A new multitalented azine ligand: Elastic bending, single-crystal-to-single-crystal transformation and a fluorescence turn-on Al(III) sensor

Article abstract of DOI:10.1039/c7cc04392a

We report a rare combination of two unique properties of an azine based ligand (H₃L): in a solid-state crystalline material it shows highly flexible and elastic behavior which on triggering with light results in slight deviation with phase tran

Full text of DOI:10.1039/c7cc04392a

View Article Online
View Journal
ChemComm
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: A. K. Saini, K.
Natarajan and S. M. Mobin, Chem. Commun., 2017, DOI: 10.1039/C7CC04392A.
Volume 52 Number
1
4
January 2016 Pages 1–216
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Chemical Communications
www.rsc.org/chemcomm
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc
first methanofullerene derivatives of Sc
3
N@C2n (2n
=
68 and 80). Synthesis of the
3
N@D5h-C80
rsc.li/chemcomm

Please do not adjust margins
Page 1 of 5
ChemComm
View Article Online
DOI: 10.1039/C7CC04392A
Journal Name
COMMUNICATION
A new multitalented azine ligand: elastic bending, single-crystal-
to-single-crystal transformation and a fluorescence turn–on Al(III)
sensor
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
a
b
a,b,c
Anoop Kumar Saini, Kaushik Natarajan and Shaikh M. Mobin,*
We report a rare combination of two unique properties of azine
based ligand (H
highly flexible and elastic behavior which on triggering with light processes from formulation to tableting. Generally, the
results slightly deviate with phase transformation at Single- flexibility of organic crystals depends on the mechanical force
Crystal-to-Single-Crystal (SCSC) level. Furthermore, in solution applied, which in turn depends on strong or weak interactions
state it acts as a highly selective, sensitive and reversible Al3+ between lattice molecules. Most of the existing reports on
Recently, mechanically flexible materials have gained much
3
L): In a solid-sate crystalline material it shows attention due to their promising application in pharmaceutical
15
sensor with the detection limit of 42 nM.
bendable crystals are results of serendipity but lately Reddy et
al. have reported a strategy for the design and synthesis of
The design and synthesis of multi-tasking materials has bendable crystals.
So far, the reports on elasticity and
8
attracted tremendous interest owing to their fascinating plasticity of molecular crystals have been revolving around the
applications and economic viability.1 Although individual following synthons: polyhalogenated N-benzylideneanilines,
properties of the material in the solid-state and the solution organic co-crystals,10 ester spacer based molecules,
16
15
8
16
state have been explored enormously, reports on combined naphthalene diimides derivatives, Schiff bases, vanillin
8
17
studies comprising of properties in both solid-state and in derivatives and pyrimidine. However, to the best of our
solution are sparse. In solid-state, crystalline materials are of knowledge, so far, no report is available on azine based elastic
paramount importance due to their potential applications in crystals. Due to the presence of flexible -C=N-N=C- azine unit,
2
3,4
the mechanical actuators, phototransistors, light-emitting it is found that these crystals exhibit efficient internal stress
5
6
7,8
diodes (LEDs), solar cells, photonics and flexible electronics
dissipation, which is important for many applications involving
etc. In addition, crystal engineering is a powerful tool that flexible substrates.18
helps organize complex materials into well-disciplined
The recent upsurge in the field of SCSC transformation
crystalline lattices via self-assembly of functional molecules. In reveals that transformed newer materials via external stimuli
fact, the engineered crystals are dominant to supramolecular like light, heat and vapor have significant applications in sensor
9
10
11
19
materials, drug formulation, artificial mechanosensors and technology and gas storage. The reversible/irreversible SCSC
12
smart nanomaterials. In crystal engineering, the major transformations in MOF and metal complexes are well
phenomena which attract attention are (i) the development of documented.20 However, in organic ligands, the SCSC
organic co-crystals (multi-component system), a prime focal transformations are rare and mostly restricted to [2+2]
point of pharmaceutical industries, (ii) single-crystal-to-single- cycloaddition of two neighboring olefinic bonds which are
crystal (SCSC) transformations which involve several bond designed to be close to each other within the range of 3.6-
breaking and formation processes that leads to unusual 5.00 Å via introduction of photo-induced strategy which has
products which may not be easily feasible by routine synthetic been extensively studied by MacGillivray and Vittal et al.21 To
methods and currently (iii) investigation of bending properties the best of our knowledge only one report is available on light
of crystals as introduced by Desiraju et al. in induced SCSC transformation of non-olefinic ligands.22
