Syntheses, Structural Studies, and Copper Iodide Complexes of Macrocycles Derived from Williamson Ether Syntheses Involving 2,9-Bis(4-hydroxyphenyl)-1,10-phenanthroline, α,ω-Dibromides, and Resorcinol or 2,7-Dihydroxynaphthalene

Article abstract of DOI:10.1071/CH16587

1,3-Bis(6-bromohexyloxy)benzene, 2,7-bis(6-bromohexyloxy)naphthalene, 1,3-bis(4-bromomethylbenzyloxy)benzene, and 1,3-bis(3-bromomethylbenzyloxy)benzene were prepared via Williamson ether synthesis using resorcinol or 2,7-dihydroxynaphthalene and 1,6-dibr

Full text of DOI:10.1071/CH16587

RESEARCH FRONT
CSIRO PUBLISHING
Aust. J. Chem. 2017, 70, 373–386
Full Paper
http://dx.doi.org/10.1071/CH16587
Syntheses, Structural Studies, and Copper Iodide
Complexes of Macrocycles Derived from Williamson
Ether Syntheses Involving 2,9-Bis(4-hydroxyphenyl)-
1,10-phenanthroline, a,v-Dibromides, and Resorcinol
or 2,7-Dihydroxynaphthalene
A
A
A
Zuzana Baranov a´ , Hashem Amini, Madhav Neupane,
A
A
A
Sydney C. Garrett, Andreas Ehnbom, Nattamai Bhuvanesh,
A
,
A B
Joseph H. Reibenspies, and John A. Gladysz
A
Department of Chemistry, Texas A&M University, PO Box 30012,
College Station, Texas 77843-3012, USA.
B
Corresponding author. Email: gladysz@mail.chem.tamu.edu
1
,3-Bis(6-bromohexyloxy)benzene, 2,7-bis(6-bromohexyloxy)naphthalene, 1,3-bis(4-bromomethylbenzyloxy)benzene,
and 1,3-bis(3-bromomethylbenzyloxy)benzene were prepared via Williamson ether synthesis using resorcinol or 2,7-
dihydroxynaphthalene and 1,6-dibromohexane, 1,4-bis(bromomethyl)benzene, or 1,3-bis(bromomethyl)benzene (21–47 %
yield). These dibromides were condensed with 2,9-bis(4-hydroxyphenyl)-1,10-phenanthroline in the presence of K CO3
2
to give the corresponding 31- to 35-membered macrocycles (3a–d, 22–63 % yield). When 3a–d were treated with CuI,
mononuclear 1 : 1 complexes formed, in which the CuI chelates to the nitrogen donor atoms of the phenanthroline moiety
(
4a–d, 40–80 % yield). The crystal structures of 3a–c and 4a–c were determined and analyzed using density functional
theory calculations and in the context of rotaxanes that could be formed by treatment of 4a–d with terminal alkynes
e.g. macrocycle dimensions, void volumes). The copper and iodide atoms in 4a–c significantly protrude from the least-
(
˚
˚
squares plane of the phenanthroline moiety (0.46–0.63 A and 1.65–2.07 A).
Manuscript received: 14 October 2016.
Manuscript accepted: 16 November 2016.
Published online: 23 December 2016.
Introduction
represent an embodiment of the ‘active metal template’ strategy
[
4d,e,g,12]
Macrocycles and metal complexes thereof play ubiquitous roles
in supramolecular chemistry and particularly the synthesis of
mechanically interlocked molecules (MIMs), a descriptor that
2,3]
encompasses catenanes, rotaxanes, and knots.
popularized by Leigh et al.
In this scenario, the copper is
believed to template the coupling partners onto opposite faces
of the macrocycle complex, thereby facilitating subsequent
elimination to a rotaxane topology.
[1]
[
Variables
such as shape, conformational flexibility, and the nature and
position of functional groups can influence the efficacy of
these processes and the properties of the topologically novel
products.
In ongoing efforts, we have sought to synthesize rotaxanes
derived from diplatinum polyynediyl axles and 2,9-disubstituted
Accordingly, in this paper we describe (1) the preparation of
three new and one previously reported 2,9-disubstituted 1,10-
phenanthroline based macrocycles, (2) the synthesis of the
corresponding CuI complexes, (3) crystallographic and density
functional theory (DFT) characterization of the macrocycles and
complexes, and (4) analyses of their geometries, particularly
features relevant to the derived rotaxanes and their proposed
mechanism of formation. Portions of the preparative chemistry
and one crystal structure have been described in the Supplemen-
[
4]
1
Scheme 1.
,10-phenanthroline-based macrocycles, as exemplified by I in
5,6]
[
The former building blocks have been the subject
[
7]
of extensive studies in our laboratory. Such complexes
are normally accessed by oxidative homocouplings of the
corresponding monoplatinum polyynyl complexes under ‘Hay
[
5,6]
tary Material of preliminary communications.
rotaxanes will be the subject of a subsequent full paper.
The resulting
[
13]
[
8]
conditions’ (O , CuCl/tetramethylethylenediamine).
2
The latter building blocks have been applied to MIMs by
several groups. The inspiration for our studies came from
Saito et al., who employed CuI complexes with polyether
Results
[4d,9–11]
Synthesis of Macrocycles
O(CH ) O (m ¼ 6, 8) and m-C H linkages to prepare rotaxanes
We sought a family of polyether macrocycles based on a 2,9-
disubstituted 1,10-phenanthroline ‘northern hemisphere’ and a
dihydroxyarene-derived ‘southern hemisphere’ with a gradation
2
m
6 4
with organic 1,3-butadiyne axles, as exemplified by II in
Fig. 1.
[10]
The copper(I) 1,10-phenanthroline precursors
Journal compilation � CSIRO 2017
www.publish.csiro.au/journals/ajc

3
74
Z. Baranov a´ et al.
F
F
F
F
P(p-tol)3
2,7-dihydroxynaphthalene moiety, thereby expanding the
macrocycle cavity to a 35-membered ring. A reaction between
2,7-dihydroxynaphthalene, 1,6-dibromohexane, and K CO3
2
F
Pt
H
N
N
z
2
Cu
I
P(p-tol)3
(1.0 : 3.0 : 2.5 mole ratio) in acetone gave the ‘southern’ precur-
sor 2b as a white solid in 41 % yield. Condensation of 1, 2b, and
K CO (1.0 : 1.0 : 14.0 mole ratio) then afforded 3b as a white
2
3
z ꢀ 0 ꢁ 2 [O]
solid in 63 % yield. The products 2b and 3b, and all other new
compounds below were characterized by NMR spectroscopy
1
13
H and C{ H}) and microanalyses, as summarized in the
1
(
Experimental section.
In the third target molecule, the previously unknown 3c
Scheme 3, top), the (CH ) linker of 3a was replaced by a more
2 6
F
F
F
N N
(p-tol) P
F
F
F
F
P(p-tol)3
3
(
F
Pt
Pt
F
rigid p-xylylyl moiety, which maintains a 33-membered ring.
Reaction between resorcinol, 1,4-bis(bromomethyl)benzene,
and K CO , similar to the analogous condensations above, gave
z
z
P(p-tol)3
(p-tol) P
3
F
2
3
I
the ‘southern’ precursor 2c in 21 % yield. This was followed by
reaction between 1, 2c, and K CO (1.0 : 1.0 : 3.0 mole ratio),
2
3
Scheme 1. Rotaxanes derived from diplatinum polyynediyl axles and
which afforded 3c in 39 % yield. In the final target molecule, 3d
(Scheme 3, bottom), the p-xylylyl moiety of 3c was replaced by
a m-xylylyl linkage, reducing the ring size to 31. An analogous
sequence gave 2d in 38 % yield and 3d in 22 % yield. All of the
new organic compounds in Scheme 3 were white or pale yellow
solids.
1,10-phenanthroline-based macrocycles (I).
N
N
Several related macrocyclic targets were contemplated. In
the course of a vigorous program involving undergraduate
research students, additional ‘southern’ precursors were pre-
pared (e.g. analogues of 2c, d derived from 2,7-dihydroxy-
naphthalene). For a variety of reasons, the macrocycle
syntheses were not completed. Nonetheless, new compounds
that were completely characterized are included in the Supple-
mentary Material.
O
O
R
R
n
R
O
O
R
R
n
m
O
m
R
O
II
Copper(I) Complexes
In accord with the preparative goals in the introduction, copper(I)
complexes of the macrocycles were sought. Various copper
halides were screened, and copper(I) iodide proved to be optimal
in terms of yield and product stability. Thus, as shown in
Schemes 2 and 3, CH Cl solutions of the macrocycles 3a–d
R ꢀ
(
) ꢀ (CH2)
m ꢀ 6, 8
n ꢀ 6, 20
or
2
2
were combined with acetonitrile solutions of CuI. Workups gave
the 1 : 1 adducts 4a–d in 40–80 % yields as orange-to-yellow
crystals or solids that were stable to .1008C.
Fig. 1. Rotaxanes synthesized by Saito et al. via oxidative homocouplings
of organic terminal monoalkynes using CuI complexes of 1,10-phenanthro-
[
17]
[10d,e,14]
line-containing macrocycles.
Spectroscopic and Structural Characterization
of dimensions and conformational degrees of freedom. The first
target molecule had been previously reported by Saito et al. as
The NMR properties of the macrocycles (see Experimental
section) were unremarkable , but nonetheless important in
providing baselines for shielding effects in the corresponding
[10a]
part of their study in Fig. 1,
summarized in Scheme 2 (top).
and the synthetic route is
The ‘northern’ precursor 1
[
14]
[
5,13]
was easily accessed via a two-step sequence starting with 1,10-
9a,15]
phenanthroline and 4-lithioanisole.
rotaxanes.
4c, d, were poorly soluble, and good quality spectra could not
The CuI complexes with the xylylyl linkers,
[
1
be obtained. With 4a, b, some of the phenanthroline H NMR
As with all of the preparations described below, the ‘southern’
precursor was accessed by a classical Williamson ether synthesis.
Thus, resorcinol, 1,6-dibromohexane, and K CO were allowed
signals were 0.1–0.2 ppm downfield from those of 3a, b. In
contrast, the p-C H protons that were ortho to the phenan-
6 4
2
3
to react in acetone (1.0 : 3.0 : 2.5 mole ratio). A chromatographic
throline shifted upfield by 0.27–0.34 ppm. Some signals also
broadened.
[16]
workup gave the diether 2a
Then, 1, 2a, and K CO were combined in wet DMSO
as a white solid in 47 % yield.
Crystals of 3a and the solvates 3bꢀ2CHCl
and 3cꢀCH
Cl
2 2
2
3
3
(
3
1.0 : 1.0 : 14.0 mole ratio). Workup gave 3a, which features a
3-membered ring in 59 % yield as an air stable white solid
could be grown as described in the Experimental section. The
crystal structures were solved as summarized in Table 1 and
the Experimental section. Out of all the solvate molecules, only
one of the two associated with 3b could be accurately modelled.
The others were removed during refinement using standard
protocols, and thus do not appear in the headers in the tables.
[14]
(literature: 41 %).
In cases where we improved on reported
yields and/or acquired new NMR data, experimental details are
provided in the Supplementary Material.
In the second target molecule, the previously unknown 3b
[
18]
(
Scheme 2, bottom), the resorcinol unit of 3a was replaced by a
Key metrical parameters are given in Table 2.

