suppmat figures tables 542

TABLES

Table 1. Comparison of calculated and measured distances of tetrabromocavitand 4a.

distance* Å

X-ray26

MNDO

PM3

AM1

Br-Br
C-C
C-C
H-H
Me-Me

9.58

7.92
5.24
4.28
7.18

9.80
8.00
5.37
4.33
7.41

9.62
7.80
5.25
4.20
7.13

9.60
7.87
5.24

4.21
7.16

(a)
(b)
(c)
(d)
(e)

* distances are defined in Figure 1.

Table 2. Guest incarceration in the methylene bridged hemicarcerand 1a.

Guest

Ecomplexation (kcal/mol)

Edeformation

Acetonitrile

Pyrrole
Dichloromethane
Furan
Dimethylformamide
Carbon disulfide
Tetrahydrofuran
Biacetyl
Pyridine
Benzene
-pyrone
Chlorobenzene
Mesitylene
1,2,4-trichlorobenzene

1.9
2.2
2.2
2.5
3.2
4.2

4.3
6.6
7.9
7.9
13.4
16.7
39.4
39.9

1.0
0.6
0.2
0.3
1.8
1.0
0.8
1.7
1.3
1.4
2.1

3.0
17.6
12.2

(kcal/mol)

Forms complex5,27,29
Yes
Yes44
Yes
Yes38
Yes
Yes
Yes
Yes 35
Yes
Yes
Yes
No
No

No

Table 3. Guest incarceration in the butane bridged hemicarcerand 2a.

Guest
6 molecules of water*
Acetone
Hydroquinone
Biacetyl
N,N-dimethylacetamide
Cyclopentanone
Benzene
2-bromophenol
-butyrolactone
o-xylene
p-xylene
4-methylcatechol
Nitrobenzene
Furan
m-xylene

2-methylhydroquinone
1,4-diiodobenzene
Diphenyl ether
1,3,5-tri-tert-butylbenzene

Ecomplexation
-10.3
-2.6
-2.3
-2.0
-1.9
-1.2
-0.1
0.5
2.7
3.8
4.3
5.3
5.3
5.6

6.5
6.8
16.8
35.7
212.3

(kcal/mol)

Edeformation

(kcal/mol)

1.1
0.6
1.9
1.1
2.4
1.5
1.4
2.2

1.5
3.5
1.7
2.8
4.6
0.2
3.2
2.8
3.3
14.7
88.6

* Ecomplexation is relative to a 6H2O cluster in the same spatial arrangement as in 2a.6H2O

Forms complex
Yes
Yes
Yes
Yes35
Yes

Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Not tested
Yes
Yes
Yes
No
No

28

Table 4. Stepwise incarceration of water in the butane bridged hemicarcerand 2a.

n H2O

Ecomplex -isolated

1
2
3
4
5
6
7

-5.8
-13.1
-22.0
-32.5
-40.8
-50.7
-59.5

*

Ecomplex -cluster

*

-4.7
-7.7
-8.6
-8.3
-10.3
-8.6

* Ecomplex-isolated = E2a.nH2O - (E2a + n x EH2O); Ecomplex-cluster = E2a.nH2O - (E2a + EnH2O)
all energies are in kcal/mol

Table 5. Comparison of structural parameters of AM1 optimized 2a.guest structures with
reported X-ray data for 2b.guest.28
Host-guest

Angle (o) of twist

Distance (Å)

Distance (Å) of

Energy (kcal/mol)

Complex

around the polar

bottom - top of

diagonal O…O,

of optimised

axis.

aryl C planes.

aryl oxygens.

complex.

11.42
(11.5)*
11.9
(12.0)
11.7
(11.8)
11.8
(11.9)
11.7
(11.8)
11.7
(11.8)
10.550.11

8.60.2
8.50.1
8.60.1
8.70.3
8.60.1
8.60.1
8.980.11

-1079.8
-602.1
-662.6
-643.1
-687.8
-716.5

11.810.01
11.430.01
11.140.20
11.210.03
11.110.03

8.640.03
9.060.06
8.920.04
8.960.13
8.960.02

2a.6H2O AM1
2a.1,4-C6H4I2 AM1
2a.p-xylene AM1
2a.C6H5NO2 AM1
2a.2-BrC6H4OH AM1
2a.Me2NCOMe AM1
2b.6H2O Xray

21.2
4.9
11.8
4.7
8.8
13.8
15

2b.1,4-C6H4I2 Xray
2b.p-xylene Xray
2b.C6H5NO2 Xray
2b.2-BrC6H4OH Xray
2b.Me2NCOMe Xray

1
0
0
1
0

1

(3.7)1
(0.0)
(0.0)
(0.0)
(0.8)
(2.0)

(8.7)*
(8.7)
(8.7)
(8.6)
(8.6)
(8.6)

Values in brackets are for the optimized hemicarceplex obtained by starting with the no-twist pseudo-D 4h
symmetry conformation of host 2a.
2
Obtained as the distance between centroids placed on the opposing poles. A centroid was placed between
the four carbons (H attached) of the aryl groups at the pole.

(-1079.7)*
(-602.6)
(-662.7)
(-640.9)
(-686.8)
(-714.6)

List of Figure Captions.

Figure 1. Tetrabromocavitand 4a.
(a) AM1 optimized structure of 4a.
(b) Schematic diagram defining inter-atomic distances in 4a.

Figure 2. Cartoon representation of the bridge conformations in hemicarcerand 1a.

Figure 3. AM1 optimized structure of 1a.furan.

Figure 4. AM1 HOMOs of (a) 1a.pyrrole (E –8.99eV) and (b) pyrrole (E –8.66eV).

Figure 5. Structures of 5a.pyrazine (a) AM1, (b) X-ray

Figure 6. Bonding Orbital (255a) of 5a.pyrazine (X-ray geometry) illustrating hostguest interactions.

Figure 7. Molecular electrostatic isosurface (-40 kcal/mol) depicting the orientation of
the lone pairs from the eight inward facing bridging oxygens of 2a (outward facing lone
pairs have been removed for clarity).

Figure 8. AM1 optimized structure of 2a.6H2O (Encapsulated H2O atoms shaded black).

Figure 9. Cartoon representation of the two different orientational pathways for reaction
of 1a with furan.

Figure 10. Energy diagram for the reaction of 1a with furan – routes 1 and 2. Relative
energies (kcal/mol) are indicated on the plot.

Figure 11. Stereoview of the AM1 structure of a pseudo transition state for 1a.furanTS*-out - (route 1).

Figure 12. Two AM1conformations of 1a.dmf - (For clarity, structures of each
conformation show only heavy atoms and the side inter-hemispheric bridges are hidden).
(a) 1a.dmf-i (b) 1a.dmf-ii

Figure 13. Energy diagram for the reaction of 1a with dmf – routes 1 and 2. Relative
energies (kcal/mol) are indicated on the plot.

Figure 14. AM1 TS* for 1a.dmf with two intra-hemispheric bridges flipped open.
(Only heavy atoms are shown).