hexachlorobenzene and further extensively explored by Nevertheless, in solution state, the relatively free movement
Naumov and Reddy et al. about their mechanical of molecules makes it convenient to explore a huge repository
1
3,14
properties.
All these features in crystal engineering are of of properties. In particular, organic luminous and non-
luminous molecules play an important role in optics,
high interest in the scientific community today.
23
electronics, materials and biosciences.
The recent
developments related to solution state have witnessed an
enormous increase in the research areas of aggregation
induced emission (AIE) and ion sensing.
Herein, we attempt to explore a unique combination of
both the crystalline solid-state properties that deals with the
bending properties of crystals which undergo SCSC
a
b
Discipline of Chemistry, Discipline of Metallurgy Engineering and Materials
c
Science, Center for Biosciences and Bio-Medical Engineering, Indian Institute of
Technology Indore, Simrol, Khandwa Road, Indore 453552, India
corresponding author
24-26
*
Email: xray@iiti.ac.in
Electronic Supplementary Information (ESI) available. CCDC 1543797, 1543798.
†
For ESI and crystallographic data in CIF or other electronic format See
DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 2 of 5
COMMUNICATION
transformation via light stimuli and further the solution state
Journal Name
View Article Online
DOI: 10.1039/C7CC04392A
3+
properties involving fluorescence turn ON for Al sensing.
A new multifunctional azine based ligand ( L) was
obtained by the reaction of synthesized (E)-3-
hydrazonomethyl)benzene-1,2-diol with 2-hydroxy-1-
napthaldehyde (1: 1) in methanol at room temperature for 15
h (Scheme 1). has been characterized by NMR, ESI MS and
is further authenticated by single crystal X–ray studies. The
TGA study indicates a two step rapid decomposition of at
H
3
(
H
3
L
–
–
3
H L
around 320°C and 630°C, while DSC studies show a two phase
transitions at 197°C and 315°C (Fig. S1-S5).
Fig. 1 The different elastic stages in the successive bending (a
i) in the
–
3
H L.
The Es will also be greater with a decrease in critical radius,
as can be seen from continuum mechanics.29,30 A simple
Scheme 1. Synthesis of H
crystallizes in monoclinic P2
Table S1). Crystal structure of reveals that naphthyl group
and benzene 1,2 diol units separated by E/Z aldazine unit
which are arranged in a same plane. Molecular crystals of
were grown in different solvents such as methanol, ethanol
and acetonitrile in all these solvents the crystals of were
3
L.
calculation was performed to find out the values of Δl and
critical radius r for the H L. The results of the calculations are
c 3
explained in-depth in the supplementary information, while a
schematic of the bending experiment along with the type of
bending experienced by the crystal is represented in Fig. S8.
The average change in translation along the 1D axis (Δl) is
H
3
L
1
/n space group (Fig. S6,
3
H L
3
H L
found to be 2.6743 Å/molecule for
length (0.43 mm). The calculation shows critical radius for
breakage of the crystal, r , was found to be 30.8 μm and the
3
H L crystal of 430 µm in
3
H L
found to be elastically bendable in nature. A systematic
evaluation of the bending characteristics of the crystal was
carried out, based on methods previously described by Ghosh
c
breaking strain is experienced on the crystal when the bending
angular rotation per molecule is 0.0006134 °/molecule. The
calculations for the bent and original crystal show only minimal
changes, during or after bending. This serves as further proof
for the earlier indications of significant and exceptional
27
and Reddy. This was demonstrated by simply bending the
crystal from both the ends by using tweezer which on releasing
it goes back to its original position (Supplementary video 1).
In order to confirm the elasticity of the
much efforts we mounted the crystal in bent position by
entrapping the crystal in the Y shaped designed glass capillary
3
H L crystal, with
elasticity of
3 3
H L.The elastic nature of H L may be due the
tensile force between naphthyl and benzene diol groups
through E/Z aldazine (-C=N-N=C-) unit followed by the
–
and recorded the diffraction patterns by employing SCXRD
techniques. Despite being bent we were able to index the unit
cell parameters, which come out to be same as that of normal
crystal (Table S2). We observed a slight decay in the intensities
of diffraction spots in the bent crystal as compared to normal
crystal, which is attributed to modified absorption and
reflection characteristics of the crystals due to a change in
effective thickness of the crystal at the critical bending points
3
1
attractive force from the van der Waals interactions.
3
2
An earlier report by Barret et al. demonstrating light
driven bending of azobenzene crystals prompted us to explore
the SCSC transformation of
light. In this regards, the crystal of
irradiation, which resulted in the phase transformed crystal
H
3
L
crystal under the influence of
3
H L
was exposed to UV
1
structure (
space group from P2
approximately twice the length of the original a-axis (Table S1).
3