Copper(I) Macrocycles
375
N
N
N
N
Br
Br
Cu
I
O
O
O
O
N
N
a
b
2a
3a
4a
5
9 %
79 %
O
O
HO
1
OH
O
O
O
O
Br
Br
N
N
N
N
Cu
I
2b
O
O
O
O
N
N
a
b
3b
4b
63 %
79 %
O
O
1
HO
OH
O
O
O
O
2 6 2 3
Scheme 2. Syntheses of macrocycles containing O(CH ) O tethers and copper complexes thereof: (a) K CO , wet DMSO; (b) CuI,
CH
3
2 2
CN/CH Cl .
N
N
N
N
Br
Br
Cu
I
N
N
a
b
O
O
O
O
2c
3c
4c
3
9 %
40 %
O
O
1
HO
OH
O
O
O
O
N
N
N
N
Br
Br
Cu
I
N
N
a
b
O
O
O
O
2
d
3d
4d
22 %
80 %
O
O
HO
1
OH
O
O
O
O
Scheme 3. Syntheses of macrocycles containing OCH
2
C
6
H
4
2 2 3 3 2 2
CH O tethers and copper complexes thereof: (a) K CO , wet DMSO; (b) CuI, CH CN/CH Cl .
Thermal ellipsoid plots and space filling representations of
a–c are provided in Fig. 2. The molecular structure of 3c
In contrast, 3a, b crystallized in chiral conformations with both
enantiomers in the unit cell. Deviating from usual procedures,
the symmetry equivalent atoms of 3c were assigned different
3
exhibited a mirror plane that bisected the resorcinol and central
phenanthroline rings, as consistent with the space group Pnma.
[
18]
numbers (see Fig. 3), similar to those of the analogous atoms

3
76
Z. Baranov a´ et al.
Table 1. Crystallographic data for 3a–c
A
B
3
B
3
a
3bꢀCHCl
45Cl
3c
Empirical formula
Formula weight
Temperature [K]
C
42
H
42
N
2
O
4
C
47
H
3
N
2
O
4
46 34 2 4
C H N O
638.78
110(2)
808.20
110(2)
1.54178
678.75
110(2)
˚
Wavelength [A]
1.54178
0.71073
Diffractometer
Crystal system
Space group
Bruker D8 GADDS
Monoclinic
Pn
Bruker D8 GADDS
Triclinic
Bruker APEX 2
Orthorhombic
Pnma
P-1
Unit cell dimensions
˚
a [A]
˚
b [A]
10.8861(9)
15.6003(14)
11.1600(10)
90
8.4044(4)
11.058(4)
23.613(8)
14.049(5)
90
14.7638(6)
18.7247(8)
73.146(3)
˚
c [A]
a [8]
b [8]
g [8]
112.189(4)
90
85.741(3)
90
81.873(3)
90
˚
Volume [A ]
3
1754.9(3)
2
2199.89(17)
2
3668(2)
Z
4
ꢁ3
rcalcd [Mg m
]
1.209
1.220
1.229
ꢁ1
m [mm
F(000)
]
0.611
2.231
0.078
680
848
1424
3
Crystal size [mm ]
Range for data collection
Index ranges
0.11 ꢂ 0.10 ꢂ 0.03
2.83 to 59.99
ꢁ12 # h # 12
0.12 ꢂ 0.06 ꢂ 0.04
2.47 to 60.00
ꢁ9 # h # 9
ꢁ16 # k # 16
ꢁ21 # l # 21
43282
0.12 ꢂ 0.10 ꢂ 0.07
2.34 to 24.99
ꢁ13 # h # 13
ꢁ28 # k # 28
ꢁ16 # l # 16
33095
ꢁ
17 # k # 17
12 # l # 12
ꢁ
Reflections collected
24948
Independent reflections
Max. and min. transmission
Data / restraints / parameters
4608 (Rint ¼ 0.0499)
0.9819 and 0.9358
4608 / 2 / 434
0.990
6414 (Rint ¼ 0.0526)
0.9161 and 0.7756
6414 / 6 / 525
1.064
3286 (Rint ¼ 0.0504)
0.9945 and 0.9906
3286 / 0 / 239
1.032
2
Goodness-of-fit on F
Final R indices [I . 2s(I)]
R indices (all data)
R1 ¼ 0.0364
wR2 ¼ 0.0832
R1 ¼ 0.0459
wR2 ¼ 0.0900
0.208 and ꢁ0.193
R1 ¼ 0.0519
wR2 ¼ 0.1416
R1 ¼ 0.0619
wR2 ¼ 0.1477
0.605 and ꢁ0.553
R1 ¼ 0.0401
wR2 ¼ 0.1031
R1 ¼ 0.0486
wR2 ¼ 0.1073
0.169 and ꢁ0.155
˚
Largest diff. peak and hole [eA
ꢁ3
]
A
This structure was described earlier in reference [6].
B
Some or all of the solvate molecules were removed during refinement as described in the Experimental section.
of 3a, b. This facilitates comparisons of metrical parameters
In all of the solvates that could be crystallographically
modelled (3b in part; 4a–c), solvent was found in the macro-
cycle cavity. Some representative motifs are depicted in Fig. 4.
However, bonding interactions with the macrocycle or CuI
moiety were not apparent. In 3a, intermolecular NꢀꢀꢀHC hydro-
gen bonds were present, as depicted in the Supplementary
Material (Fig. S2). In 4a–c, p stacking interactions were also
obvious (Figs S3–S5). Additional analyses of the structural data
are provided in the Discussion section.
The compounds in Figs. 2 and 3 were also modelled by DFT
calculations as described in the Experimental section. In all
cases, the optimized geometries very closely corresponded to
those found in the crystals. The similarities were so striking that
these data are simply represented by overlays in the Supplemen-
tary Material (Figures S8–S10). In particular, the CuI moieties
were again displaced from the planes of the 1,10-phenanthroline
units. The distances of the copper and iodide atoms from the
(
Table 2). The oxygen lone pairs in 3b, c and most of those in 3a
were exo to the macrocycle cavity, analogous to the dominant
[
5]
orientation in the corresponding rotaxanes.
Crystals of solvates of the corresponding CuI complexes –
4
These structures were similarly solved, giving the represen-
aꢀCH Cl , 4bꢀ2CHCl , and 4cꢀCH Cl – were also obtained.
2
2
3
2
2
[18]
tations in Fig. 3 and metrical parameters in Table 2.
In all
cases, the solvent molecules could be accurately modelled. The
oxygen lone pairs in 4b, c and most of those in 4a were exo to the
macrocycle cavity, paralleling the situation with 3a–c.
The copper atoms of 4a–c exhibited distorted trigonal planar
coordination geometries, with the N–Cu–N bond angles
(82.46(14)8–83.17(10)8) being much smaller than the N–Cu–I
bond angles (133.86(8)8–140.52(10)8). The sums of the three
bond angles (355.518–357.118; see Table 2) were close to 3608.
In all cases, the CuI moieties markedly protruded on one side of
the planar C N 1,10-phenanthroline units. The distances of the
˚
least-squares planes ranged from 0.51 to 0.57 A and from 1.69 to
1
2 2
˚
1.86 A, respectively (folding angles 24.48-26.88).
copper and iodide atoms from the phenanthroline least-squares
˚
˚
planes ranged from 0.46 to 0.63 A and from 1.65 to 2.07 A,
Analogous calculations were also carried out with 3d and
4d, and analogues of 3c, d and 4c, d in which the ‘southern
hemispheres’ were derived from 2,7-dihydroxynaphthalene as
opposed to resorcinol (species not yet synthesized). Given the
excellent agreement of theory and experiment with 3a–c and
respectively (Table 2). The CuIN units were roughly planar
2
(
maximum atomic deviations from least-squares planes: 0.14–
˚
.15 A). Thus, the folding angles with the phenanthroline least-
0
squares planes were calculated and ranged from 24.38 to 31.08.

