A multi-component CuAAC 'click' approach to an exo functionalised pyridyl-1,2,3-triazole macrocycle: Synthesis, characterisation, Cu(I) and Ag(I) complexes

Article abstract of DOI:10.1080/10610278.2012.688126

A one-pot, multi-component CuAAC reaction was exploited for the safe generation of an exo alcohol-functionalised pyridyl-1,2,3-triazole click macrocycle in good yield. The macrocycle was characterised by elemental analysis, HR-ES-MS, ¹H and ¹³C NMR spectrometry, and the molecular structure was confirmed by X-ray crystallography. Efforts to use the click macrocycle in both passive and active metal template syntheses of [2]rotaxanes were unsuccessful, and this appears to be connected to the coordinating ability of the 1,2,3-triazole units in the macrocycle. The coordination chemistry of the macrocycle with Cu(I) and Ag(I) was examined. It has been demonstrated using HR-ES-MS, ¹H NMR spectrometry and X-ray crystallography that the macrocycle can form both discrete and polymeric coordination compounds with Cu(I) and Ag(I) and in all cases the 1,2,3-triazolyl units of the macrocycle are coordinated to the metal ions.

Full text of DOI:10.1080/10610278.2012.688126

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Supramolecular Chemistry
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A multi-component CuAAC ‘click’ approach to an exo
functionalised pyridyl-1,2,3-triazole macrocycle:
synthesis, characterisation, Cu(I) and Ag(I) complexes
Asif Noor a , James E.M. Lewis a , Scott A. Cameron a , Stephen C. Moratti a & James D.
Crowley a
a Department of Chemistry, University of Otago, P.O. Box 56, Dunedin, New Zealand
Version of record first published: 21 May 2012
To cite this article: Asif Noor, James E.M. Lewis, Scott A. Cameron, Stephen C. Moratti & James D. Crowley (2012): A multi-
component CuAAC ‘click’ approach to an exo functionalised pyridyl-1,2,3-triazole macrocycle: synthesis, characterisation,
Cu(I) and Ag(I) complexes, Supramolecular Chemistry, 24:7, 492-498
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Supramolecular Chemistry
Vol. 24, No. 7, July 2012, 492–498
A multi-component CuAAC ‘click’ approach to an exo functionalised pyridyl-1,2,3-triazole
macrocycle: synthesis, characterisation, Cu(I) and Ag(I) complexes
Asif Noor, James E.M. Lewis, Scott A. Cameron, Stephen C. Moratti and James D. Crowley*
Department of Chemistry, University of Otago, P.O. Box 56, Dunedin, New Zealand
(Received 11 March 2012; final version received 11 April 2012)
A one-pot, multi-component CuAAC reaction was exploited for the safe generation of an exo alcohol-functionalised
pyridyl-1,2,3-triazole ‘click’ macrocycle in good yield. The macrocycle was characterised by elemental analysis, HR-ES-
MS, 1H and 13C NMR spectrometry, and the molecular structure was confirmed by X-ray crystallography. Efforts to use the
‘click’ macrocycle in both passive and active metal template syntheses of [2]rotaxanes were unsuccessful, and this appears
to be connected to the coordinating ability of the 1,2,3-triazole units in the macrocycle. The coordination chemistry of the
1
macrocycle with Cu(I) and Ag(I) was examined. It has been demonstrated using HR-ES-MS, H NMR spectrometry and
X-ray crystallography that the macrocycle can form both discrete and polymeric coordination compounds with Cu(I) and
Ag(I) and in all cases the 1,2,3-triazolyl units of the macrocycle are coordinated to the metal ions.
Keywords: macrocycles; CuAAC; click; Ag(I); 1,2,3-triazole; pyridyl
Introduction
Efforts to use the ‘click’ macrocycle in both passive and
active metal template syntheses of [2]rotaxanes were
unsuccessful, and this appears to be connected to the
coordinating ability of the 1,2,3-triazole units within the
macrocycle. In addition, the coordination chemistry of this
newmacrocyclic‘click’ligandwithCu(I) andAg(I)hasbeen
examined, and it is shown that both discrete and polymeric
complexes involving 1,2,3-triazolyl units can be formed.
