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New Supramolecular Complex of C60 Based on Calix[5]areneЧIts Structure in the Crystal and in Solution.

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(41 For recent papera see, for example: a) M. A. McKervey. M. Pitarch, Chem.
Commun. 1996. 1689; b) S. F. Martin, H.-J. Chen, A. K. Courtney, Y. Liao. M.
Pitzel. M. N . Ramser. A. S Wagman, Tetrahedron 1996, 52, 7251: c) A.
Fiirstner. K. Langemann, 1 O r g Cl7em. 1996, 61, 3942; d) J D. Winkler. J. E.
Stelmdch. J. Axten. Terrahedron Lerf. 1996.37.4317; e) C. M. Huwe, 0 Kiehl.
S. Blechert. S v h r r 1996, 65; f) S. Holder, S. Blechert, &id. 1996, 505.
[ S ] W. E. Crowe. Z.J Zhang. J: Am. Chem. SOC.1993,115, 10998.
[6] W. E. Crowe. D. R. Goldberg, 1 Am. Chrm. SOC.1995, 117, 5162.
[7] W. E. Crowe. D. R Goldberg. 2.J. Zhang, Terruhedron Lerl. 1996. 2117
181 M. F. Schneider. S. Blechert. Angni. Chrm 1996, 108. 479; Angric.. Chrm. I n /
Ed. EngI. 1996. 35. 410
191 a ) Anonym. Plastics World, May 1985.22; b) Plastics Technology, April 1985,
19.
[lo] B. M. Trost. Angew. Chem. 1995, 107, 285, Angebi Chem. Int. Ed. Engl. 1995.
34. 259.
[ll] J L. Hkrisson. Y. Chauvin, Mukromol. Chem. 1970, 141, 161.
[I21 P. Schwab. R H. Grubbs, J. W. Ziller. 1 Am. Chem. SOC.1996, 118. 100.
t
A
0.04
390
I
I
440
490
A/nm
New Supramolecular Complex of C,, Based on
Calix[S]arene-Its Structure in the Crystal and
in Solution
Takeharu Haino, Manabu Yanase, and
Yoshimasa Fukazawa*
Buckminsterfullerene and its related fullerenes have generated a rapidly growing and active research area."] The former is
one of the most impressive molecules because of its cagelike,
truncated icosahedral structure. This molecule, a weak electronacceptor, forms clathrates in the solid state."] The selective formation of a clathrate from C,, and calix[8]arenes was excellently utilized for the separation of C,, and C,0.[31Supramolecular
complexes of C,, in solution are limited in the aqueous systhough extremely weak charge transfer (CT) complexes['] are known in organic solvents. Quite recently weak inclusion complexes of C,, and calix[6]arenes have been reported.16]
Because of the smooth and dense surface of C,,, it can be bound
through an accumulation of weak van der Waals interactions,
even in organic solvents, if a host with a suitably complementary
shape is selected. In this paper we report the binding of calix[5]arene['] receptors to C,, in organic solvents and the crystal
structure of the inclusion complex.
A color change (purple +pale yellow) was observed in the
solution of C,, upon addition of the receptor (1). The intensity
of the shoulder in the guest's absorption band in the 400-470 nm
region increased (Figure 1) with the addition of the receptor (1).
I
X
Me
1: X=l
2: X=Me 3: X=H
I*] Prof. Dr. Y
Fukazawa, Dr. T. Haino. M. Yanase
Department of Chemistry. Faculty of Science
Hiroshima University
1-3-1 Kagamiyama Higashi. Hiroshima City 739 (Japan)
Fax: I n t . code +(824)24-0724
e-mail. fukarawacci sci.hiroshimd-u ac.jp
Anget! Chc.m. lnr Ed Engl. 1991, 36, No. 3
540
590
4
640
Figure 1. Absorption spectra ofC,, (1.07 x
moldm-') in the presence of 1 in
CS,. Theconcentrationsofl arefromthebottom(curves1-6):0.0, 1.12,2.23,3.35,
4.46, 5.58 ( x
m~ldm-~).
The isosbestic point at 478 nm as well as a J o b s plot provided
evidence for a 1:1 complex in solution.rs1The association constant of the complexes (Table 1) determined by the BenesiHildebrand method confirmed a 1 : 1 stoichiometry for the hostguest complexes in all cases. To our knowledge the association
constant of 1 with C,, (2.1 k0.1 x lO3dm3mol-') is the largest
yet reported for organic solvents.
Table 1. Association constants [dm3mol-'] obtained by titration of 1-3 with C,,,
at 298 K (i= 430-440 nm)
Toluene
Benzene
cs,
o-Dichlorobenzene
2120+_110
1673 i 70
588 i 70
1840f130
1 5 0 7 1 84
459 f 74
660130
600i 3
284 +_ 70
308+_41
2 7 7 i 14
207 +_ 11
~~
1
2
3
The association constants are solvent dependent. The solubility of the guest increases along the series benzene, toluene, CS,,
and o-dichlorobenzene. The more weakly solvated guest is more
strongly bound in the host. The Gibbs energies of complexation
plotted against the logarithm of guest solubility (mgmL- ' ) r l a l
gave good linear relationships (correlation coefficients R2: 1
0.943; 2 0.952; 3 0.845). Thus, complex formation competes
against the solvation of the guest in these apolar solvents.
The association constants are also dependent on the substituents of the host (K,(l) > K,(2) > K J 3 ) in every solvent).