Copper(I) Macrocycles
377
˚
˚
3
Table 2. Key crystallographic distances (A), angles (8), and void volumes (A ) for 3a–c and 4a–c
A
B
3
B
3a
3bUCHCl
3c
4aUCH
2
Cl
2
4bU2CHCl
3
2 2
4cUCH Cl
Cu–N1
–
–
–
–
–
–
–
2.077(3)
2.051(4)
2.4306(7)
1.346(6)
1.373(6)
1.437(6)
1.370(5)
1.349(5)
1.478(6)
1.364(5)
1.443(5)
1.494(6)
1.530(6)
1.528(6)
1.528(6)
1.501(6)
1.439(5)
1.376(5)
1.374(5)
1.445(5)
1.513(6)
1.516(6)
1.528(6)
1.526(6)
1.524(6)
1.437(5)
1.369(5)
1.478(6)
134.06(10)
140.52(10)
82.46(14)
131.5(3)
107.6(3)
108.8(3)
131.0(3)
131.5(3)
107.6(3)
108.8(3)
131.0(3)
119.1(4)
118.6(4)
118.1(3)
117.7(3)
116.6(3)
118.7(3)
357.04
2.053(3)
2.054(2)
2.4347(8)
1.346(6)
1.373(6)
1.437(6)
1.370(5)
1.349(5)
1.473(5)
1.361(4)
1.433(4)
1.493(5)
1.521(5)
1.515(5)
1.522(4)
1.509(4)
1.431(4)
1.367(4)
1.365(4)
1.427(4)
1.516(5)
1.517(4)
1.528(4)
1.502(4)
1.520(4)
1.451(3)
1.363(3)
1.484(4)
2.059(3)
2.072(3)
Cu–N2
–
–
Cu–I
2.4325(5)
1.338(4)
1.369(5)
1.443(5)
1.358(5)
1.344(5)
1.474(6)
1.375(5)
1.427(5)
1.506(6)
C1–N1
1.330(3)
1.357(3)
1.448(4)
1.356(3)
1.338(3)
1.481(4)
1.373(3)
1.438(3)
1.501(4)
1.511(4)
1.508(4)
1.533(4)
1.503(4)
1.435(3)
1.385(3)
1.376(3)
1.440(3)
1.505(4)
1.521(3)
1.528(4)
1.524(3)
1.500(4)
1.437(3)
1.375(3)
1.485(4)
–
1.332(3)
1.358(3)
1.457(4)
1.364(3)
1.336(3)
1.483(4)
1.365(3)
1.442(3)
1.505(4)
1.529(4)
1.533(4)
1.528(4)
1.505(4)
1.445(3)
1.367(3)
1.372(3)
1.431(3)
1.507(4)
1.534(4)
1.516(4)
1.521(4)
1.501(4)
1.439(3)
1.364(3)
1.485(4)
–
1.321(2)
N1–C5
1.3581(19)
1.450(3)
1.3581(19)
1.321(2)
1.492(2)
1.3808(18)
1.432(2)
1.507(2)
1.390(2)/1.382(2)
1.386(2)/1.393(2)
1.390(2)/1.389(2)
1.513(2)
1.4243(18)
1.3761(17)
1.3761(17)
1.4243(18)
1.513(2)
1.390(2)/1.389(2)
1.386(2)/1.393(2)
1.390(2)/1.382(2)
1.507(2)
1.432(2)
1.3808(18)
1.492(2)
–
C5–C9
C9–N2
N2–C12
C12–C13
C16–O1
O1–C19
C19–C20
C20–C21
C21–C22
C22–C23
C23–C24
C24–O2
C
C
C
C
1.390(6)/1.390(6)
1.387(6)/1.383(6)
1.394(6)/1.391(6)
1.495(6)
C
C
1.432(5)
O2–C25
1.381(5)
C29–O3
1.368(5)
O3–C31
1.445(5)
C31–C32
C32–C33
C33–C34
C34–C35
C35–C36
C36–O4
1.505(6)
C
C
C
C
C
C
1.399(6)/1.371(6)
1.374(6)/1.398(6)
1.408(6)/1.366(6)
1.503(6)
1.440(5)
O4–C37
1.359(5)
C1–C40
1.479(5)
N1–Cu–I
N2–Cu–I
N1–Cu–N2
C1–N1–Cu
C5–N1–Cu
C9–N2–Cu
C12–N2–Cu
C1–N1–Cu
C5–N1–Cu
C9–N2–Cu
C12–N2–Cu
C1–N1–C5
C9–N2–C12
C16–O1–C19
C24–O2–C25
C29–O3–C31
C36–O4–C37
Sum of angles N–Cu–N/I
136.54(7)
139.10(8)
–
–
–
137.40(8)
83.17(10)
131.5(2)
109.0(2)
109.3(2)
130.7(2)
131.5(2)
109.0(2)
109.3(2)
130.7(2)
118.3(3)
118.5(3)
118.7(3)
116.7(2)
118.7(2)
116.7(2)
357.11
0.462
133.86(8)
82.55(12)
131.3(3)
108.0(2)
108.0(2)
130.4(3)
131.3(3)
108.0(2)
108.0(2)
130.4(3)
119.1(3)
119.4(3)
117.8(3)
116.2(3)
117.6(3)
120.8(3)
355.51
0.603
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
118.8(2)
118.7(2)
119.25(12)
119.25(12)
117.72(12)
118.10(11)
118.10(11)
117.72(12)
–
118.9(2)
118.8(2)
117.1(2)
117.5(2)
117.4(2)
–
118.6(2)
119.55(19)
117.10(19)
116.59(19)
117.89(19)
–
D
CuUUUphen
IUUUphen
CuIN1N2 vs phen
–
–
–
0.630
D
–
–
–
1.989
1.651
2.067
E
–
–
–
29.14
24.33
30.97
N1–C1–C40–C41
N2–C12–C13–C18
ꢁ29.24
ꢁ18.75
19.04
59.62
30.43
10.365
4.768
10.746
10.642
10.886
11.054
10.331
8.426
6.630
20
ꢁ19.32
10.67
ꢁ19.97
19.97
26.05
37.92
21.94
ꢁ26.01
23.09
ꢁ32.40
32.67
ꢁ24.83
26.65
F
Plane A vs phen
9.59
20.97
F
Plane B vs phen
25.29
1.09
33.50
2.28
44.68
F
Plane C vs phen
19.59
20.97
ꢁ22.78
10.747
ꢁ36.02
10.850
7.350
ꢁ20.48
10.746
4.849
O1UUUO4
O2UUUO3
N1UUUO3
N2UUUO2
11.136
7.316
10.372
4.634
4.758
13.105
12.714
12.696
12.634
12.644
11.574
6.935
10.223
10.670
12.619
12.201
11.955
12.119
12.998
10.230
7.110
11.996
10.496
11.953
11.451
11.509
8.036
10.223
11.534
G
N1UUUCdistal
9.519 (8.487)
9.519 (8.487)
10.176
11.618
G
N2UUUCdistal
11.751
O1UUUO3
O2UUUO4
C17UUUC42
Void volume
7.835
10.176
11.834
6.379
6.808
6.710
474
354
344
482
155
A
This structure was described earlier in reference [6].
B
C
Some or all of the solvate molecules were removed during refinement as described in the Experimental section.
The second value is for the atoms C211, C221, C331, and C341 of the same arene ring.
D
E
2
The distance from the C12N least-squares plane.
The angle defined by the CuIN1N2 least-squares plane and the C12
N
2
least-squares plane.
F
These represent the absolute values of the angles between the C12
the arene ring containing C37–C40 (plane C).
N least-squares plane and those of the arene ring containing C13–C16 (plane A), the dihydroxyarene (plane B), and
2
G
The carbon atoms distal to N1 and N2 are taken as C29 and C25 (3a), C301 and C303 (3b), and C25 and C29 (C26 and C28, values in parenthesis) (3c), respectively; the analogous
atoms are employed for 4a–c.