Pyridine-containing macrocycles continue to engender
great interest due to potential applications in catalysis (1),
molecular recognition (2, 3), biology (3, 4) and self-
assembly (5). One area in which the use of pyridine-
containing macrocycles has seen rapid development is the
synthesis of mechanically interlocked architectures (MIAs)
(6) and molecular machines (7). Pyridine macrocycles such
as 1 have been extensively used in both passive (8) and
active metal template (9) syntheses of MIAs (Figure 1).
However, the vast majority of this class of pyridine
macrocycles contain no additional functionality, making it
difficult to further elaborate the MIAs. As part of work
towards novel MIAs, we requiredpyridine macrocycles that
retained the core pyridine-binding motif of 1 but that also
contained functional exo substituents. The mild and
functional group tolerant Cu(I)-catalysed 1,3-cycloaddi-
tion of organic azides with terminal alkynes (10) (the
CuAAC reaction) has recently shown great potential as an
efficient, reliable method for the formation of macrocycles
(11), and as such we postulated that it may provide a facile
synthetic approach to the desired exo functionalised
pyridine macrocycles.
Results and discussion
Macrocycle synthesis
The pyridyl-1,2,3-triazole ‘click’ macrocycle, 2, was
synthesised from the dialkyne, 3 (12), and dibromide, 4,
precursors using a one-pot, multi-component CuAAC
method (Scheme 1) (13–15). The potentially explosive
diazide (required for the formation of 2) was generated
in situ by heating dibromide 4 (1 equiv.) and NaN3 (3 equiv.)
at 908C in DMF for 48 h. The resulting diazide (1 equiv.)
solution and an equimolar DMF solution of the dialkyne, 3,
were added dropwise slowly to a solution of CuSO4·5H2O,
Na2CO3 and ascorbic acid in DMF–water (4:1) over a
period of 16 h, resulting in a 30% yield of the macrocycle, 2.
The yield could be further improved by slowing the rate of
addition of diazide and dialkyne reagents. The use of a
syringe pump allowed 3 and 4 to be added to the
DMF–water (4:1) solution containing the Cu(I) catalyst
over a 48-h period, and this modification resulted in a
respectable 44% isolated yield of 2. The ‘click’ macrocycle
was characterised by 1H and 13C NMR spectroscopy,
Here, it is demonstrated that a one-pot, multi-component
CuAAC method can be used to safely generate an exo
functionalised pyridyl-1,2,3-triazole ‘click’ macrocycle (2,
Figure 1). The potentially dangerous diazide synthon is
generatedinsituthen capturedbycopper(I)acetylides, safely
providing the desired ‘click’ macrocycle in good yield.
*Corresponding author. Email: jcrowley@chemistry.otago.ac.nz
ISSN 1061-0278 print/ISSN 1029-0478 online
q 2012 Taylor & Francis
http://dx.doi.org/10.1080/10610278.2012.688126
http://www.tandfonline.com

Supramolecular Chemistry
493
N
N
O
O
O
N
O
N
1
2
N N
N N
O
O
O
O
n
OH
Figure 1. The pyridine-containing macrocycles 1 and 2. The
2,6-bis[(alkyloxy)methyl]pyridine macrocycle motif, 1, is
commonly used in the passive and active template syntheses of
MIAs. The CuAAC ‘click’ derived exo functionalised pyridyl-
1,2,3-triazole, 2, is a potentially readily synthesised surrogate of 1.
elemental analysis and HR-ES-MS, and the molecular
structurewas confirmed using X-ray crystallography. X-ray
quality crystals of 2 were obtained by vapour diffusion of
diethyl ether into an acetone solution of the macrocycle.
