Threading of various 'U' shaped bidentate axles into a heteroditopic macrocyclic wheel: Via NiII/CuII templation

Article abstract of DOI:10.1039/c7dt00699c

The threading of 'U' shaped bent axles having diverse functionalities (Axle1-Axle10) is investigated by using a heteroditopic amido-amine macrocyclic (MC) wheel via Ni^II or Cu^II metal ion templation. These bent shaped axles are the derivatives of 4,4′-substituted 2,2′-bipyridine, which are composed of various terminal groups like alkene, alkyne, bromide, hydroxyl and azide. Such metallo [2]pseudorotaxanes are well characterised by ESI-MS, EPR and FT-IR spectroscopic studies, UV-Vis absorption studies, elemental analysis and single-crystal X-ray diffraction studies wherever possible. Experimental evidence supports 1:1:1 ternary complexation between MC, the metal ion and axle. The single crystal X-ray structures of three Cu^II templated ternary complexes (PR1′, PR3′ and PR7′) show the penta-coordination arrangement around the templating metal ion. Interestingly, judicious selection of chemical functionalities in the complementary wheel and axle components enables to show the existence of various covalent and non-covalent interactions.

Full text of DOI:10.1039/c7dt00699c

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Threading of various ‘U’ shaped bidentate axles into a
heteroditopic macrocyclic wheel via NiII/ CuII
templation
Mandira Nandi, Saikat Santra, Bidyut Akhuli, Pradyut Ghosh
*
Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, 2A & 2B
Raja S. C. Mullick Road, Kolkata 700032, India.
Eꢀmail: icpg@iacs.res.in
Abstract
Threading of ‘U’ shaped bent axles having diverse functionalities (Axle1ꢀAxle10) is investigated
by using a heteroditopic amidoꢀamine macrocyclic (MC) wheel via NiII or CuII metal ion
templation. These bent shaped axles are the derivatives of 4, 4' substituted 2, 2' bipyridine, which
are composed of various terminal groups like alkene, alkyne, bromide, hydroxyl and azide. Such
metallo [2]pseudorotaxanes are well characterised by ESIꢀMS, EPR and FTꢀIR spectroscopic
studies, UVꢀVis absorption studies, elemental analysis and Singleꢀcrystal Xꢀray diffraction
studies wherever possible. Experimental evidences support 1:1:1 ternary complexation between
MC, metal ion and axle. The single crystal Xꢀray structures of three CuII templated ternary
complexes (PR1', PR3' and PR7') show the pentaꢀcoordination arrangement around the
templating metal ion. Interestingly, judicious selection of chemical functionalities in the
complementary wheel and axle components enables to show the existence of various covalent
and non covalent interactions.

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Introduction
In the field of supramolecular chemistry, pseudorotaxanes are considered as a primary building
block to construct mechanically interlocked molecules (MIM’s)1 such as rotaxanes,2 and
catenanes3 which attract enormous research interest owing to their potential applications in the
various fields.4 These building blocks are constructed via different templation strategies such as
cation/ anion,5 hydrogen bonding,6 πꢀπ stacking,7 and halogen bonding8 interactions. However,
use of metal ion as a template is one of the popular approaches to synthesize multiꢀfunctional
pseudorotaxanes through the involvement of [2+2], [3+1], [3+2] or [3+3] orthogonal sets of
ligands.4b, 9 In this context over the last few years, Sauvage and coꢀworkers have extensively
utilised CuI as templating agent to develop multifunctional mononuclear/ multinuclear
pseudorotaxanes by using bidentate chelating unit containing wheel and axle components ([2+2]
donor sets).10 On the other hand, Leigh et al. has explored PdII metal ion templated threaded
architectures11 based on pyridine and bisꢀamide functionalised macrocylic wheel ([3+1] donor
sets). Moreover, CuII,12 NiII,12 ZnII,12ꢀ13 FeII,14 RuII,15 RhII,16 CoIII,11b, 16 AuI 5f have also been
explored as templates to construct threaded assemblies upon judicious choice of complimentary
wheel and axle units. Generally, pseudorotaxanes having linear axles are preferred to synthesise
rotaxanes,17 whereas bent shaped threaded axles are utilised as a potential candidate towards the
development of catenanes via threading followed by clipping method.18 Recently, our group has
reported multiꢀfunctional [2]pseudorotaxanes and [2]rotaxanes by using heteroditopic
macrocyclic wheels and various linear rod shaped axles derived from 5, 5' dimethyl 2, 2'
bipyridine precursor.17c, 19 In this regard, our interest is to develop bent shaped axles based
threaded assemblies that can be used as a precursor to construct interlocked systems like
catenane with multiple functionalities. Thus, it would be advantageous to explore the derivatives

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of 4, 4' substituted 2, 2' bipyridine with various chemical functionalities in the axle backbone to
introduce versatilities within the threaded assemblies. Herein, we report NiII and CuII templated
threading of a series of relatively uncommon ‘U’ shaped axles based on the derivatives of 4, 4'
dimethyl 2, 2' bipyridine in the amidoꢀamine macrocyclic wheel to develop two new generation
of [2]pseudorotaxanes through [3+2] metal ion chelation assisted by other nonꢀcovalent
interactions .
Result and discussion
Axle designing aspects
4, 4' dimethyl 2, 2' bipyridine (Axle1) and its derivatives (Fig. 1) are chosen as the ‘U’ shaped
axles to coordinate with the metalloꢀmacrocycle complexes of MC via [3+2] orthogonal mode of
orientation where tris and bis chelation are satisfied by the wheel and axle components
respectively. Threaded axles having alkene,10c, 18b alkyne,18c hydroxyl,18c, 20 halide,21 or azide3a, 18c
terminal groups are well known to act as a precursor for the clipping reactions to develop
Fig. 1 Chemical structure of MC and ‘U’ shaped bidentate axles (Axle1 ꢀ Axle10)

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catenated structures hence, we have designed a series of amide/ester functionalised bipyridine
axles by incorporating (i) bromide (Axle3), (ii) alkyne (Axle4, Axle6), (iii) alkene (Axle5) (iv)
hydroxyl (Axle8), (v) azide (Axle9), and (vi) aromatic (Axle10) unit termini.
(a) General procedure for the synthesis of ‘U’ shaped bidentate axles
Axle3, Axle4, Axle8, Axle9, Axle10 are synthesised in moderate yields by following Scheme 1A
whereas Axle5 and Axle6 are synthesised according to Scheme 1B by using 4, 4' dimethyl 2, 2'
bipyridine (Axle1) as a starting material. 4, 4' dimethyl 2, 2' bipyridine is reacted with K2Cr2O7
Scheme 1A and 1B. Synthetic route for the synthesis of Axle1 ꢀ Axle10

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H2SO4 to synthesise 4, 4' diacid 2, 2' bipyridine (BPy4COOH) followed by reaction with SOCl2,
Et3N and respective chemical precursors to afford different bidentate axles. BPy4COOH, Axle2
and Axle7 are synthesised by following the literature procedure.22 All the axles are characterized
1
by usual spectroscopic methods such as ESIꢀMS, H NMR, 13C NMR and FTꢀIR (Fig. 1S ꢀ 28S,
ESI†) studies. The details of synthetic procedures and characterization are presented in the
experimental section and in the supporting information.
(b) General procedure for the synthesis of [2]pseudorotaxanes (PR1 ꢀ PR10, PR1'ꢀ PR10')
Scheme 2 shows the ternary complex formations upon treatment of respective axles (Axle1ꢀ
Axle10) in the stirring solution of corresponding metallo ꢀ macrocycle complexes (MCꢀNiII,
Scheme 2. Synthesis of NiII and CuII templated [2]pseudorotaxanes with their corresponding
abbreviations.