3
78
Z. Baranov a´ et al.
(a)
(a)
C9
C5
N2 N1
C9
C5
C12
C1
C12
C1
C13 N2
N1 C40
C13
C18
C17
Cu
C40
C41
C42
C18
C17
C41
C42
C37
O4
C36
C16
I
C37
C36
O4
C16
C19
O1
C19
O1
C24
O3
C31
C29
O2
C25
C26
O2
C29 C31
C28
O3
C25
C24
C26
C28
(b)
(b)
C9
C5
N2 N1
C9
C5
C12
C13
C18
C17
C12
C1
C1
N2
C13
N1 C40
C40
Cu
C18
C41
C42
C41
C42
C16
O1
I
C37
O4
C16
C37
C17
O1
O4
C37
C19
C19
C36
C24
O2
C25
C26
C303 C301
C31
O3
C24
O2
C303 C301
C31
O3
C29
C29
C25
C28
C26
C28
(c)
C9
C5
(
c)
C9
C12
C1
N2
C13
N1
Cu
C41
C5
N2 N1
C40
C12
C1
C40
C13
C18
C17
C19
C18
C17
C16
O1
I
C41
C42
C37
O4
C37
C16
O1
C42
O4
C36
C19
C20
C211
C221
C21
C22
C23
C36
C35
C20
C35
C34
C33
C341
C331
C32
C21
C34
C211
C341
C331
C31
C22 C27
C26
C33
C28
C24
O2
C25
C26
C32
C221
C23
C24
C29
C31
C25 C29
O3
C28
O3
O2
Fig. 2. Thermal ellipsoid plots (50 % probability levels) and space filling
representations of the molecular structures of (a) 3a, (b) 3b, and (c) 3c. With
the last two, solvent molecules are either omitted or removed during
refinement. Hydrogen atoms are omitted for clarity.
Fig. 3. Thermal ellipsoid plots (50 % probability levels) and space filling
representations of the molecular structures of (a) 4a, (b) 4b, and (c) 4c;
solvate molecules and hydrogen atoms are omitted for clarity.
4
a–c, it can be anticipated that the optimized structures closely
the theoretical mass (þ1) was noticed in the mass spectrum of
3d. However, no traces of a second species could be found by
NMR analysis.
model those of the real compounds. These data are presented
in the Supplementary Material.
The structures of 4a–c differ significantly from those
obtained from reactions between 1,10-phenanthroline and CuI.
The latter educts react in acetonitrile to give a dimeric complex
with bridging iodide ligands and a distorted tetrahedral coordi-
nation environment. The copper atoms lie in the plane of the
phenanthroline ligand; the Cu–I vectors define angles of 53.58–
65.68 (two different solvates) with the plane. These features are
closely modelled by DFT calculations, analogous to those
described above (59.78 plane/Cu–I vector angle; D2h symmetry).
A solvothermal synthesis affords a polymeric allotrope with a
Discussion
The syntheses of 2a–d and 3a–d (Schemes 2 and 3) illustrate the
versatility of the Williamson ether synthesis for the assembly of
macrocycles. With regard to 2a–d and related bis(ethers)
described in the Supplementary Material, the highest yields
were obtained in reactions with the aliphatic a,v-dibromide Br
[
19]
(
CH ) Br (41–47 %) as opposed to reactions with xylylyl
2 6
dibromides (21–38 %). Possible side reactions include the par-
ticipation of both primary bromide atoms in ether formation and
the generation of dimeric macrocycles derived from two
molecules of 1 and two molecules of 2a–d. A weak peak of twice
zig-zag (Cu–I–Cu–I–) chain and similar tetrahedral copper
n
[20]
coordination geometry.

Copper(I) Macrocycles
379
(a)
(b)
Fig. 4. Representations of crystal structures with solvate molecules included: (a) 3b with one of the two CHCl
3
molecules;
(b) 4b with both CHCl molecules.
3
(a)
(b)
Fig. 5. Folding of (a) the free macrocycle 3c (empty ‘taco shell’) and (b) the more opened conformation of the corresponding CuI
complex 4c (stuffed taco). Solvate molecules have been omitted in both cases.
However, the CuI adduct of 2,9-bis(t-butyl)-1,10-
phenanthroline crystallizes as a monomer, with the copper and
iodine atoms markedly removed from the plane of the phenan-
reflect various geometric parameters such as the dimensions
of rigid units, folding, and the efficiency of crystal packing.
For example, the ‘southern hemisphere’ of 3b features a 2,7-
dioxanaphthalene moiety, the oxygen-to-oxygen ‘wingspan’ of
˚
˚
˚
throline ligand (0.72 A and 2.32 A versus 0.46–0.63 A and
1
[
21]
˚
.65–2.07 A for 4a–c).
˚
Thus, 2,9-substituents can sterically
which is 7.316 A (O2ꢀꢀꢀO3). Accordingly, 3b exhibits a larger
interfere with in-plane copper coordination. This effect is not
conducive to rotaxane syntheses as it renders it more difficult for
the two alkynyl coupling partners to interact effectively from
opposite faces of the phenanthroline moiety. These data suggest
that macrocycles based on 3,8-disubstituted 1,10 phenanthro-
lines may be more effective for ‘active metal template’ rotaxane
void volume than 3a, c, which contain 1,3-OC H O moieties
4
6
˚
with oxygen-to-oxygen wingspans of 4.768–4.634 A (corre-
sponding to a reduction of 35–37 %). However, the rigor of this
comparison is compromised by the different number of solvent
molecules present in each crystal.
Interestingly, in the ‘northern hemisphere’, the O1ꢀꢀꢀO4
[12]
syntheses.
wingspan associated with the C H O groups bound to the
4
6
Evaluation of the void space available within the macro-
cycles of 3a–c and 4a–c was desirable. This was performed,
after removing all solvate molecules, with the program
phenanthroline is 7 % greater in 3b than in 3c (11.136 versus
˚
10.372 A). These and a variety of related data are compiled in
the final series of entries in Table 2. For example, the distances
between the nitrogen donor atoms in 3b and opposing aromatic
carbon atoms in the ‘southern hemisphere’ are 12.696–
[
22]
3
˚
Mercury,
using a probe volume of 7.24 A , a probe radius
˚
˚
of 1.2 A, and a grid spacing of 0.7 A. The macrocycle 3a, the
˚
crystal of which did not incorporate any solvent, exhibited a void
3
volume of 20 A (Table 2). In contrast, 3b and 3c, which
12.634 A. The corresponding distances for 3a, c are shorter
˚
˚
i.e. 11.054–10.886 A (corresponding to a reduction of 13–14 %)
˚
and 9.519–8.487 A (corresponding to a reduction of 25–33 %),
respectively. The corresponding distances in the CuI com-
plexes 4a–c are much more comparable (Table 2).
In the crystal, 3c exhibits a motif that is reminiscent of the
framework of a hard taco shell (Fig. 5a). These motifs stack on
top of each other, thus creating extended tunnel-like voids as
represented in Fig. 6. In contrast, in the corresponding complex
crystallized as a disolvate and monosolvate, respectively, gave
3
void volumes of 474 and 354 A . With 4a–c, the largest void
[23]
˚
volume was associated with the complex that crystallized as a
3
disolvate (4b, 482 A ). The voids in the complexes that were
˚
3
monosolvates were smaller (4a, 344 A ; 4c, 155 A ).
3
˚
˚
In addition to the void volumes displaying a correlation to
the number of solvent molecules originally present, they

