bands in absorption spectra nor the red shift of the fluorescence emission. However, one cannot completely rule out the existence of excitons because the splitting of Frenkel and CT excitons could be small (,0.16 eV) and only contribute to line broadening. Thereby, the broadening of the absorption and emission peaks at high concentration (31 mM) may be due to exciton coupling and mixing within the self-assembled nanostructures. The blue shift in absorption and red shift in emission can only be explained by the Franck-Condon principle. Dynamic light scattering results (Figure 5) showed that monomer 5 self-organizes into particles with a very broad size distribution. However, these large assemblies readily pass through filters with specified pore sizes of 1, 0.5, and 0.1 m, confirming the dynamic nature of these rapidly exchanging assemblies. In summary, the absorption, fluorescence, and NMR spectroscopies, as well as light scattering, suggest that

NL025976J

458

Nano Lett., Vol. 3, No. 4, 2003