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MCꢀCuII) in a DCMꢀMeOH binary solvent mixture. NiII templated and CuII templated
[2]pseudorotaxanes are isolated as greenishꢀyellow and blue colour solid upon evaporating the
solvent and successive washing with DCM. Threaded ternary complexes are characterized by
ESIꢀMS, EPR, FTꢀIR and UVꢀVis spectroscopic studies, elemental analysis and single crystal Xꢀ
Ray diffraction studies (wherever possible). The details of synthetic procedures and
characterization are described in the experimental section and supporting information.
ESIꢀMS studies
Electrospray ionisation (ESIꢀMS) analysis is carried out to characterise [2]pseudorotaxanes (PR1
ꢀ PR10 and PR1' ꢀ PR10'). ESIꢀMS spectra of PR1, PR5, PR7, PR2', PR6' and PR8' are
(c)
(b)
(a)
(f)
(e)
(d)
Fig. 2 ESIꢀMS spectra of (a) Axle1 vs MCꢀNiII (PR1), (b) Axle5 vs MCꢀNiII (PR5), (c) Axle7 vs
MCꢀNiII (PR7), (d) Axle2 vs MCꢀCuII (PR2'), (e) Axle6 vs MCꢀCuII (PR6'), (f) Axle8 vs MCꢀCuII
(PR8') templated [2]pseudorotaxanes.

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shown in Fig. 2 and rest of the ESI ꢀ MS spectra are presented in the supporting information (Fig.
29Sꢀ48S, ESI†). The inset pictures show merging of isotopic pattern with the experimental
pattern (Fig. 2, 29Sꢀ48S, ESI†). In each of the NiII templated ESIꢀMS, Axle1 ꢀ Axle10 threaded
ternary complexes show molecular ion peak at m/z 872.3, 988.3, 1148.1, 1008.2, 1236.5, 1231.4,
1013.3, 1047.3, 1069.3, 1110.3 respectively that correspond to single charged ([MCꢀNiꢀAxleXꢀ
ClO4]+) (X = 1 ꢀ 10) species. Similarly, CuII templated heteroleptic complexes (PR1' ꢀ PR10')
show respective signature peaks at m/z 877.3, 993.3, 1151.1, 1013.2, 1242.4, 1237.5, 1018.3,
1050.3, 1072.3, 1115.3 which also reveal the existence of single charged species ([MCꢀCuꢀXꢀ
ClO4]+) (X = 1 ꢀ 10). In each case isotopic distribution pattern shows good agreement with the
experimental pattern, which supports the involvement of 1:1:1 MC, metal and corresponding
bidentate axles.
EPR Studies
Fig. 3 Simulated Xꢀband EPR spectra of PR1', PR5', PR7' and PR9' at 80K.

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CuII templated [2]pseudorotaxanes (PR1' ꢀ PR10') show well resolved X band EPR spectrum at
80K. X band EPR spectra of PR1', PR5', PR7', PR9' are presented in Fig. 3 and other spectra
are given in supporting information (Fig. 49S, ESI†). The EPR spectra of the CuII templated
pseudorotaxanes are found to be anisotropic in nature as depicted by comparing with the
simulated EPR spectra (dotted line), as given in Figure 3. However, all of the X band EPR
spectra data show the pattern with g|| > g⊥ invariably in all cases, which indicates a pentaꢀ
coordinated distorted square pyramidal geometrical arrangement around CuII metal centre upon
coordination of MC and axles in threaded complexes.19b, c
Absorption spectroscopic Studies
Absorption spectroscopic studies are carried out to investigate the binding efficiency of ‘U’
shaped axles (Axle1 ꢀ Axle10) with the metalloꢀmacrocycle complexes in heteroleptic fashion.
Binding stoichiometry of the ternary complexes and the association constant values are evaluated
via titration experiments. A similar spectral feature is observed in all of the titration experiments.
Titrations are performed in binary solvent mixtures (CH3CN ꢀ DMF/ DMSO) (9:1 v/v) by using
bidentate axles as host and MCꢀNiII complex as guest. However, UVꢀVis spectra of the bidentate
ligands (host) in CH3CN show absorption peak maxima (initial λmax) in the range of 280 nm ꢀ
300 nm that corresponds to n ꢀ π* transition. With the gradual addition of the guest (MCꢀNiII)
into the solution of bidentate axles, absorption peak is red shifted and a new absorption peak
(final λmax) is generated upon complex formation between axles and MCꢀNiII (Table 1).
However, it is shown from the Table 1 that initial λmax values in cases of PR2 ꢀ PR10 are quite
similar as well as the final λmax values also remain in close proximity. But, only in case of PR1
the initial and also the final λmax values differ from those above mentioned λmax values. Such
difference could be attributed to the nature of substituents on bipyridyl moiety, i.e. in PR1 only

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methyl substitution is present in the axle, whereas in PR2ꢀPR10 ester or amide functionalities
along with different substituents are involved. During titration, a single isosbestic point is
(d)
(a)
(e)
(f)
(b)
(c)
(g)
(j)
(k)
(l)
(h)
(i)
Fig. 4 (i) UVꢀVis titration profile of (a) Axle3 (6
10ꢀ5) vs. MCꢀNiII complex (6.2 10ꢀ4), (g) Axle8 (6.0
10ꢀ4), (j) Axle10 (6.0 10ꢀ5) vs. MCꢀNiII complex (6.2 10ꢀ4); (ii) corresponding 1:1
X
10ꢀ5) vs. MCꢀNiII complex (6.5
X
10ꢀ4) (d)
Axle6 (6.0
X
X
X
10ꢀ5) vs. MCꢀNiII complex
(6.2
X
X
X
equivalence plot (b, e, h and k); (iii) nonꢀlinear 1:1 curve fitting of (c, f, i and l) absorption
titration data.
observed in nꢀπ* region in all cases, that reveals the existence of single equilibrium for every NiII
templated ternary complexation (Fig. 4, 50S, ESI†). Further, the equivalence plot analysis (Fig.