3
80
Z. Baranov a´ et al.
(a)
In conclusion, this study has optimized and extended
Williamson ether syntheses that enable access to a variety of
macrocycles based on the 2,9-bis(4-hydroxyphenyl)-1,10-
phenanthroline building block 1. The corresponding CuI com-
plexes have been prepared, which, as described elsewhere, serve
as ‘active metal template’ precursors to rotaxanes derived from
[
5]
the oxidative homocoupling of terminal alkynes. The struc-
tural properties of all of these compounds, as well as the NMR
properties of the uncomplexed macrocycles, have been charac-
terized in detail. These data provide a solid foundation for the
analysis and interpretation of a variety of properties of the
resulting rotaxanes, which include MIMs derived from diplati-
num polyynediyl complexes. These efforts will soon be detailed
[
13]
in a comprehensive full paper.
Experimental
General Data
Organic reactions were conducted under ambient conditions,
and the copper complexes were prepared under nitrogen atmo-
spheres using Schlenk techniques. Prior to use, THF (Fisher
Scientific) was dried using a Glass Contour solvent purification
system. Other chemicals CH Cl , CHCl , methanol (MeOH)
(b)
2
2
3
(EMD), acetone, hexanes, ethyl acetate (BDH), CDCl (Cam-
bridge Isotope Laboratories), K CO (anhydrous, BDH), CuI
3
2
3
(
99.998 %, Alfa Aesar), 2,7-dihydroxynaphthalene (97 %, Alfa
Aesar), 1,6-dibromohexane (97 %, Alfa Aesar), resorcinol
99 %, Alfa Aesar), 1,4-bis(bromomethyl)benzene (97 %, Alfa
Aesar), 1,3-bis(bromomethyl)benzene (97 %, Alfa Aesar), silica
40–63 mm, 230–400 mesh, Silicycle), and alumina (neutral,
(
(
Brockmann I, 50–200 mm, Acros) were used as received. Thin
layer chromatography (TLC) was carried out on EMD silica gel
60 F254 or EMD aluminium oxide 60 F254 (neutral) plates that
were visualized with 254 nm or 365 nm UV light.
NMR spectra were recorded on a Varian NMRS 500 MHz
ambient probe temperatures) or a Bruker Avance III 500 MHz
(
(cryoprobe conditions) spectrometers and referenced as follows
(c)
1
13
1
(
d, ppm): H, residual internal CHCl (7.26); C{ H}, internal
3
CDCl3 (77.16). Mass spectra were recorded on a Thermo
Scientific LCQ-DECA (atmospheric pressure chemical ioniza-
tion (APCI) conditions) or an Applied Biosystems PE SCIEX
QSTAR (electrospray ionization (ESI) conditions) spectro-
meters. Ion assignments were verified against calculated isotope
[
24]
patterns.
Melting points were determined on a Stanford
Research Systems (SRS) MPA100 (Opti-Melt) automated
device. Microanalyses were conducted by Atlantic Microlab.
2
,7-Bis(6-bromohexyloxy)naphthalene (2b)
A round-bottom flask was charged with acetone solutions
96 mL total)of2,7-dihydroxynaphthalene(3.850 g, 24.04 mmol)
(
Fig. 6. Tunnel-like voids in the crystal structure of the free macrocycle 3c
after removal of solvate molecules: view along the (a) a-, (b) b-, and (c) c-
axes, respectively.
and 1,6-dibromohexane (17.594 g, 72.112 mmol) and fitted with
a condenser. Then, K CO (8.306 g, 60.09 mmol) was added
2
3
with stirring. The mixture was refluxed. After 3 days, the solvent
was removed by rotary evaporation. Water (250 mL) was added.
The residue was extracted with CH Cl (1200 mL total). The
2
2
4c, which is also a monosolvate, the CuI moiety intrudes into the
less severely folded macrocycle cavity. Accordingly, the void
extract was washed with aqueous NaOH (200 mL, 10 % w/v)
and brine (200 mL) and dried over Na SO . The solvent was
removed by rotary evaporation. The residue was chromato-
2
4
3
volume decreases by more than 50 % (344 versus 155 A ).
˚
Regardless, despite the intrinsically qualitative nature of these
void volume comparisons, they help to define the dimensional
limits that can be realized with these macrocycles in MIMs.
Additional crystallographic features of ancillary interest are
illustrated in figures in the Supplementary Material.
graphed (silica gel, 6.5 cm ꢂ 31 cm column, packed in hexanes
and eluted with a CH Cl /hexanes gradient). The solvent was
2 2
removed from the product containing fractions (assayed by
TLC, eluent 1 : 2 v/v CH Cl /hexanes) by rotary evaporation to
give 2b as a white crystalline solid (4.831 g, 9.934 mmol, 41 %),
2
2