The molecular structure of the macrocycle (Figure 2) is
unremarkable but demonstrates that 2 contains a large,
flexible central cavity that should potentially enable its use
in the syntheses of MIAs using metal template strategies.
Figure 2. A labelled ORTEP diagram of the exo functionalised
pyridyl-1,2,3-triazole ‘click’ macrocycle, 2. The thermal
ellipsoids are shown at the 50% probability level. Selected
˚
atom distances (A) for 2; N2ZC25 7.819(6), N3ZN1 5.789(5).
Attempted active and passive metal template syntheses of
[2]rotaxanes using the pyridyl-1,2,3-triazole ‘click’
macrocycle
alkyne, 6 (2 equiv.) ‘stoppers’ were added to a CH2Cl2
solution containing [Cu(CH3CN)4](PF6) (1 equiv.), and the
resulting reaction mixture was stirred at room temperature
(Scheme 2). The ‘click’ reaction was monitored using TLC
and HR-ES-MS and proceeded to completion after 48h.
However, no trace of the interlocked product, 8, could be
detected and only the non-interlocked linear thread, 7, and
macrocycle could be recovered from the reaction mixture. In
an attempt to drive the formation of the [2]rotaxane, 8, the
reaction was repeated using an excess (4 equiv.) of the azide
and alkyne stoppers. Once again the ‘click’ reaction
proceeded to completion but only non-interlocked linear
thread, 7, and macrocycle, 2, could be detected in the
reaction mixture. Somewhat surprisingly, despite the
structural similarity of the ‘click’ macrocycle, 2, to 2,6-
bis[(alkyloxy)methyl]pyridine macrocycle, 1, no rotaxanes
are formed under CuAAC active metal template conditions;
this lack offormation of the expected MIA may be explained
if the complexation of Cu(I) to the macrocycle is weak and
therefore the metal ion does not direct the CuAAC reaction
through the cavity of the macrocycle. Thus, we examined the
complexation of Cu(I) and, the larger but isoelectronic,
Ag(I) ions with the ‘click’ macrocycle using 1H NMR and
HR-ES-MS experiments (Scheme 3). HR-ES-MS exper-
iments on 1:1 mixtures of either [Cu(CH3CN)4](PF6)
(1 equiv.) or AgOTf (1 equiv.) and macrocycle, 2 (1 equiv.),
As the parent 2,6-bis[(alkyloxy)methyl]pyridine macro-
cycle, 1, has been successfully exploited to synthesise
[2]rotaxanes and [3]rotaxanes using the CuAAC active
metal template method (16, 17), we set out to use the same
approach to synthesise the alcohol-functionalised [2]rotax-
ane, 8. The macrocycle, 2 (1 equiv.), azide, 5 (2 equiv.) and
a
b
c
N
Br
Br
O
O
N
d
N
e
f
O
O
N
N N
O
O
2
(i)
N N
g
h
OH
i
O
O
3
4
j
k
OH
l
Scheme 1. The one-pot, multi-component CuAAC synthesis of
the exo functionalised pyridyl-1,2,3-triazole ‘click’ macrocycle,
2; (i) (a) 4, NaN3 (3 equiv.), DMF, 908C, 48 h, (b) 3,
CuSO4·5H2O, ascorbic acid, Na2CO3, DMF–H2O (4:1), RT,
48 h.

494
A. Noor et al.
N
N
N
O
O
7
N
O
O
N
O
N
N3
(i)
5
2
N N
N N
N
O
N
O
N
O
O
O
N
6
N
N
N N
N N
O
O
OH
8
O
O
OH
Scheme 2. Attempted CuAAC active metal template rotaxane synthesis using the exo functionalised pyridyl-1,2,3-triazole ‘click’
macrocycle, 2; (i) [Cu(CH3CN)4](PF6) (1 equiv.), CH2Cl2, RT, 48 h.