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4, 50S, ESI†) clearly indicates the formation of 1:1:1 ternary complexes in solution state. Nonꢀ
linear 1:1 curve fitting method (Fig. 4 and Fig. 51S, ESI†) is utilised to evaluate the association
constant values (Ka) for each of the ternary complex formation, which are within the range of
2.37
X X
104 ꢀ 8.70 104 Mꢀ1. For each of the PR1 ꢀ PR10 ternary complexes λmax, association
constant (Ka), molar extinction coefficient (ε) and free energy of complexation (∆G°) values are
tabulated in Table 1.
Table 1. λmax values, isosbestic point, molar extinction coefficient (ε), association constant (Ka)
and free energy change values (∆G0) obtained from absorption spectroscopic data for PR1ꢀ
PR10 at 298K.
Ternary
Initial
λmax
(nm)
Final
λmax
(nm)
Isosbestic Molar extinction
Ka
∆G°
complexesa
point
(nm)
coefficient, ε
(Mꢀ1)b
(Kcal.Mꢀ1)
at 298K
(L molꢀ1 cmꢀ1)c
280
297
298
298
297
297
292
292
292
292
304
323
323
324
323
323
323
320
319
321
293
309
309
309
309
309
307
304
304
305
9.29 × 103
1.29 × 104
1.21 × 104
9.97 × 103
1.50 × 104
1.29 × 104
1.17 × 104
1.12 × 104
1.19 × 104
1.29 × 104
2.37× 104
4.26 × 104
4.14 × 104
3.76 × 104
8.70 × 104
6.97 × 104
4.08 × 104
4.34 × 104
6.70 × 104
6.68 × 104
ꢀ6.00
ꢀ6.35
ꢀ6.34
ꢀ6.28
ꢀ6.78
ꢀ6.65
ꢀ6.33
ꢀ6.36
ꢀ6.62
ꢀ6.62
PR1
PR2
PR3
PR4
PR5
PR6
PR7
PR8
PR9
PR10
a For PR1 ꢀ PR8 threaded complexes absorption titration are performed in CH3CN ꢀ DMF mixture and PR9 ꢀ PR10 complexes
titrations are obtained in CH3CN ꢀ DMSO mixture.
b Errors are estimated to be approximately less than 10% for association constant values calculated from nonꢀlinear 1:1 curve
fitting.

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c Molar extinction coefficient values are evaluated in n ꢀ π* transition region.
On the other hand, our previous report has shown that, the absorption peak maxima of MC ꢀ CuII
complex appeared at 600 nm in CH3CN, which corresponds to the dꢀd transition. At present
studies, each of the UVꢀVis spectra of the isolated 1:1 (MCꢀCuII : axle) CuII templated ternary
complexes (1
X
10ꢀ3) show absorption peak maxima (λmax ) in the range of 630 nm to 660 nm
(Fig. 5, 52S, ESI†), which indicates the red shifting of the previous absorption peak from 600 nm
(a)
(b)
(c)
Fig. 5 UVꢀVis spectra of PR2' (1
X
10ꢀ3 M), PR5' (1
X
10ꢀ3 M) and PR8' (1
X
10ꢀ3 M) in CH3CN.
upon 1:1 ternary complexes formation (PR1' ꢀ PR10'). However, in case of only Axle1 threaded
10ꢀ2 M
10ꢀ3 M), in which
ternary complex (PR1'), the binding stoichiometry is monitored upon titration of 1.06
solution of corresponding axle (guest) with the MCꢀCuII (host) complex (1
X
X
1:1 equivalence plot shows complete 1:1:1 ternary complexation (MC : CuII : Axle1) with λmax
and isosbestic point values at 668 nm and 649 nm (Fig. 53S, ESI†) respectively. But, our
repeated attempts to carry out the UVꢀVis absorption titration between MCꢀCuII and other axles
(Axle2 ꢀ Axle10) remain unsuccessful due to appearance of precipitate in higher order of
concentration under experimental condition. For each of the CuII threaded ternary complexes λmax
values and molar extinction coefficient values (ε) are tabulated in Table 2. Thus, absorption
spectroscopic studies in solution state for both NiII and CuII templated [2]pseudorotaxanes

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supports the formation of 1:1 ternary heteroleptic single complexation between the bidentate
axles and metalloꢀmacrocycle complexes.
Table 2. λmax values and molar extinction coefficient (ε) (L molꢀ1 cmꢀ1) values for PR1' ꢀ PR10'
at 298K.
Ternary
λmax
Molar extinction
Ternary
λmax
Molar extinction
coefficient Ɛ
complexesa
coefficient ε
complexesa
(nm)
(nm)
(L molꢀ1 cmꢀ1)b
2.24 × 102
3.14 × 102
3.57 × 102
3.14 × 102
3.69 × 102
(L molꢀ1 cmꢀ1)b
3.31 × 102
3.53 × 102
3.75 × 102
3.50 × 102
3.32× 102
668
629
631
631
635
629
641
645
643
648
PR1'
PR2'
PR3'
PR4'
PR5'
PR6'
PR7'
PR8'
PR9'
PR10'
a
absorption spectroscopic studies are performed in CH3CN
c Molar extinction coefficient values are evaluated in dꢀd transition region.
Single Crystal Xꢀ Ray analysis
Single crystals suitable for XꢀRay crystallographic analysis, are isolated for CuII templated PR1',
PR3' and PR7' threaded complexes. Block size greenish PR1' and PR3' crystals are obtained by
ꢀ
slow evaporation of CH3CN by using ClO4 as the counter anion whereas crystal of PR7' is
ꢀ
ꢀ
found by slow evaporation of DMF ꢀ CH3CN mixture by exchanging ClO4 anion with PF6
counter anion. All the crystals are generated after several weeks of crystallization from the
multiple data sets of crystals. Thermal ellipsoid model of all the crystal structures (Fig. 6)
indicate the complete threading of ‘U’ shaped axles into the MC via 1:1:1 (MC: metal ion: axle)
complex formation followed by [3+2] orthogonal orientation. Due to the poor crystal quality and

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(a)
(b)
(c)
Fig. 6 Thermal ellipsoids model of the (a) PR1', (b) PR3' and (c) PR7' single Xꢀ Ray crystal
structures at the 50% probability level. Hydrogen atoms, solvent molecules and anions have
been removed for clarity.
low resolution these values should be discussed with the greatest care, and we abstain from a
more detailed discussion of structural parameters. Detailed crystallographic details of all the
crystal structures are given in supporting information (Fig. 74Sꢀ75S, Table S1ꢀS6, ESI†).
Conclusions
In conclusion, we have successfully demonstrated the threading of ‘U’ shaped axles having
diverse chemical functionalities, into a bis (amido) tris (amine) wheel (MC) assisted by NiII or
CuII as templating metal ion. Consequently, the characterization studies confirm the suitability of
heteroditopic MC towards the bent ‘U’ shaped bidentate axles to construct [2]pseudorotaxanes
via [3+2] ternary complex formation. We envisage that these [2]pseudorotaxanes would act as
precursors towards the development of catenated structures with multiple functionalities which
can be easily be derivatised in different direction for the generation of new smart materials.
Presently, we are focusing on the development of interlocked systems having complex
functionalities by suitably choosing ‘U’ shaped axle and complementary heteroditopic wheel.

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Experimental Section
Materials and methods
All the starting materials 4, 4'ꢀDimethylꢀ2, 2'ꢀBipyridine, 10ꢀ undecene ꢀ1ꢀol, 10ꢀundecynꢀ1ꢀol,
3ꢀaminoꢀ1ꢀpropanol, 2bromoethanol, benzylamine, propargyl alcohol, nꢀpropylamine,
Ni(ClO4)2.6H2O, Cu(ClO4)2.6H2O, and deuterated solvents were purchased from Sigmaꢀ Aldrich
and used as received. Solvents like THF, acetone, DCM, CHCl3, petroleum Ether, ethylacetate,
DMF and DMSO were procured from Spectrochem India Limited. THF, DCM and CHCl3 were
distilled via usual procedure prior to use. All other materials Et3N, SOCl2, K2Cr2O7, H2SO4,
Tosyl chloride, NaI, Tetraꢀnꢀbutylammonium fluoride (TBAF), NaOH were also obtained from
Sigma ꢀ Aldrich. Reactions were carried out under nitrogen atmosphere and workup procedure
were done at ambient conditions. In each case, column chromatography was performed by using
1
60ꢀ120 mesh silica gel which was purchased from Merck private limited. H, 13C NMR
spectroscopy experiments were carried out on a FTꢀNMR Bruker DPX 300/400/500 MHz NMR
spectrometer and the residual protons of each deuterated solvents were granted as the internal
standards where the coupling constants were calculated in hertz (Hz) and chemical shifts in ppm.
Electrospray ionization mass spectrometry (ESIꢀMS) analysis was performed with a Waters
QtoF Model YA 263 spectrometer in positive ion ESI mode. Fourier transform infrared (FTꢀIR)
spectra were recorded on a SHIMADZU FTIRꢀ8400S IR spectrophotometer with KBr pellets.
The absorption spectra were recorded in a PerkinꢀElmer Lambda 900 UV/Vis/NIR spectrometer
(NIR = nearꢀinfrared) (with a quartz cuvette of path length 1 cm). EPR experiment was carried
out by using a JEOL JESꢀFA200 spectrometer with an X band micro web unit. The elemental
analyses was carried out using a PerkinꢀElmer 2400 SeriesꢀII CHN analyser. Crystals were
solved by using a Bruker SMART APEX diffractometer, equipped with a CCD area detector at