Copper(I) Macrocycles
381
3
mp 748C. dH (CDCl , 500 MHz) 7.64 (2H, d, JHH 8.9,
2.4, OCCHC), 6.98 (2H, dd,
þ [25]
(9 ꢂ s, aryl), 69.8 (s, OCH ), 33.4 (s, BrCH ). m/z (ESI ) 477
þ
22 20 2 2
3
2
2
4
OCCHCH), 7.03 (2H, d, J
(1 %, [2d þ 1] ). Anal. Calc. for C H Br O (476.2076):
HH
3
4
2
JHH 8.9, J 2.4, OCCHCH), 4.06 (4H, t, J 6.4, OCH2),
C 55.49, H 4.23. Found: C 54.83, H 4.07 %.
HH
HH
2
3
m, OCH CH , BrCH CH ), 1.58–1.51 (8H, m, OCH CH CH ,
.44 (4H, t, J 6.8, BrCH ), 1.94–1.83 (8H, 2 overlapping
HH 2
2
2
2
2
2
2
2
(2,9-(1,10-Phenanthrolinediyl))(4-C H O(CH ) O) (2,7-
6 4 2 6 2
BrCH CH CH ). d (CDCl , 125 MHz) 157.7 (s, OCCH),
3
2
2
2
C
naphthdiyl) (3b)
1
36.1, 129.2, 124.3, 116.4, 106.1 (5 ꢂ s, aryl), 67.8 (s,
2 2 2 2
A round-bottom flask was charged with DMSO solutions
(573 mL total) of 2b (1.393 g, 2.865 mmol) and 2,9-bis
OCH ), 34.0, 32.8, 29.2, 28.1, 25.5 (5 ꢂ s, OCH CH CH ,
þ [25]
þ
BrCH CH CH ). m/z (APCI )
2
487 (100 %, [2b þ 1] ), 407
[9a,15]
2
2
þ
þ
(4-hydroxyphenyl)-1,10-phenanthroline (1
;
.865 mmol) that had been neutralized as reported earlier.
1.044 g,
[9a]
(
3 %, [2b ꢁ Br] ), 161 (20 %, [dihydroxynaphthalene þ 1] ).
2
Then, K CO (5.544 g, 40.11 mmol) and water (5.7 mL) were
Anal. Calc. for C H Br O (486.2870): C 54.34, H 6.22, Br
2
2
30
2 2
2
3
3
2.86. Found: C 54.29, H 6.11, Br 32.78 %.
added with stirring. The sample was stirred at 658C for 19 h. The
solvent was removed by rotary evaporation. Water (100 mL)
was added, and the mixture was extracted with CH Cl2
2
1
,3-Bis(4-bromomethylbenzyloxy)benzene (2c)
A round-bottom flask was charged with a solution of resorcinol
1.016 g, 9.229 mmol) in acetone (15 mL) and fitted with a
condenser. Then, K CO (3.189 g, 23.21 mmol) was added with
(400 mL). The extract was dried over Na SO . The solvent was
2
4
(
removed by rotary evaporation. The residue was chromato-
graphed (alumina, 4.5 cm ꢂ 25 cm column, packed and eluted
with CH Cl ). The solvent was removed from the product
2
3
stirring, followed by a solution of 1,4-bis(bromomethyl)ben-
zene (7.309 g, 27.69 mmol) in acetone (25 mL). The mixture
was refluxed in the dark. After 3.5 days, the solvent was
removed by rotary evaporation. Water (200 mL) was added. The
mixture was extracted with ethyl acetate (400 mL). The extract
was washed with aqueous NaOH (10 % w/v) and dried over
2
2
containing fractions (assayed by TLC, eluent 1 : 1 v/v CH Cl /
2
2
hexanes) by rotary evaporation to give 3b as a moderately light
sensitive white solid (1.242 g, 1.803 mmol, 63 %) that was
stored in the dark, mp 2408C. d (CDCl , 500 MHz) 8.43 (4H, d,
H
3
3
[26]
3
[26]
JHH 8.8, H ),
o
8.25 (2H, d, J 8.4, H or H ),
HH
8.08
7.65
4
7
3
(2H, d, J 8.4, H or H ),
[26]
[26]
MgSO . The solvent was removed by rotary evaporation. The
4
7.73 (2H, s, H or H ),
5 6
HH
3
8
3
4
residue was chromatographed (silica gel, 4.5 cm ꢂ 23 cm,
(2H, d, J 8.9, OCCHCH of naphthyl), 7.12 (2H, d, J 2.4,
HH HH
3
[26]
packed in hexanes and eluted with a CH Cl /hexanes gradient
2
OCCHCC), 7.11–7.09 (4H, dm, J 8.8, Hm), 7.00 (2H, dd,
HH
2
3
4
3
1
0 : 90 - 20 : 80 - 30 : 70 - 40 : 60 - 50 : 50 v/v). The
solvent was removed from the product containing fractions
assayed by TLC, eluent both 1 : 2 and 2 : 1 v/v CH Cl /hexanes)
JHH 8.9, J 2.4, OCCHCH of naphthyl), 4.14 (4H, t, J 6.8,
HH HH
3
OCH ), 4.08 (4H, t, J 6.4, O C H ), 1.96 (4H, overlapping
0
0
2
HH
2
3
3
(
p, JHH 6.5, OCH CH ), 1.90 (4H, overlapping p, JHH
2 2
2
2
0 0
6.7, O C H C H ), 1.67–1.60 (8H, m, OCH CH CH ,
2 2 2 2
0
by rotary evaporation to give 2c as a white powder (0.928 g,
2
0 0 0
O C H C H C H ). d (CDCl , 125 MHz) 160.6, 157.8, 156.5,
2 2 C 3
0
1
7
6
.95 mmol, 21 %), mp 107.7–111.88C. d (CDCl , 500 MHz)
3
H
2
3
.41 (8H, br s, p-C H ), 7.20 (1H, t, J 7.2, OCCHCH), 6.58–
.57 (2H, m, OCCHCH), 6.60 (1H, m, OCCHCO), 5.03 (4H, s,
146.1, 136.9, 136.1, 132.1, 129.2, 129.1, 127.6, 125.7, 124.3,
6
4
HH
119.3, 116.8, 114.8, 105.8 (16 ꢂ s, aryl), 68.3, 67.4 (2 ꢂ s,
0
0
0
0
0
2
OCH ), 4.51 (4H, s, BrCH ). d (CDCl , 125 MHz) 160.0 (s,
C
OCH , O C H ), 29.5, 29.1 (2 ꢂ s, OCH CH , O C H C H ),
0 0 0 0
2 2 2 2 2 2
2
2
3
2
2
2
2
2
OCCH), 137.6, 137.4, 130.1 (3 ꢂ s, aryl), 129.4, 128.0 (2 ꢂ s,
CH of p-C H ), 107.6, 102.4 (2 ꢂ s, aryl), 69.7 (s, OCH ), 33.3
26.0, 25.7 (2 ꢂ s, OCH CH CH , O C H C H C H ). m/z
þ [25] þ
46 44 2 4
(ESI ) 689 (100 %, [3b þ 1] ). Anal. Calc. for C H N O
6
4
2
þ [25]
þ
(
s, BrCH ). m/z (ESI )
2
[2c þ 1] ). Anal. Calc. for C H Br O (476.2076): C 55.49,
H 4.23. Found: C 55.22, H 4.13 %.
538 (16 %, [2c þ 62] ), 477 (7 %,
(688.8664): C 80.20, H 6.44, N 4.07. Found: C 79.70, H 6.26,
N 4.12 %.
þ
2
2
20
2 2
(
2,9-(1,10-Phenanthrolinediyl))(4-C H OCH -4-
6 4 2
1
,3-Bis(3-bromomethylbenzyloxy)benzene (2d)
C H CH O) (1,3-C H ) (3c)
6
4
2
2
6
4
A round-bottom flask was charged with resorcinol (2.565 g,
A round-bottom flask was charged with DMSO solutions
(210 mL total) of 2c (0.501 g, 1.05 mmol) and 1 (0.383 g,
2
6
3.30 mmol),
9.896 mmol), and acetone (93 mL) and fitted with a condenser.
1,3-bis(bromomethyl)benzene
(18.449 g,
[9a]
1.05 mmol) that had been neutralized as reported earlier.
Then, K CO (0.435 g, 3.15 mmol) and water (2.1 mL) were
added with stirring. The sample was stirred at 658C in the dark
Then, K CO (8.050 g, 58.25 mmol) was added with stirring.
2
3
2
3
The mixture was refluxed in the dark. After 3 days, the solvent
was removed by rotary evaporation. Water (200 mL) was added.
The mixture was extracted with ethyl acetate (7 ꢂ 100 mL). The
extract was washed with aqueous NaOH (100 mL, 10 % w/v)
for 4 h. The solvent was removed by rotary evaporation. Water
(50 mL) was added, and the mixture was extracted with CH Cl2
2
(5 ꢂ 50 mL). The extract was washed with water (2 ꢂ 50 mL)
and brine (200 mL) and dried over MgSO . The solvent was
4
and brine (50 mL) and dried over MgSO . The solvent was
4
removed by rotary evaporation. The residue was chromato-
graphed (silica gel, 4.5 cm ꢂ 25 cm, packed in hexanes, eluted
with a CH Cl /hexanes gradient 5 : 95 - 20 : 80 v/v). The sol-
removed by rotary evaporation. The residue was chromato-
graphed (silica gel, 3 cm ꢂ 26 cm, packed in CH Cl , eluted
2
2
with MeOH/CH Cl gradient 1 : 999 - 2 : 998 v/v). The solvent
2
2
2
2
vent was removed from the product containing fractions
assayed by TLC, eluent 1 : 2 v/v CH Cl /hexanes) by rotary
was removed from the product containing fractions (assayed by
TLC, eluent 1 : 99 v/v MeOH/CH Cl ) by rotary evaporation to
give 3c as a moderately light sensitive very pale yellow powder
(
2
2
2
2
evaporation to give 2d as a white solid (4.190 g, 8.799 mmol,
8 %), mp 74.7–79.88C. d (CDCl , 500 MHz) 7.47 (2H, br s,
CH CCHCCH ), 7.36 (6H, br, BrCH CCHCHCH) 7.21 (1H, t,
3
(0.278 g, 0.410 mmol, 39 %) that was stored in the dark and
darkened slightly at 1158C and melted at 1658C. d (CDCl3,
H
3
2
2
2
H
3
4
3
[26]
3
JHH 8.2, OCCHCH), 6.63 (1H, t, J 2.1, OCCHCO), 6.61
HH
3
2H, dd, J 8.1, J 2.2, OCCHCH), 5.04 (4H, s, OCH2),
500 MHz) 8.33 (4H, dm, J 8.8, Ho), 8.26 (2H, d, J 8.4,
HH HH
4
[26]
H or H ), 8.07 (2H, d, J 8.4, H or H ), 7.73 (2H, s, H5
3
[26]
(
HH
HH
4
7
HH
3
8
[
26]
3
4
1
.52 (4H, s, BrCH ). d (CDCl , 125 MHz) 160.0 (s, OCCH),
2
38.3, 137.8, 130.2, 129.2, 128.8, 128.2, 127.6, 107.6, 102.3
or H6),
OCCHCH of m-C H O ), 7.11 (4H, d, J 8.8, Hm),
7.36 (8H, br, p-C H CH O), 7.17 (1H, t, J 8.2,
6 4 2
C
3
HH
[26]
3
6.59
6
4
2
HH