displayed prominent peaks due to metal ion complexation at
m/z ¼ 584 [2 þ Cu]þ or 628 [2 þ Ag]þ along with weak
peaks at m/z ¼ 522 [2 þ H]þ and 544 [2 þ Na]þ, suggesting
that the ‘click’ macrocycle forms stable complexes with
these metal ions. 1H NMR spectra of the 1:1 mixtures were
also indicative of metal ion complexation with large
downfield shifts observed for the pyridyl protons Ha and
Hb. A similar shift was observed for the He proton of the
macrocycle, suggesting that the 1,2,3-triazole units are
involved in the metal ion complexation (Figure 3 and
Supporting Information). The 1H NMR and HR-ES-MS data
are consistent with ‘click’ macrocycle, 2, acting as a
tridentate chelating ligand and this binding mode was
confirmed by X-ray crystallography. X-ray quality crystals
of the AgOTf complex (9b) were obtained by vapour
diffusion of diethyl ether into a methanol solution of the
silver(I) macrocycle complex (Figure 4). The macrocycle, 2,
acts as a tridentate chelate ligand complexing the silver(I)
ions through its pyridyl and 1,2,3-triazolyl donor units in a
trigonal-planar coordination mode (Figure 4). Although
a
(X)
b
c
N
N
O
N
O
N
O
N
O
N
d
M
(i or ii)
e
f
2
N N
N N
N N
N N
g
h
i
O
O
O
O
j
k
OH
OH
l
9a (M = Cu(I), X = PF6–)
9b (M = Ag(I), X = OTf–)
Scheme 3. Synthesis of Cu(I) and Ag(I) metal complexes of 2;
(i) [Cu(CH3CN)4](PF6) (1 equiv.), CH2Cl2, RT, 1 h, or (ii) AgOTf
(1 equiv.), CH2Cl2, RT, 1 h.
Figure 3. Partial 1H NMR spectra (400 MHz, CD2Cl2, 300 K) of
(a) macrocycle 2, (b) Ag(I) complex 9b. The assignments
correspond to the lettering shown in Scheme 3.

Supramolecular Chemistry
495
coordination mode when coordinated to 2. These obser-
vationsprovide arationaleforthelackofrotaxaneformation
with2 undertheCuAACactivemetaltemplateconditions. If
2 forms a strong tridentate complex with Cu(I), it lacks the
vacant coordination sites necessary to bind both azide and
alkyne required for the CuAAC active metal template
reaction to proceed. A similar lack of reactivity in the
CuAAC active metal template reaction has been observed
previously with other tridentate macrocycles (16).
Ag(I) complexes are known to be coordinatively
flexible and are readily able to interact with two to six
ligands (21). Furthermore, close inspection of the
molecular structure of 9b suggested that a suitably designed
ligand could potentially coordinate to and thread through
the centre of the tridentate silver(I) macrocycle complex to
form a pseudorotaxane architecture (SPARTAN Molecular
Models, Supporting Information). Based on this we
reasoned that 9b could potentially be used to synthesise
[2]rotaxane 12 using a [3 þ 1] (22) passive template
approach (Scheme 4). The silver(I) complex, 9b (1 equiv.),
and pyridyl dialkyne ligand, 3 (1 equiv.), were added to
CH2Cl2, and the resulting reaction mixture was stirred at
room temperature for 1 h (Scheme 4). The azide stopper
(2.5 equiv.) 5, [Cu(CH3CN)4](PF6) (1 equiv.) and tris(ben-
zyltriazolylmethyl)amine (TBTA 1 equiv.) were added to
the CH2Cl2 solution containing 10, and the ‘click’ reaction
was monitored using TLC and HR-ES-MS. However, as
with the CuAAC active metal template method, the [3 þ 1]
passive template approach (Scheme 4) only resulted in the
formation of the non-interlocked linear thread, 11, in
stoichiometric yield, with no trace of the interlocked
product [2]rotaxane, 12, detected in the reaction mixture.