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150 K. The bis (amide) tris (amine) macrocycle (MC),19a BPy4COOH,22a BPy4COCl,23
Axle2,22b AllI,24 PropI,25 Axle722c and 2ꢀaminoethyl azide17c were prepared by using the known
procedure reported in literature. All the characterization data of the known compounds properly
matched with the reported characterization details.
Synthesis of the compounds:
4, 4'ꢀDimethylꢀ2, 2'ꢀBipyridine was first oxidized to diꢀacid (BPy4COOH) by using K2Cr2O7 in
concentrated sulphuric acid (H2SO4) at 80˚C, which was utilised to synthesise Axle2, Axle5 and
Axle6. Afterwards, the reaction of diꢀacid with thionyl chloride (SOCl2) affords corresponding
diꢀacid chloride (BPy4COCl). Now the reactions of BPy4COCl with suitable respective chemical
precursors produce Axle3, Axle4, Axle7 ꢀ Axle10.
(a) Synthesis of Axle3, Axle4, Axle7 ꢀ Axle10: BPy4COCl (1 mmol) in dry THF was added
dropwise to the stirring solution of dry Et3N (2.2 mmol) and respective chemical compounds (2.2
mmol) like 2ꢀbromoethanol, propargyl alcohol, nꢀpropyl amine, 3ꢀaminoꢀ1ꢀpropanol, 2ꢀ
aminoethyl azide or benzyl amine in dry THF. The solution mixture was allowed to stir at room
temperature in ice cold condition for 24h under N2 atmosphere, followed by removal of solvent
in vaccuo. The reaction mixture was then stirred with saturated NaHCO3 solution (25 ml) for 6h
and appearing precipitate was collected by filtration. Finally after drying the precipitate solid
Axle3, Axle4, Axle7 – Axle10 were obtained in moderate yields. Detail experimental procedures
and characterization spectra are given in supporting information.
(b) Synthesis of Axle5, Axle6: To the stirring solution of BPy4COOH (1 mmol) and TBAF (3
mmol) in dry THF (20 ml), AllI or PropI (2.2 mmol) was added dropwise by dissolving it in the
same solvent (25 ml). The mixture was allowed to reflux under N2 atmosphere at 70°C for 48h
followed by removal of solvent in vaccuo. The reaction mixture was extracted 3 times with

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CHCl3 from the aqueous layer (50
X
3). Organic extracts were combined and washed several
times by using saturated NaHCO3 solution (200ml) and brine solution (200 ml), dried over
Na2SO4 and concentrated under reduced pressure. Final purification was done by silica gel
column chromatography using petroleum ether/ ethylacetate as eluent to afford solid Axle5 and
Axle6. Detail experimental procedures and characterization spectra are given in supporting
information.
Characterization Data
Axle3: M.P: 144°Cꢀ146°C. HRMS (ESIꢀMS): m/z calculated for C16H15Br2N2O4 [M + H]+
458.9300, found 458.9372. IR (KBr, ʋ cmꢀ1): 470, 567, 690, 723, 763, 815, 860, 918, 945, 987,
1064, 1124, 1230, 1257, 1280, 1365, 1384, 1440, 1554, 1595, 1724 (ester C=0), 2854, 2923,
1
3028, 3072. H NMR (400 MHz, CDCl3): δ (ppm) 3.69 (t, 4H, J = 8 Hz, ꢀCH2), 4.71 (t, 4H, J =
8 Hz, ꢀCH2), 7.93ꢀ7.94 (m, 2H, ArꢀH), 8.89 (d, 2H, J = 4 Hz, ArꢀH), 8.98 (s, 2H, ArꢀH). 13C
NMR (400 MHz, CDCl3): δ (ppm) 28.3, 65.1, 120.8, 123.5, 138.3, 150.3, 156.7, 164.8. Yield:
71%.
Axle4: M.P: 140°C. HRMS (ESIꢀ MS): m/z calculated for C18H13N2O4 [M + H]+ 321.0797, found
321.0869. IR (KBr, ʋ cmꢀ1): 663, 690, 759, 860, 962, 999, 1064, 1095, 1124, 1164, 1247, 1286,
1369, 1442, 1460, 1554, 1591, 1662, 1720 (ester C=0), 1743, 2129 (C≡C), 2732, 2854, 2923,
1
3004, 3095, 3253, 3284 (HꢀC≡). H NMR (400 MHz, CDCl3): δ (ppm) 2.56 (t, 2H, J = 4 Hz, ꢀ
CH), 5.00 (d, 4H, J = 2.4 Hz, ꢀCH2), 7.93ꢀ7.95 (m, 2H, ArꢀH), 8.88 (d, 2H, J = 4 Hz, ArꢀH), 8.99
(s, 2H, ArꢀH). 13C NMR (400 MHz, CDCl3): δ (ppm) 29.8, 53.3, 75.8, 120.9, 123.5, 138.1,
150.4, 156.7, 164.6. Yield: 80%
Axle5: M.P: 55°C. HRMS (ESIꢀMS): m/z calculated for C34H49N2O4 [M + H]+ 549.3614, found
549.3688. IR (KBr, ʋ cmꢀ1): 410, 667, 692, 725, 761, 862, 908, 952, 995, 1064, 1134, 1251,