3
82
Z. Baranov a´ et al.
3
2H, dd, J 8.2, J 2.3, OCCHCH of m-C H O ), 6.41 (1H,
4
0
0
0
0
[ 28]
C
(
t, JHH 2.3, OCCHCO), 5.32 (4H, s, OCH ), 5.07 (4H, s,
O C H C H C H ). d
2
(CDCl , 125 MHz, cryoprobe) 161.4,
3
HH
HH
6
4
2
2
2
4
158.6, 157.8, 138.0, 136.3, 131.4, 129.1, 127.6, 126.0, 124.3,
116.8, 115.0, 106.2 (13 ꢂ s, aryl), 68.1, 67.5 (2 ꢂ s, OCH ,
2
0
0
O C H ). d (CDCl , 125 MHz) 160.3, 159.8, 156.3, 145.8,
3
2
C
2
0
0
0
0
0
2
1
1
37.3, 136.9, 136.5, 129.9, 129.1, 127.5, 127.3, 126.6, 125.7,
19.5, 116.0, 107.9, 103.0 (17 ꢂ s, aryl), 70.2, 69.8 (2 ꢂ s,
O C H ), 29.2, 28.9 (2 ꢂ s, OCH CH , O C H C H ), 25.6, 25.5
2
2
0
2
2
0
0
0
þ [25]
(2 ꢂ s, OCH CH CH , O C H C H C H ). m/z (ESI )
751
(60 %, [(3b)Cu] ), 689 (100 %, [3b þ 1] ). Anal. Calc. for
2
2
þ
2
2
2
2
0
0
þ [25]
þ
þ
OCH , O C H ). m/z (ESI )
2
679 (100 %, [3c þ 1] ). Anal.
2
Calc. for C H N O (678.7870): C 81.40, H 5.05, N 4.13.
4
C H CuIN O (879.3168): C 62.83, H 5.04, N 3.19. Found:
46 44
6
34
2
4
2 4
Calc. for C H N O ꢀH O (696.8022): C 79.29, H 5.21, N 4.02.
C 63.38, H 5.34, N 3.13 %.
4
6
34
2
4
2
[
27]
Found: C 79.30, H 5.16, N 3.97 %.
(
3c)CuI (4c)
(
2,9-(1,10-Phenanthrolinediyl))(4-C H OCH -3-
A solution of CuI (0.035 g, 0.18 mmol) in CH CN (3.5 mL) and
3
6
4
2
C H CH O) (1,3-C H ) (3d)
a solution of 3c (0.035 g, 0.18 mmol) in CH Cl (8 mL) were
2
6
4
2
2
6
4
2
combined using the same procedure as that used for preparing 4b
(3 h stirring). An identical workup gave 4c as a pale orange solid
A round-bottom flask was charged with DMSO solutions
(422 mL total) of 2d (1.005 g, 2.109 mmol) and 1 (0.769 g,
þ
[
9a]
(
7
0.061 g, 0.073 mmol, 40 %), mp 107.7–111.88C. m/z (ESI )
ꢁ
2
Then, K CO (2.187 g, 15.82 mmol) and water (4.2 mL) were
.110 mmol) that had been neutralized as reported earlier.
þ
þ
41 (50 %, [(3c)Cu] ), 679 (100 %, [3c þ 1] ). m/z (ESI ) 127
2
3
ꢁ
(100 %, [I] ). Anal. Calc. for C H CuIN O (869.2374):
2 4
added with stirring. The sample was stirred at 658C in the dark
for 5 h. The solvent was removed by rotary evaporation. Water
46 34
C 63.56, H 3.94, N 3.22. Calc. for C H CuIN O ꢀCH Cl
46 34
2
4
2
2
(954.1643): C 59.16, H 3.80, N 2.94. Found C 60.04, H 3.92,
N 2.90 %.
(300 mL) was added and the mixture was extracted with CH Cl2
2
[
29]
(
6 ꢂ 100 mL). The extract was washed with brine (100 mL) and
water (100 mL) and dried over Na SO . The solvent was
2
4
(
3d)CuI (4d)
removed by rotary evaporation. The residue was chromato-
graphed (silica gel, 4.5 cm ꢂ 25 cm, packed in CH Cl , eluted
A solution of CuI (0.019 g, 0.098 mmol) in CH CN (1 mL) and a
3
2
2
with a MeOH/CH Cl gradient 1 : 999 - 2:998 - 3 : 997 v/v).
solution of 3d (0.067 g, 0.098 mmol) in CH Cl (4 mL) were
2
2
2
2
The solvent was removed from the product containing fractions
assayed by TLC, eluent 1 : 99 v/v MeOH/CH Cl ) by rotary
combined using the same procedure as that used for preparing 4b
(0.5 h stirring). The precipitate was isolated by filtration
and dried by oil pump vacuum to give 4d as a yellow solid
(0.068 g, 0.078 mmol, 80 %), mp 107.7–111.88C. Anal. Calc. for
C H CuIN O (869.2374): C 63.56, H 3.94, N 3.22. Calc.
(
2
2
evaporation to give 3d as a moderately light sensitive white solid
0.308 g, 0.454 mmol, 22 %) that was stored in the dark and
darkened slightly at 1208C and melted at 1618C. d (CDCl3,
(
H
46 34
2 4
3
[26]
3
500 MHz) 8.37 (4H, dm, J 8.9, Ho), 8.24 (2H, d, J 8.4,
[
H or H ), 8.05 (2H, d, J 8.4, H or H ), 7.72 (2H, s, H5
for C H CuIN O UCH Cl U0.75H O (967.6758): C 58.34,
HH
HH
46 34
2
4
2
2
2
26]
3
[26]
[30]
H 3.91, N 2.89. Found: C 58.59, H 4.01, N 2.92 %.
4
7
HH
3
8
[
26]
or H6), 7.66 (2H, br s, CH CCHC), 7.40–7.34 (6H, m,
2
CH CCHCHCHC), 7.23 (1H, t, JHH 8.2, OCCHCH of
3
Crystallography A
2
3
m-C H O ), 7.16 (4H, dm, J 8.9, H ),
[26]
4
6.85 (1H, t, J
HH
6
4
2
HH
3
m
4
A CH Cl solution of 3a was allowed to evaporate slowly at
2 2
2
.4, OCCHCO), 6.65 (2H, dd, JHH 8.2, J 2.4, OCCHCH of
HH
room temperature. After 3 days, the resulting colourless plates
were analyzed as outlined in Table 1. Cell parameters were
[31]
obtained from 1080 frames using a 0.58 scan and refined with
0
0
m-C H O ), 5.30 (4H, s, OCH ), 5.13 (4H, s, O C H ). d
C
6
4
2
2
2
(CDCl , 125 MHz) 160.2, 159.8, 156.5, 146.2, 137.9, 137.6,
3
1
1
36.8, 132.8, 130.1, 129.1, 128.9, 127.6, 126.6, 126.2, 125.7,
19.4, 115.7, 107.4, 102.9 (19 ꢂ s, aryl), 69.9, 69.7 (2 ꢂ s,
2
4948 reflections. Integrated intensity information for each
reflection was obtained by reduction of the data frames
0
0
þ [25]
þ
OCH , O C H ). m/z (ESI )
2
679 (100 %, [3d þ 1] ), 757
[32]
2
with APEX2.
dimensional profiling algorithm. All data were corrected for
The integration method employed a three-
þ
þ
(
9 %, [3d þ 78] ), 1358 (7 %, [2 ꢂ 3d þ 1] ). Anal. Calc. for
C H N O (678.7870): C 81.40, H 5.05, N 4.13. Calc. for
2
4
6
34
4
Lorentz and polarization factors as well as crystal decay effects.
[33]
C H N O ꢀ2H O (714.8175): C 77.29, H 5.36, N 3.92. Found:
4
6
34
2
4
2
SADABS was used for absorption corrections.
The space
[
27]
C 77.58, H 5.34, N 3.99 %.
group was determined from systematic reflection conditions and
statistical tests. The structure was solved by direct methods
[34]
(
3b)CuI (4b)
using SHELXTL (SHELXS).
Non-hydrogen atoms were
refined with anisotropic thermal parameters. Hydrogen atoms
were placed in idealized positions and refined using a riding
model. The structure was refined (weighted least-squares
A solution of CuI (0.140 g, 0.734 mmol) in CH CN (14 mL) was
3
transferred via a Teflon cannula to a solution of 3b (0.505 g,
0
.734 mmol) in CH Cl (33 mL) in a Schlenk flask. The mixture
2 2
2
[34]
refinement on F ) to convergence. The absence of additional
symmetry or voids was confirmed using PLATON
was stirred in the dark. After 1 h, the solvent was removed by
rotary evaporation to give a pale orange solid. The residue was
recrystallized from hot CH Cl (refrigerator storage). The pre-
[
35]
(ADDSYM).
2
2
cipitate was isolated by filtration and dried by oil pump vacuum
to give 4b as a bright orange crystalline solid (0.508 g,
Crystallography B
0
1
.577 mmol, 79 %), which darkened slightly (contraction) at
248C and melted at 2268C. d (CDCl , 500 MHz) 8.42 (2H, br
A CHCl solution of 3b was allowed to evaporate slowly at room
3
temperature. After 3 days, the resulting colourless prisms were
analyzed as outlined in Table 1. Cell parameters were obtained
H
3
3
s, w1/2 27), 8.16 (4H, overlapping br d, J 7.9, p-C H ), 8.12
HH
6 4
[
31]
(
2H, overlapping br s, w1/2 23), 7.88 (2H, br s), 7.63 (2H, d,
3
JHH 8.8), 7.16 (2H, br s, w 36), 7.13 (4H, br d, J 7.5,
from 180 frames using a 0.58 scan.
information for each reflection was obtained by reduction of the
Integrated intensity
3
1/2
HH
3
p-C H ), 6.97 (2H, br d, J 8.8), 4.20–4.02 (8H, overlapping
3
br s and t, J
[32]
data frames with the program APEX2. SADABS was used for
absorption corrections. The space group was determined
from systematic reflection conditions and statistical tests.
6
4
HH
0
0
[33]
6.7, OCH , O C H ), 2.02–1.82 (8H, br m,
2
HH
0
2
0
0
OCH CH , O C H C H ), 1.69–1.56 (8H, br, OCH CH CH ,
2
2
2
2
2
2
2