There are two potential reasons for the failure of the
[3 þ 1] passive template approach to the [2]rotaxane, 12: (1)
the silver(I)-pyridine interaction is known to be very labile;
thus, the CuAAC ‘click’ reaction may occur on uncoordi-
nated 3 leading to the non-interlocked linear thread, 11, or
(2) the pyridyl dialkyne ligand, 3, has not threaded through
the cavity of the silver(I) macrocycle complex to form the
required pseudorotaxane architecture that would lead to
capture of the mechanical bond. The 1H NMR spectrum of a
1:1 mixture of 9b and 3 (CD2Cl2, Supporting Information)
indicates that the pyridyl dialkyne ligand, 3, coordinates to
the silver(I) macrocycle complex, 9b. However, HR-ES-MS
experiments only display prominent peaks due to a silver(I)
pyridyl dialkyne ligand adduct (m/z ¼ 322 [3 þ Ag]þ) and
the silver(I) macrocycle complex (m/z ¼ 628 [9b]þ). No ion
due to the [9b þ 3]þ complex could be detected suggesting
that any interaction between silver(I) ‘click’ macrocycle
complex, 9b, and the pyridyl dialkyne ligand, 3, is weak.
Vapour diffusion of diethyl ether into a methanol solution
containing a 1:1 mixture of 9b and 3 provided X-ray quality
crystals. However, the molecular structure was not the
expected pseudorotaxane 10, in fact the crystals contained
none of the pyridyl dialkyne ligand, 3. Under these
Figure 4. A labelled ORTEP diagram of ‘click’ macrocycle
silver(I) triflate complex, 9b. The thermal ellipsoids are shown at
the 50% probability level. The solvent molecules and counter ions
˚
have been omitted for clarity. Selected bond lengths (A) and
angles (8) for 9b; Ag1ZN7 2.245(2), Ag1ZN3 2.265(2), Ag1ZN4
2.303(2), Ag1ZO4 2.843(2), Ag1ZO5 2.923(2), N7ZAg1ZN3
122.87(8), N7ZAg1ZN4 116.25(8), N4ZAg1ZN3 120.77(8).
1,2,3-triazolyl coordination chemistry is now well docu-
mented in the literature (18), this coordination environment
was somewhat unexpected as it leads to the formation of the
rather rare 8- and 18-membered chelate rings. The 1,2,3-
triazolyl units are coordinated to the silver(I) ion through the
more electron-rich N3 nitrogen and the AgZN distances
(Ag1ZN7 2.245(2), Ag1ZN3 2.265(2), Ag1ZN4 2.303(2))
are consistent with those previously observed for non-
macrocyclic Ag(I) pyridyl-1,2,3-triazole complexes (14, 15,
19). The ether oxygen atoms of the macrocycle could also
potentially coordinate to the Ag(I) ions but the AgZO
˚
distances (Ag1ZO4 2.843(2), Ag1ZO5 2.923(2) A) are
outside the range that would normally constitute a bonding
interaction. In the extended crystal structure, the [(2)Ag]þ
cations form a 1D slip stack (Supporting Information)
that is supported by weak CZHZN hydrogen bonding
interactions (15, 20) between neighbouring 1,2,3-triazolyl
˚
units (H23ZN2, 2.695(3), C23ZN2 3.372(4) A,
C23ZH23ZN2 128.8(2)8, H11ZN6, 2.794(2), C11ZN6
˚
3.383(2) A, C11ZH11ZN2 121.0(2)8). There is no evidence
of stabilising Ag(I)ZAg(I) interactions (the shortest
˚
Ag(I)ZAg(I) distance is 6.0188(4) A).