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1288, 1365, 1396, 1471, 1556, 1593, 1639 (C=C), 1724 (ester C=0), 2852, 2923, 2966, 3072. 1H
NMR (400 MHz, CDCl3): δ (ppm) 1.30ꢀ1.47 (m, 24H, ꢀCH2), 1.78ꢀ1.83 (m, 4H, ꢀCH2), 1.99ꢀ
2.06 (m, 4H, ꢀCH2), 4.39 (t, 4H, J = 10 Hz, ꢀCH2), 4.89ꢀ5.02 (m, 4H, ꢀCH2), 5.73ꢀ5.85 (m, 2H, ꢀ
13
CH), 7.89ꢀ7.91 (m, 2H, ArꢀH), 8.85 (d, 2H, J = 8Hz, ArꢀH), 8.94 (s, 2H, ArꢀH). C NMR (400
MHz, CDCl3): δ (ppm) 26.1, 28.8 ꢀ 29.6, 33.9, 66.2, 114.3, 120.7, 123.3, 139.2, 139.3, 150.2,
156.8, 165.4. Yield: 80%
Axle6: M.P: 85°C. HRMS (ESI)): m/z calculated for C34H45N2O4 [M + H]+ 545.3301, found
545.3372. IR (KBr, ʋ cmꢀ1): 364, 534, 644, 667, 692, 723, 767, 875, 954, 1004, 1062, 1103,
1134, 1255, 1284, 1367, 1394, 1475, 1558, 1593, 1726 (ester C=0), 2109 (C≡C), 2854, 2923,
2962, 3083, 3286 (HꢀC≡). 1H NMR (500 MHz, CDCl3): δ (ppm) 1.25ꢀ1.35(m, 24H, ꢀCH2), 1.79ꢀ
1.84 (m, 4H, ꢀCH2), 1.93 (s, 2H, ꢀCH), 2.15ꢀ2.19 (m, 4H, ꢀCH2), 4.39 (t, 4H, J = 10Hz, ꢀCH2),
7.89ꢀ7.91 (m, 2H, ArꢀH), 8.86 (d, 2H, J = 10Hz, ArꢀH), 8.94 (s, 2H, ArꢀH). 13C NMR (400 MHz,
CDCl3): δ (ppm) 18.5, 26.1, 28.6 ꢀ 29.5, 66.2, 68.2, 84.9, 120.7, 123.3, 139.2, 150.2, 156.7,
165.4. Yield: 73%
Axle8: M.P: 250°C. HRMS (ESIꢀMS): m/z calculated for C18H22N4NaO4 [M + Na]+ 381.1539
found 381.1538. IR (KBr, ʋ cmꢀ1): 663, 692, 858, 894, 925, 995, 1072, 1099, 1332, 1352, 1407,
1446, 1467, 1537, 1591, 1637 (amide C=O), 1741, 2854, 2923, 3087, 3282 (NꢀH), 3577 (OꢀH).
1H NMR (400 MHz, DMSOꢀd6): δ (ppm) 3.44ꢀ 3.51 (m, 8H, ꢀCH2), 3.57 (t, 4H, J = 6 Hz, ꢀCH2),
4.59 (t, 2H, J = 6 Hz, ꢀOH), 7.84ꢀ7.85 (m, 2H, ꢀArꢀH), 8.78 (s, 2H, ArꢀH), 8.85 (d, 2H, J = 4
13
Hz, ArꢀH), 8.99 (t, 2H, J = 6 Hz, ꢀNH). C NMR (400 MHz, DMSOꢀd6): δ (ppm) 60.2, 68.6,
72.1, 118.2, 121.8, 142.8, 150.0, 155.5, 164. 7. Yield: 68%
Axle9: M.P: 220ꢀ222°C. HRMS (ESIꢀMS): m/z calculated for C16H16N10NaO2 [M + Na]+
403.1355 found 403.1354. IR (KBr, ʋ cmꢀ1): 493, 553, 665, 713, 738, 860, 898, 989, 1095, 1217,

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1253, 1298, 1321, 1352, 1444, 1539, 1591, 1645 (amide C=O), 1728, 2100 (azide), 2854, 2929,
3066, 3272 (NꢀH). 1H NMR (400 MHz, DMSOꢀd6): δ (ppm) 3.53 (s, 8H, ꢀCH2), 7.87 (d, 2H, J =
2Hz, ꢀArꢀH), 8.82 (s, 2H, ArꢀH), 8.90 (d, 2H, J = 2Hz, Ar–H), 9.20 (s, 2H, ꢀNH). 13C NMR (400
MHz, DMSOꢀd6): δ (ppm) 49.5, 118.1, 121.9, 142.6, 150.1, 155.5, 164.9. Yield: 60%
Axle10: M.P: 290°C. HRMS (ESIꢀMS): m/z calculated for C26H23N4O2 [M + H]+ 423.1743
found 423.1816. IR (KBr, ʋ cmꢀ1): 480, 694, 742, 862, 892, 1074, 1238, 1317, 1361, 1452, 1535,
1591, 1639 (amide C=O), 1747, 2854, 2923, 3031, 3087, 3278 (NꢀH), 3413. 1H NMR (400 MHz,
DMSOꢀd6): δ (ppm) 4.53 (d, 4H, J = 8 Hz, ꢀCH2), 7.27 (s, 2H, ArꢀH), 7.36 (d, 8H, J = 4 Hz, Arꢀ
13
H), 7.90 (d, 2H, J = 4Hz, ArꢀH), 8.88 (t, 4H, J = 8Hz, ArꢀH), 9.53 (t, 2H, J = 4Hz, ꢀNH). C
NMR (400 MHz, DMSOꢀd6): δ (ppm) 42.8, 118.2, 121.9, 126.9, 127.3, 128.3, 139.1, 142.7,
150.1, 155.5, 164.6. Yield: 80%.
Synthesis of NiII templated PR1 ꢀ PR10 complexes
To the stirring solution of MC (0.1 mmol) in DCMꢀMeOH (1:1, 5ml), the solution of
Ni(ClO4)2·6H2O (0.1 mmol) in MeOH (5 ml) was added at room temperature and allowed to stir
for 6h. To the reaction mixture, each of the axles (0.1 mmol) (Axle1 ꢀ Axle10) was added
separately at room temperature and stirred for 24h, followed by removal of solvent at vaccuo.
Appearing precipitate was washed several times with DCM and finally after drying, pure product
was obtained as yellowish coloured solid in high yields. NiII templated [2]pseudorotaxanes
complexes were abbreviated as PR1 [{MC.NiII(ClO4)2} @ Axle1], PR2 [{MC.NiII(ClO4)2} @
Axle2], PR3 [{MC.NiII(ClO4)2} @ Axle3], PR4 [{MC.NiII(ClO4)2} @ Axle4], PR5
[{MC.NiII(ClO4)2} @ Axle5], PR6 [{MC.NiII(ClO4)2} @ Axle6], PR7 [{MC.NiII(ClO4)2} @
Axle7], PR8 [{MC.NiII(ClO4)2} @ Axle8], PR9 [{MC.NiII(ClO4)2} @ Axle9], PR10