Copper(I) Macrocycles
383
Table 3. Crystallographic data for 4a–c
4
aꢀCH
2
Cl
2
4bꢀ2CHCl
46Cl
3
4cꢀCH
2 2
Cl
Empirical formula
Formula weight
Temperature [K]
C
43
H44Cl
2
CuIN
2
O
4
C
48
H
6
CuIN
2
O
4
C
47
H36Cl CuIN O
2 2 4
914.14
110(2)
1.54178
1118.01
110(2)
954.12
110(2)
0.71073
˚
Wavelength [A]
0.71073
Diffractometer
Crystal system
Space group
Bruker D8 GADDS
Monoclinic
Bruker APEX 2
Triclinic
P-1
Bruker APEX 2
Triclinic
P-1
P2(1)/c
Unit cell dimensions
˚
a [A]
˚
b [A]
13.8010(10)
8.1146(7)
35.376(2)
90
11.888(3)
14.904(4)
14.905(4)
112.140(7)
102.331(7)
91.793(6)
2371.5(11)
2
7.5981(2)
12.5786(2)
21.1089(4)
82.7280(10)
88.1180(10)
80.7170(10)
1974.86(7)
2
˚
c [A]
a [8]
b [8]
g [8]
95.820(4)
90
˚
Volume [A ]
3
3941.3(5)
4
Z
ꢁ3
r
calcd [Mg m
]
1.541
1.566
1.605
ꢁ
1
m [mm
F(000)
]
8.536
1.495
1.519
1856
1128
960
3
Crystal size [mm ]
Range for data collection
Index ranges
0.13 ꢂ 0.11 ꢂ 0.02
3.22 to 60.00
ꢁ15 # h # 15
0.18 ꢂ 0.12 ꢂ 0.12
1.767 to 27.527
ꢁ15 # h # 15
ꢁ19 # k # 19
ꢁ19 # l # 19
24046
0.20 ꢂ 0.12 ꢂ 0.03
2.39 to 27.56
ꢁ9 # h # 9
ꢁ16 # k # 16
ꢁ27 # l # 27
43439
ꢁ
9 # k # 8
ꢁ39 # l # 39
Reflections collected
46266
Independent reflections
Max. and min. transmission
Data / restraints / parameters
5803 (Rint ¼ 0.0878)
0.8478 and 0.4033
5803 / 0 / 478
1.038
10655 (Rint ¼ 0.0365)
0.7456 and 0.6326
10655 / 0 / 559
1.051
9006 (Rint ¼ 0.0624)
0.9858 and 0.8325
9006 / 9 / 530
1.034
2
Goodness-of-fit on F
Final R indices [I . 2s(I)]
R indices (all data)
R1 ¼ 0.0442
wR2 ¼ 0.1104
R1 ¼ 0.0545
wR2 ¼ 0.1141
1.034 and ꢁ0.836
R1 ¼ 0.0401
R1 ¼ 0.0470
wR2 ¼ 0.0856
R1 ¼ 0.0591
wR2 ¼ 0.1131
R1 ¼ 0.0723
wR2 ¼ 0.0948
0.993 and ꢁ0.596
wR2 ¼ 0.1282
1.746 and ꢁ1.821
˚
Largest diff. peak and hole [eA
ꢁ3
]
The structure was solved by direct methods using SHELXTL
from systematic reflection conditions and statistical tests. The
structure was solved by direct methods using SHELXTL
[
34]
(
SHELXS).
molecule of 3b. One molecule was successfully modelled
disordered over two positions). The other molecule could not be
modelled so the electron density contribution was extracted with
Two CHCl molecules were found for each
3
[
(SHELXS). One molecule of CH Cl was present, however,
34]
2
2
(
was disordered and could not be successfully modelled. Thus,
the electron density contribution was extracted with the program
[35]
PLATON/SQUEEZE. Restraints were used to keep the bond
[
35]
the program PLATON/SQUEEZE.
Restraints were used to
keep the bond distances and thermal ellipsoids chemically
meaningful. Note that the formula and density reported in the
CIF file reflect the results using SQUEEZE. Non-hydrogen
atoms were refined with anisotropic thermal parameters.
Hydrogen atoms were placed in idealized positions and refined
using a riding model. The structure was refined (weighted least-
distances and thermal ellipsoids chemically meaningful. Non-
hydrogen atoms were refined with anisotropic thermal para-
meters. Hydrogen atoms were placed in idealized positions and
refined using a riding model. The structure was refined
(weighted least-squares refinement on F ) to convergence.
The absence of additional symmetry or voids was confirmed
[35]
using PLATON (ADDSYM).
2
[34]
2
[34]
squares refinement on F ) to convergence.
additional symmetry or voids was confirmed using PLATON
The absence of
[35]
(ADDSYM).
Crystallography D
A CH Cl solution of 4a was allowed to evaporate slowly at
2
2
Crystallography C
room temperature. After 1 day, the resulting red plates were
analyzed as outlined in Table3. Cell parameters were obtained
A CH Cl solution of 3c was allowed to evaporate slowly at
2
2
[
31]
room temperature. After 4 days, the resulting colourless plates
were analyzed as outlined in Table 1. Cell parameters were
obtained from 60 frames using a 0.58 scan. Integrated intensity
information for each reflection was obtained by reduction of the
data frames with the program APEX2. SADABS was used for
[
absorption corrections.
from 180 frames using a 0.58 scan.
information for each reflection was obtained by reduction of the
Integrated intensity
[
32]
data frames with the program APEX2. SADABS was used for
absorption corrections. The space group was determined
from systematic reflection conditions and statistical tests. The
structure was solved by direct methods using SHELXTL
[33]
[
32]
33]
The space group was determined

3
84
Z. Baranov a´ et al.
[
34]
(SHELXS).
A CH Cl molecule was found for nearly every
2
obtained free of charge via www.ccdc.cam.ac.uk/data_request/
cif (or from the Cambridge Crystallographic Data Centre
(CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax:
þ44(0) 1223 336033; email: deposit@ccdc.cam.ac.uk). Addi-
tional views of the crystal structures, experimental procedures,
and Cartesian coordinates are also provided as well as a
2
molecule of 4a (refined with an occupancy value close to 1).
Non-hydrogen atoms were refined with anisotropic thermal
parameters. Hydrogen atoms were placed in idealized positions
and refined using a riding model. The structure was refined
(weighted least-squares refinement on F ) to convergence.
The absence of additional symmetry or voids was confirmed
2
[34]
molecular structure file that can be read by the program
[22]
[
35]
using PLATON (ADDSYM).
Mercury
puted structures.
and contains the optimized geometries of all com-
38]
[
Crystallography E
A CHCl solution of 4b was allowed to evaporate slowly at room
3
Acknowledgements
temperature. After 3 days, the resulting red prisms were ana-
lyzed as outlined in Table 3. Cell parameters were obtained from
We thank the US National Science Foundation (grant nos CHE-1153085
and CHE-1566601) for support, the Laboratory for Molecular Simulation
and Texas A&M High Performance Research Computing, Mr Joseph S.
Villalpando and Mr Alex J. Kalin (undergraduate researchers) for the syn-
thesis of precursors, and Dr Tobias Fiedler for preparing the graphical
abstract.
[31]
6
0 frames using a 0.58 scan. Integrated intensity information
for each reflection was obtained by reduction of the data frames
[
32]
with the program APEX2.
SADABS was used for absorption
The space group was determined from system-
atic reflection conditions and statistical tests. The structure was
[
33]
corrections.
[
34]
solved by direct methods using SHELXTL (SHELXS).
CHCl molecules were located and refined for each molecule of
Two
References
3
[
1] C. J. Bruns, J. F. Stoddart, The Nature of the Mechanical Bond: From
Molecules to Machines 2017 (John Wiley & Sons, Inc.: Hoboken, NJ).
2] (a) J.-M. Lehn, Supramolecular Chemistry: Concepts and Perspec-
tives 1995 (VCH: Weinheim, Germany).
4
b. Non-hydrogen atoms were refined with anisotropic thermal
parameters. Hydrogen atoms were placed in idealized positions
and refined using a riding model. The structure was refined
[
2
weighted least-squares refinement on F ) to convergence.
[34]
(
The absence of additional symmetry or voids was confirmed
(b) J.-P. Sauvage, C. Dietrich-Buchecker (Eds), Molecular Catenanes,
Rotaxanes and Knots: A Journey Through the World of Molecular
Topology 1999 (Wiley-VCH: Weinheim, Germany).
[
35]
using PLATON (ADDSYM).
[
3] (a) T. J. Hubin, D. H. Busch, Coord. Chem. Rev. 2000, 200–202, 5.
doi:10.1016/S0010-8545(99)00242-8
(b) R. S. Forgan, J.-P. Sauvage, J. F. Stoddart, Chem. Rev. 2011, 111,
Crystallography F
5
434. doi:10.1021/CR200034U
c) L. F. Lindoy, K.-M. Park, S. S. Lee, Chem. Soc. Rev. 2013, 42,
713. doi:10.1039/C2CS35218D
d) N. H. Evans, P. D. Beer, Chem. Soc. Rev. 2014, 43, 4658.
doi:10.1039/C4CS00029C
e) G. Gil-Ram ´ı rez, D. A. Leigh, A. J. Stephens, Angew. Chem., Int.
A CH Cl solution of 4c was allowed to evaporate slowly at
2
room temperature. After 3 days, the resulting orange plates were
analyzed as outlined in Table 3. Cell parameters were obtained
2
(
1
(
[
31]
from 60 frames using a 0.58 scan.
Integrated intensity
information for each reflection was obtained by reduction of the
(
[
data frames with the program APEX2. SADABS was used for
32]
Ed. 2015, 54, 6110. doi:10.1002/ANIE.201411619 [Angew. Chem.
2015, 127, 6208 doi:10.1002/ange.201411619]
[4] (a) M. P e´ rez-Alvarez, F. M. Raymo, S. J. Rowan, D. Schiraldi, J. F.
[
33]
absorption corrections.
The space group was determined
from systematic reflection conditions and statistical tests. The
structure was solved by direct methods using SHELXTL
A disordered CH Cl molecule was found for
2 2
Stoddart, Z.-H. Wang, A. J. P. White, D. J. Williams, Tetrahedron
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Computations were performed using the Gaussian09 program
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(
1
(
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˚
˚
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7
(
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