Since the guest molecule is a weak electron-acceptor, chargetransfer type interaction may play a role in the complexation. To
examine this idea, the HOMO energies of the host (1 -8.819,
2 -8.843, 3 -8.875 eV) were evaluated with PM3 MO calculations. The plot of HOMO energies against the Gibbs energies
gave a good linear relationship in every solvent (average correlation coefficient for 4 solvents: R2 = 0.925k0.032).
Van der Waals interactions between the host and guest are
also operative, since the host with the substituent of the highest
polarizability (X = I) binds the guest most strongly. The magnitude of the van der Waals interaction was estimated by means of
molecular mechanics calculations (with the program AMBER*,
\%: VCH Verlug.sge.~ellschu~r
mhH. 0-69451 Weinheim. 1997
O57O-0833197/36O3-0259 $ 15 00+ .25!0
259
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implemented in MacroModel V.5.0) .['I The relative steric energies ofassociation are -3.51 kcal mol-' (l),-2.33 kcal mol(2), and 0.0 kcal mol-' (3). A plot of the Gibbs energies of the
complexation versus the relative steric energies gave an excellent
correlation in every solvent (R2= 0.951 (toluene), 0.961 (benzene), 0.975 (CS,), and 0.998 (o-dichlorobenzene)). We therefore conclude that the van der Waals interactions between host
and guest play an important role in these complexations.
Slow concentration of a solution of 1 and an equimolar
amount of the guest molecule in CS, gave purple prisms of the
inclusion complex. The X-ray crystallographic analysis["] provided an unexpected result: the ratio of the host and C,, was 2: 1
in the solid state! The guest molecule is encapsulated within a
cavity composed of the two host molecules (Figure 2). Due to
b
C
b
C
Figure 2. A stereoscopic view of the crystal packing of 1:2 complex of C,, with 1.
the positional disorder of the two iodine atoms over the para
positions of the five phenols, this C60.(l)zcomplex has pseudo
D,, symmetry in the solid state. Judging from the symmetry,
there are only four nonequivalent carbons for the guest molecule. In this complex, there are altogether 144 short interatomic
distances ( < 4.0 A) between the sp2carbons in the guest and two
hosts, which suggests a strong binding of this complex.["]
A complexation-induced upfield shift of 3CNMR signals"
for the guest can be observed if the structure of the 1:1 complex
in solution is similar to that of C,, in the solid state. Based on
the X-ray structure of C60.(l)z, we evaluated the local anisotropic contributions of the five benzene rings of calix[5]arenes
upon the 13C chemical shifts for the included C,, by our ring
current method" 'I. The symmetry of the inclusion complex was
reduced to C,, and the number of nonequivalent carbon atoms
of C,, increased from 4 to 8 when one of the host molecules was
eliminated. The complexation-induced chemical shifts of these
eight different carbons (the number of carbon atoms in each
environment is given in parentheses) were estimated: 6 = 2.83
(5), 2.61 ( 5 ) , 1.56 (lo), 0.79 (lo), 0.50 (lo), 0.38 (lo), 0.33 (5),
0.31 (5): the average of 60 carbons is 6 ~ 1 . 0 4 4 .
The observed complexation-induced shift A6 of C,, is
0.35, when the equimolar amount of the guest ( 1 . 7 4 ~
moldm-3)andhost(1.75x
moldm-3)arepresentin
CS,. Judging from the association constant, 41 % of the guest is
bound by the host in the solution. The calculated shift A6 induced by the complexation of the guest molecule is thus 0.43.
The good agreement of the observed and calculated induced
shifts supports our assumed inclusion structure in solution.
260
0 VCH Verlagsgeseilschaff mbH, 0-69451 Weinheim,1997
Of course, a rapid association-dissociation equilibrium makes
all the carbon atoms of the molecule equivalent in solution.
In summary, the structure of the complex in solution was
disclosed by the ring current method based on X-ray crystallographic analysis. The experiments presented here have shown
that van der Waals interactions between the host and guest play
an important role in the complexation in solution.
Received: August 6, 1996 [Z94291E]
German version: Angew. Chem 1997, 109,288-290
Keywords: calixarenes * fullerenes
supramolecular chemistry
*
host -guest chemistry
-
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[lo] Crystal structure analysis of C 6 , . ( l ) Z- 8 H 2 0C,,,H,,O,,I,,
:
monoclinic space
group P2,/n, a =18.172(11), b =18.473(13), c =16.292(17)A, h = 89.98(11",
V = 5469(7) A3, pealed = 1.526 g ~ r n - ~(CU,,)
~,
= 9.53 cm-'. 2 = 2. RigakuAFC6 diffractometer with graphite-monochromated Cu,. radiatlon,
A =1.54178 A, T = 293(2) K, 0129 scan, 7732 reflections measured
(3.4<0 <60.12"), 7511 independent reflections, 4601 reflections measured with
I,> 2u(I0). Structure solution by direct method (SIR92), refinement on Fh
(SHELXL93), hydrogen atoms isotropic and in a rigid model, 719 parameters,
a R 2 = 0.416 (observed reflections), corresponds to conventional R = 0.168
using reflection with IF,/ > 4 OolF,l.Largest peak and hole in the final difference map 2.51 and - 1.08 e k ' . Crystallographic data (excluding structure
factors) for the structure reported in this paper have been deposited with the
Cambridge Crystallographic Data Centre a s supplementary publication no.
CCDC-179.162. Copies of the data can be obtained free of charge on application to The Director, CCDC, 12 Union Road, Cambridge CB2 lE2,UK (fax:
Int. code + (1223)336-033; e-mail: deposit@cherncrys.cam.ac.uk).
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Lett. 1995, 36, 3349-3352.
OS70-0833f97f3603-0260$15.00+.25/0
Angew. Chem. Int. Ed. Engl. 1997,36, No. 3
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