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[{MC.NiII(ClO4)2} @ Axle10]. All the complexes were well characterized by ESIꢀMS, IR and
UVꢀVis absorption titration studies.
(i) Synthesis and characterization of PR1: MC= 53 mg (0.1mmol); Ni(ClO4)2·6H2O = 36 mg
(0.1mmol); Axle1= 18 mg (0.1mmol). Yield: 77 mg (80%). Molar extinction coefficient value in
CH3CN (ε) = 9.29
X
103 M−1 cm−1, λmax = 304 nm. HRMS (ESIꢀMS): m/z calculated for
C42H49ClN7NiO8 [M]+ 872.2685, found 872.2683. IR (KBr, ʋ cmꢀ1): 393, 511, 561, 626, 676,
705, 740, 827, 1024, 1085, 1116, 1139, 1244, 1294, 1355, 1444, 1512, 1541, 1618, 1662, 2854,
2925, 3282, 3409. C42H49Cl2N7NiO12: calcd. C, 51.82; H, 5.07; N, 10.07; found C 51.97, H 5.10,
N 10.01. M.P: 179°Cꢀ180°C.
(ii) Characterization of PR2: MC= 53 mg (0.1mmol); Ni(ClO4)2·6H2O = 36 mg (0.1mmol);
Axle2= 30 mg (0.1mmol). Yield: 76 mg (70%). Molar extinction coefficient value in CH3CN (ε)
= 1.29
X
104 M−1 cm−1, λmax = 323 nm. HRMS (ESIꢀMS): m/z calculated for C46H53ClN7NiO12
[M]+ 988.2794, found 988.2792. IR (KBr, ʋ cmꢀ1): 628, 651, 673, 717, 827, 1022, 1085, 1116,
1255, 1406, 1444, 1469, 1602, 1666, 1728, 2854, 2923, 3055, 3407. C46H53Cl2N7NiO16 : calcd.
C, 50.71; H, 4.90; N, 9.00; found C 50.68, H 4.84, N 9.05. M.P: 194°Cꢀ196°C.
(iii) Characterization of PR3: MC = 53 mg (0.1mmol); Ni(ClO4)2·6H2O = 36 mg (0.1mmol);
Axle3 = 30 mg (0.1mmol). Yield: 90 mg (73%). Molar extinction coefficient value in CH3CN (ε)
= 1.21
X
104 M−1 cm−1, λmax = 323 nm. HRMS (ESIꢀMS): m/z calculated for
C46H53Br2ClN7NiO12 [M+2H]+ 1148.0984, found 1148.0964. IR (KBr, ʋ cmꢀ1): 368, 433, 514,
628, 673, 759, 853, 1085, 1116, 1253, 1323, 1404, 1442, 1512, 1604, 1664, 1730, 2952, 3269,
3384, 3454, 3533. C46H51Br2Cl2N7NiO16 : calcd. C, 44.29; H, 4.12; N, 7.86; found C 44.42, H
4.14, N 7.81. M.P: 188°Cꢀ190°C.

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(iv) Characterization of PR4: MC = 53 mg (0.1mmol); Ni(ClO4)2·6H2O = 36 mg (0.1mmol);
Axle4 = 32 mg (0.1mmol). Yield: 91 mg (83%). Molar extinction coefficient value in CH3CN (ε)
= 9.97
X
103 M−1 cm−1, λmax = 324 nm. HRMS (ESIꢀMS): m/z calculated for C48H49ClN7NiO12
[M]+ 1008.2481, found 1008.2483. IR (KBr, ʋ cmꢀ1): 590, 622, 673, 756, 831, 1024, 1085, 1097,
1114, 1247, 1313, 1404, 1440, 1514, 1556, 1616, 1666, 1737, 2125, 2862, 2931, 3284, 3413.
C48H49Cl2N7NiO16 : calcd. C, 51.96; H, 4.45; N, 8.84; found C 52.09, H 4.49, N 8.90. M.P:
183°C ꢀ186°C.
(v) Characterization of PR5: MC = 53 mg (0.1mmol); Ni(ClO4)2·6H2O = 36 mg (0.1mmol);
Axle5 = 55 mg (0.1mmol). Yield: 113 mg (85%). Molar extinction coefficient value in CH3CN
(ε) = 1.50
X
104 M−1 cm−1, λmax = 323 nm. HRMS (ESIꢀMS): m/z calculated for
C64H85ClN7NiO12 [M]+ 1236.5298, found 1236.5052. IR (KBr, ʋ cmꢀ1): 516, 624, 671, 698, 763,
825, 908, 952, 993, 1085, 1116, 1182, 1251, 1319, 1400,1444, 1514, 1544, 1610, 1666, 1730,
2852, 2923, 3076, 3282, 3384. C64H85Cl2N7NiO16 (1335.48): calcd. C, 57.45; H, 6.40; N, 7.33;
found C 57.64, H 6.46, N 7.29. M.P: 99°Cꢀ101°C.
(vi) Characterization of PR6: MC = 53 mg (0.1mmol); Ni(ClO4)2·6H2O = 36 mg (0.1mmol);
Axle6 = 54 mg (0.1mmol). Yield: 111 mg (84%). Molar extinction coefficient value in CH3CN
(ε) = 1.29
X
104 M−1 cm−1, λmax = 323 nm. HRMS (ESIꢀMS): m/z calculated for C64H80ClN7NiO12
[MꢀH]+ 1231.4985, found 1231.4203. IR (KBr, ʋ cmꢀ1): 379, 518, 624, 669, 765, 835, 960, 1085,
1116, 1180, 1253, 1321, 1400, 1444, 1461, 1514, 1544, 1610, 1666, 1731, 2854, 2923, 3031,
3284, 3359. Despite several attempts unsatisfactory elemental analysis result has been obtained.
M.P: 96°Cꢀ98°C.
(vii) Characterization of PR7: MC = 53 mg (0.1mmol); Ni(ClO4)2·6H2O = 36 mg (0.1mmol);
Axle7 = 33 mg (0.1mmol). Yield: 83 mg (72%). Molar extinction coefficient value in CH3CN (ε)

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= 1.17
X
104 M−1 cm−1, λmax = 323 nm. HRMS (ESIꢀMS): m/z calculated for C48H58ClN9NiO10
[MꢀH]+ 1013.3427, found 1013.3295. IR (KBr, ʋ cmꢀ1): 435, 624, 675, 754, 823, 1085, 1114,
1244, 1402, 1440, 1488, 1558, 1593, 1664, 2854, 2952, 3082, 3290, 3377. C48H59Cl2N9NiO14
calcd. C, 51.68; H, 5.33; N, 11.30; found C 51.73, H 5.29, N 11.28. M.P: 198°Cꢀ200°C.
:
(viii) Characterization of PR8: MC = 53 mg (0.1mmol); Ni(ClO4)2·6H2O = 36 mg (0.1mmol);
Axle8 = 36 mg (0.1mmol). Yield: 79 mg (70%). Molar extinction coefficient value in CH3CN (ε)
= 1.12
X
104 M−1 cm−1, λmax = 320 nm. HRMS (ESIꢀMS): m/z calculated for C48H60ClN9NiO12
[M+H]+ 1047.3325, found 1047.3396. IR (KBr, ʋ cmꢀ1): 391, 590, 630, 651, 671, 756, 827, 950,
1026, 1083, 1118, 1145, 1238, 1313, 1398, 1442, 1514, 1546, 1654, 1745, 2856, 2925, 3080,
3286, 3421. Despite several attempts unsatisfactory elemental analysis result has been obtained.
M.P: 204°Cꢀ206°C
(ix) Characterization of PR9: MC = 53 mg (0.1mmol); Ni(ClO4)2·6H2O = 36 mg (0.1mmol);
Axle9 = 38 mg (0.1mmol). Yield: 94 mg (81%). Molar extinction coefficient value in CH3CN (ε)
= 1.19
X
104 M−1 cm−1, λmax= 319 nm. HRMS (ESIꢀMS): m/z calculated for C46H54ClN15NiO10
[M+H]+ 1069.3142, found 1069.3215. IR (KBr, ʋ cmꢀ1): 443, 514, 626, 694, 757, 829, 960, 1085,
1114, 1180, 1247, 1276, 1303, 1398, 1442, 1514, 1546, 1614, 1660, 2104, 2852, 2923, 3080,
3280, 3352. C46H53Cl2N15NiO14 : calcd. C, 47.24; H, 4.57; N, 17.96; found C 47.35, H 4.53, N
17.99. M.P: 213°Cꢀ215°C.
(x) Characterization of PR10: MC = 53 mg (0.1mmol); Ni(ClO4)2·6H2O = 36 mg (0.1mmol);
Axle10 = 42 mg (0.1mmol). Yield: 91 mg (76%). Molar extinction coefficient value in CH3CN
(ε) = 1.29
X
104 M−1 cm−1, λmax = 321 nm. HRMS (ESIꢀMS): m/z calculated for
C56H59ClN9NiO10 [M]+ 1110.3427, found 1110.3428. IR (KBr, ʋ cmꢀ1): 626, 673, 694, 738, 825,
1027, 1085, 1114, 1242, 1286, 1355, 1402, 1442, 1544, 1606, 1621, 2856, 2927, 3093, 3290,