We have been unable to generate X-ray quality crystals
of the analogous Cu(I) complex (9a), but on the basis of the
1
similar H NMR and HR-ES-MS data the copper(I) ion
presumably adopts a similar tridentate, trigonal-planar

496
A. Noor et al.
N
O
N
O
N
Ag
(ii)
(i)
9b+3
N N
N N
N
O
O
O
O
10
OH
N
O
O
O
N
N
N
N
N
O
N
11
+
N
O
N
O
N
N N
O
N N
O
N
O
N
N
N
N
N
O
N
O
O
12
OH
Scheme 4. Attempted [3 þ 1] passive metal template rotaxane synthesis using the exo functionalised pyridyl-1,2,3-triazole ‘click’
macrocycle, 2; (i) CH2Cl2, RT, 1 h, (ii) [Cu(CH3CN)4](PF6) (2.2 equiv.), tris(benzyltriazolylmethyl)amine (TBTA), (1 equiv.), azide
stopper 5 (2.5 equiv.), CH2Cl2, RT, 48 h.
crystallisation conditions, a coordination polymer between
AgOTfandthe‘click’macrocycle, 2, isformed(Figure5(a)).
There are two different silver(I) coordination environments
in the coordination polymer; one silver(I) ion (Ag2) is
sandwiched between two ‘click’ macrocycles and coordi-
nated to four 1,2,3-triazolyl nitrogen atoms (two from each
macrocycle) in a distorted tetrahedral arrangement
(t4 ¼ 0.89) (23) forming a [(2)2Ag]þ cation (Figure 5(b)).
Each one of these sandwiched cations is linked to a
neighbouring [(2)2Ag]þ unit by a second silver(I) ion (Ag1).
This silver ion is coordinated to two pyridyl units (one from
each adjacent macrocycle) in a linear fashion linking
adjacent [(2)2Ag]þ cations and generating the coordination
polymer (Figure 5(a)). Two ether oxygen atoms make close
contacts to Ag1 (Ag1ZO4 2.586(4), Ag1ZO34 2.631(4)),
but the coordination environment is best described as linear
two coordinate (N4ZAg1ZN34 179.4(2), Figure 5(c)) –
a motif that is common in Ag(I)-pyridyl complexes (21).
Based on the observed results, we postulate that the lack of
templation to form the desired [2]rotaxane using the [3 þ 1]
passive template approach is connected to both the lability of
the Ag(I)–pyridyl interactionand the coordinative flexibility
of the ‘click’ macrocycle 2.
Conclusion
It has been demonstrated that a one-pot, multi-component
CuAAC method can be used to safely generate an exo
functionalised pyridyl-1,2,3-triazole ‘click’ macrocycle (2)
in good yield. Efforts to use the ‘click’ macrocycle in both
passive and active metal template syntheses of [2]rotaxanes
were unsuccessful, and this appears to be connected to
the coordinating ability of the 1,2,3-triazolyl units in the
macrocycle. Two different silver(I) triflate complexes of the
‘click’ macrocycle were characterised using single crystal
X-ray diffraction. The coordination chemistry of the ‘click’

Supramolecular Chemistry
497
architectures needs to be carefully designed in order to
enable the desired templation effects. Efforts towards these
types of ‘click’ macrocycles are now underway.
Supporting information
Full experimental details, molecular models, spectro-
scopic and crystallographic data are available free of
charge via the Internet at http://pubs.acs.org. The CIF files
for the compounds have been deposited with the
Cambridge Crystallographic Data Centre (CCDC 871005
- 871007). These data may be obtained free of charge on
request from the CCDC, 12 Union Road, Cambridge CB2
1EZ, UK. Tel: þ44-1233-336408; Fax: þ44-1233-
336033; E-mail: deposit@ccdc.cam.uk.
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˚
bond lengths (A) and angles (8) for silver(I) triflate 2 coordination
polymer; Ag1ZN4 2.197(5), Ag1ZN34 2.186(5), Ag2ZN3
2.422(4), Ag2ZN5 2.289(5), Ag2ZN33 2.349(5), Ag2ZN35
2.272(5), Ag1ZO4 2.586(4), Ag1ZO34 2.631(4), N4ZAg1ZN34
179.4(2), N3ZAg2ZN5 93.3(3), N3ZAg2ZN33 91.4(2),
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