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3352, 3407. C56H59Cl2N9NiO14 (1209.26): calcd. C, 55.51; H, 4.91; N, 10.40; found C 55.43, H
4.89, N 10.35. M.P: 218°Cꢀ220°C.
Synthesis of CuII templated PR1' ꢀ PR10' complexes
To the stirring solution of MC (0.1 mmol) in DCM ꢀ MeOH (1:1, 5ml), the solution of
Cu(ClO4)2·6H2O (0.1 mmol) in MeOH (5 ml) was added at room temperature and allowed to stir
for 6h. To the reaction mixture, each of the axles (0.1 mmol) (Axle1 ꢀ Axle10) was added
seperately at room temperature and stirred for 24h, followed by removal of solvent at vaccuo.
Appearing precipitate was washed several times with DCM and finally after drying, pure solid
product was obtained as blue coloured solid in high yields (90%). CuII templated
[2]pseudorotaxanes complexes were abbreviated as PR1' [{MC.CuII(ClO4)2} @ Axle1], PR2'
[{MC.CuII(ClO4)2} @ Axle2], PR3' [{MC.CuII(ClO4)2} @ Axle3], PR4' [{MC.CuII(ClO4)2}@
Axle4], PR5' [{MC.CuII(ClO4)2} @ Axle5], PR6' [{MC.CuII(ClO4)2} @ Axle6], PR7'
[{MC.CuII(ClO4)2} @ Axle7], PR8' [{MC.CuII(ClO4)2} @ Axle8], PR9' [{MC.CuII(ClO4)2} @
Axle9], PR10' [{MC.CuII(ClO4)2} @ Axle10]. All the complexes were well characterized by
ESIꢀ MS, EPR and absorption spectra studies.
(i) Characterization of PR1': MC= 53 mg (0.1mmol); Cu(ClO4)2·6H2O = 37 mg (0.1mmol);
Axle1= 18 mg (0.1mmol). Yield: 78 mg (81%). Molar extinction coefficient value in CH3CN (ε)
= 2.24
X
102 M−1 cm−1, λmax = 668 nm. HRMS (ESIꢀMS): m/z calculated for C42H49ClCuN7O8
[M]+ 877.2627, found 877.2624. IR (KBr, ʋ cmꢀ1): 514, 628, 673, 744, 831, 1085, 1116, 1247,
1298, 1361, 1444, 1512, 1544, 1614, 1664, 2856, 2952, 3080, 3259, 3407. C42H49Cl2CuN7O12 :
calcd. C, 51.56; H, 5.05; N, 10.02; found C 51.64, H 5.03, N 10.09. M.P: 205°Cꢀ207°C.
(ii) Characterization of PR2': MC= 53 mg (0.1mmol); Cu(ClO4)2·6H2O = 37 mg (0.1mmol);
Axle2= 30 mg (0.1mmol). Yield: 78 mg (75%). Molar extinction coefficient value in CH3CN (ε)

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= 3.14
X
102 M−1 cm−1, λmax = 629 nm. HRMS (ESIꢀMS): m/z calculated for C46H53ClCuN7O12
[M]+ 993.2737, found 993.2739. IR (KBr, ʋ cmꢀ1): 514, 626, 651, 673, 717, 761, 833, 1018,
1087, 1114, 1253, 1290, 1369, 1400, 1442, 1514, 1552, 1608, 1664, 1728, 2927, 2958, 3269,
3392, 3409, 3595. C46H53Cl2CuN7O16 (1092.22): calcd. C, 50.48; H, 4.88; N, 8.96; found C
50.60, H 4.95, 9.03. M.P: 169°C ꢀ170°C.
(iii) Characterization of PR3': MC = 53 mg (0.1mmol); Cu(ClO4)2·6H2O = 37 mg (0.1mmol);
Axle3 = 30 mg (0.1mmol). Yield: 93 mg (75%). Molar extinction coefficient value in CH3CN (ε)
= 3.57
X
102 M−1 cm−1, λmax = 631 nm. HRMS (ESIꢀMS): m/z calculated for
C46H51Br2ClCuN7O12 [M]+ 1151.0927, found 1151.0839. IR (KBr, ʋ cmꢀ1): 439, 626, 759, 831,
1083, 1114, 1251, 1438, 1598, 1666, 1731, 2853, 2927, 3406, 3463. C46H51Br2Cl2CuN7O16 :
calcd. C, 44.12; H, 4.11; N, 7.83; found C 44.01, H 4.08, N 7.87. M.P: 174°Cꢀ176°C.
(iv) Characterization of PR4': MC = 53 mg (0.1mmol); Cu(ClO4)2·6H2O = 37 mg (0.1mmol);
Axle4 = 32 mg (0.1mmol). Yield: 91 mg (83%). Molar extinction coefficient value in CH3CN (ε)
= 3.14
X
102 M−1 cm−1, λmax = 631 nm. HRMS (ESIꢀMS): m/z calculated for C48H49ClCuN7O12
[M]+ 1013.2424, found 1013.2422. IR (KBr, ʋ cmꢀ1): 372, 522, 576, 622, 651, 673, 761, 831,
929, 983, 1089, 1251, 1315, 1373, 1406, 1440, 1514, 1548, 1612, 1662, 1739, 2146, 2854, 2923,
3265, 3398. C48H49Cl2CuN7O16 : calcd. C, 51.73; H, 4.43; N, 8.80; found C 51.86, H 4.39, N
8.75. M.P: 210°Cꢀ212°C
(v) Characterization of PR5': MC = 53 mg (0.1mmol); Cu(ClO4)2·6H2O = 37 mg (0.1mmol);
Axle5 = 55 mg (0.1mmol). Yield: 109 mg (82%). Molar extinction coefficient value in CH3CN
(ε) = 3.69
X
102 M−1 cm−1, λmax = 635 nm. HRMS (ESIꢀMS): m/z calculated for
C64H86ClCuN7O12 [M+H]+ 1242.5241, found 1242.3867. IR (KBr, ʋ cmꢀ1): 630, 700, 761, 865,
910, 954, 995, 1089, 1128, 1186, 1253, 1296, 1357, 1396, 1467, 1514, 1554, 1593, 1612, 1647,

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1668, 1718, 2852, 2921, 3076, 3444. C64H85Cl2CuN7O16 : calcd. C, 57.24; H, 6.38; N, 7.30;
found C 57.32, H 6.42, N 7.32. M.P: 94°Cꢀ96°C.
(vi) Characterization of PR6': MC = 53 mg (0.1mmol); Cu(ClO4)2·6H2O = 37 mg (0.1mmol);
Axle6 = 54 mg (0.1mmol). Yield: 106 mg (80%). Molar extinction coefficient value in CH3CN
(ε) = 3.31
X
102 M−1 cm−1, λmax = 629 nm. HRMS (ESIꢀMS): m/z calculated for
C64H81ClCuN7O12 [M]+ 1237.4928, found 1237.4926. IR (KBr, ʋ cmꢀ1): 622, 669, 696, 721, 763,
860, 954, 1087, 1118, 1137, 1182, 1245, 1259, 1294, 1359, 1402, 1446, 1463, 1514, 1548, 1596,
1662, 1728, 2852, 2923, 3228. C64H81Cl2CuN7O16 : calcd. C, 57.42; H, 6.10; N, 7.32; found C
57.34, H 6.13, N 7.37. M.P: 98°Cꢀ100°C.
(vii) Characterization of PR7': MC = 53 mg (0.1mmol); Cu(ClO4)2·6H2O = 37 mg (0.1mmol);
Axle7 = 33 mg (0.1mmol). Yield: 80 mg (72%). Molar extinction coefficient value in CH3CN (ε)
= 3.53
X
102 M−1 cm−1, λmax = 641 nm. HRMS (ESIꢀMS): m/z calculated for C48H58ClCuN9O10
[MꢀH]+ 1018.3369, found 1018.3293. IR (KBr, ʋ cmꢀ1): 437, 532, 557, 580, 609, 665, 1081,
1245, 1296, 1409, 1440, 1481, 1595, 1664, 1724, 1812, 2852, 2952, 3346, 3465. Despite several
attempts unsatisfactory elemental analysis result has been obtained. M.P: 164°Cꢀ166°C.
(viii) Characterization of PR8': MC = 53 mg (0.1mmol); Cu(ClO4)2·6H2O = 37 mg (0.1mmol);
Axle8 = 36 mg (0.1mmol). Yield: 87 mg (76%). Molar extinction coefficient value in CH3CN (ε)
= 3.75
X
102 M−1 cm−1, λmax = 645 nm. HRMS (ESIꢀMS): m/z calculated for C48H58ClCuN9O12
[MꢀH]+ 1050.3268, found 1050.3191. IR (KBr, ʋ cmꢀ1): 395, 426, 466, 516, 572, 595, 626, 648,
675, 752, 825, 1083, 1114, 1244, 1284, 1309, 1402, 1442, 1514, 1546, 1614, 1660, 1741, 2854,
2923, 3085, 3407, 3583, 3624. C48H59Cl2CuN9O16 : calcd. C, 50.02; H, 5.16; N, 10.94; found C
49.97, H 5.10, N 10.90. M.P: 170°Cꢀ172°C

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(ix) Characterization of PR9': MC = 53 mg (0.1mmol); Cu(ClO4)2·6H2O = 37 mg (0.1mmol);
Axle9 = 38 mg (0.1mmol). Yield: 98 mg (84%). Molar extinction coefficient value in CH3CN (ε)
= 3.50
X
102 M−1 cm−1, λmax= 643 nm. HRMS (ESIꢀMS): m/z calculated for C46H52ClCuN15O10
[MꢀH]+ 1072.3084, found 1072.3004. IR (KBr, ʋ cmꢀ1): 403, 524, 624, 648, 673, 696, 748, 823,
1020, 1078, 1116, 1245, 1294, 1400, 1444, 1514, 1546, 1664, 1745, 2102, 2852, 2921, 2076,
3257, 3367. C46H53Cl2CuN15O14 : calcd. C, 47.04; H, 4.55; N, 17.89; found C 47.16, H 4.61, N
17.81. M.P: 175°Cꢀ177°C.
(x) Characterization of PR10': MC = 53 mg (0.1mmol); Cu(ClO4)2·6H2O = 37 mg (0.1mmol);
Axle10 = 42 mg (0.1mmol). Yield: 96 mg (80%). Molar extinction coefficient value in CH3CN
(ε) = 3.32
X
102 M−1 cm−1, λmax = 648 nm. HRMS (ESIꢀMS): m/z calculated for
C56H59ClCuN9O10 [M]+ 1115.3369, found 1115.3202. IR (KBr, ʋ cmꢀ1): 621, 667, 694, 744, 823,
1085, 1114, 1244, 1309, 1359, 1406, 1444, 1514, 1546, 1604, 1660, 2854, 2952, 3082, 3269,
3350. C56H59Cl2CuN9O14 : calcd. C, 55.29; H, 4.89; N, 10.36; found C 55.35, H 4.86, N 10.32.
M.P: 189°Cꢀ191°C.
Calculation of Association Constant (Ka)
Upon addition of the MCꢀNiII complex solution (guest) into the bidentate axle solution (host),
absorption spectra changes gradually due to the binding of bidentate axle with the metalloꢀ
macrocycle complexes. The association constant (Ka) values of these bindings were determined
by nonlinear fitting of the curves obtained by plotting the absorbance changes (∆A) at a fixed λ
value (where the absorption changes were maximal i.e λmax value) against the guest
concentration. All the absorption titration data were fitted to the following equation (1) for 1:1
binding:
∆A = A· {([H] + [Xꢀ] + (1/Ka)) – {([H] + [Xꢀ] + (1/Ka))2 – (4·[H]·[Xꢀ])}1/2} / (2·[H])…… (1)

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A = absorbance value upon each addition of the guest, ∆A = (AꢀA0), [H] = concentration of host
and [Xꢀ] = concentration of guest.
Xꢀray Crystallographic Refinement Details
The crystallographic details of PR1', PR3', PR7' and the refinement parameters are given in
Table S1. Crystal structures suitable for single crystal XꢀRay diffraction studies were collected
from either CH3CN or DMFꢀCH3CN mixture. The crystals were chosen from the mother liquor
among the multiple sets of data collection, dipped in paratone oil and cemented on the tip of a
glass fiber using epoxy resin. Intensity data for the complexes (PR1', PR3' and PR7') were
collected using graphiteꢀmonochromatized Mo Kα radiation (0.71073 Å) at 150 K equipped with
a CCD area detector at 150 K. Crystal data integration and reduction were processed on a Bruker
SMART APEX II CCD diffractometer using the SAINT software28 provided with the SMART
APEX II software package. The structures were solved by using the direct method of SHELXSꢀ
9729 and the refinements are carried out on F2 by the fullꢀmatrix leastꢀsquares technique using the
SHELXLꢀ2014 programme package.30 Empirical absorption corrections were applied with
SADABS.31 PLATON32 and MERCURY 3.733 were used to generate graphics. For all the three
complexes all nonꢀhydrogen atoms were refined with anisotropic displacement coefficients and
all hydrogen atoms were geometrically fixed at idealized positions. CCDC no. of the crystal
structures (1534186ꢀ 1534188) contains the supplementary crystallographic data for this paper.
Acknowledgements
P. G. gratefully acknowledges the Science and Engineering Research Board (SERB), New Delhi
(project SR/S1/ICꢀ39/2012) for financial support. M. N. acknowledges DST, Inspire (IF150113)
for JRF and S. Santra acknowledges the Council of Scientific & Industrial Research (CSIR) New
Delhi and Indian Association for the Cultivation of Science (IACS), Kolkata for doctoral

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fellowship. Authors acknowledge Dr. Subrata Saha for synthesising PR1' and PR3'. Authors are
thankful to Mr. Koushik Sarkar for improving the data quality of the crystal structures. Xꢀray
crystallographic data collection was performed at the DSTꢀfunded National Single Crystal Xꢀray
facility at the Department of Inorganic Chemistry, IACS, India.
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