H L ). This SCSC transformation involved change in
1
28
1
/n in
H
3
L
to C2/c in
H
3
L
with
during elastic bending or elongation (Fig. S7). However, we
could not solve the structure with this quality of very weak
diffraction. This confirms that even at bent position the
molecules are still intact in the lattice, thus retaining the
crystallinity. Further, on relaxation the same crystal shows
original unit cell. This provides strong indication for significant
elastic stretching property of the crystal (Supplementary Video
1
The overlay molecular structure of
3
H L shows deviation of
1
1.77° from plane (Fig. 2a and 2b).
3
H L
2
–
4). The different elastic stages of the successive bending in
the crystal are shown in Fig 1.
Bending experiments have been performed on the
crystal. A model has been assumed wherein elastic bending
introduces strain energy (E ) due to compression and
3
H L
3
H L
s
stretching of outer and inner arcs, respectively. Interestingly,
the thinner crystals can be bent to a greater extent compared
to thicker crystals due to the fact that the thicker crystals
3 3
L and H
L1. (b) Molecular overlay
experience a greater level of strain energy, as the magnitude Fig. 2 (a) Packing diagram of H
of change in Δl (where l represents the length of the crystal) structure of H L (blue) and H
L1 (red).
Packing features of and
intra and intermolecular
3
3
for inner and outer arcs will be greater for the same extent of
bending.
L1 shows the presence of
–bonding interactions. The
H
3
L
H
3
H
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Page 3 of 5
ChemComm
Journal Name
COMMUNICATION
intramolecular O
–H···N interactions involves both the N atoms importance in biological assays and environmentaVliewmAortnicilteoOrnilninge
of an azine unit and the H atoms of hydroxy groups of naphthyl due to potential health implications ca
D
u
O
s
I
e
:
d
10.
b
10
y
39
o
/Cve7Crd
C
o
0
s
4
e of
392
A
3
4-36
and diol unit (Fig. S9). The intermolecular O
in involves an H-atom of diol group and an O atom of
adjacent diol group, O(3) H(103)···O(3), 1.998(1) Å leading to absorption and emission studies. The absorption spectra of
–
H···O, interaction aluminium.
H
3
L
The photophysical behavior of
3
H L was investigated via
–
3
H L
the formation of dimer with single hand shake position. in acetonitrile (ACN) mixture (7:3 v/v in 10 μM HEPES buffer at
Further, each dimeric unit is connected to neighbouring dimer pH = 7.2) was dominated by two absorption peaks at 325 and
forming 1D–polymeric chain (Fig. S10 and Table S3). However, 382 nm wavelength corresponding to the π–π* and n–π*
1
3+
in
atoms of diol group from one molecule to the H and O atoms form of Al(NO
of adjacent diol group, O(3) H(103)···O(2), 2.106(9) forming a absorption maxima at 325 and simultaneously increases at 382
dimer with both hand in hand handshake position with nm with an isosbestic point at 344 nm. This provides strong
H
3
L
an intramolecular interactions are between O and H transition, respectively. The subsequent addition of Al in the
3
)
3
·9H O results in a gradual decrease of
2
–
3+
additional C
of napthyl unit and hydrogen atom of neighboring molecule, S12). The emission spectra of
C(12) H(12)···O(1), 2.602(13) Å, leading to the formation of peak at 500 nm. The titration of
polymeric chain (Fig. S11 and Table S3). This H–bonded gradual enhancement in fluorescence intensity at 555 nm with
D–polymeric chain structures suggest that relaxation 50 nm bathochromic shift (Fig. 3a). A plausible reason for the
–
H···O, H
–
bonding interaction between an O atom evidence for enhanced binding of
3
H L towards Al ion (Fig.
exhibit a weak fluorescence
H L with Al resulted in a
3
3
H L
3+
–
1
1
D–
3+
processes are dominant which is favorable for elastic fluorescence turn on towards Al may be due to (i) the photo
bending. Moreover, other azine based ligands
33
3+
1 2
L and L in induced electron transfer (PET) suppressed by Al
absence of –OH groups do not undergo photo-induced SCSC coordination and (ii) large bathochromic shift and (iii)
35
transformation (Scheme S1 and S2). It is observed that the isosbestic point appear in absorption spectrum. Thus, the
intramolecular H(101)···N(1) and H(2)···N(2) distances in results obtained from absorption and emission studies clearly
are found to be 1.769(5) Å and 1.903(5) Å , respectively, indicate that the sensing behavior of
is specific to Al3+ ions.
whereas the similar intramolecular H(101)···N(1) and The limit of detection (LOD) was determined to be 42 nM and
3
H L
3
H L
1
H(2)···N(2) distances in
H
3
L
are found to be enhanced fluorescence response time was found to be 50 s (Fig. S13).
The selectivity test was also performed towards various
can be explain by metal ions with concentration four times the concentration of
considerably, 1.830(5) Å and 1.927(3) Å, respectively (Fig. S9).
1
The SCSC transformation of
3 3
H L to H L
3
the probable mechanistic pathways as shown in Scheme 2. In Al . However, the fluorescence intensity is turned-on only in
the first step, on exposure of
3+
3
H L to UV light the O–H···O presence of Al ion with about 30 fold enhancements (Fig.
hydrogen bonding interaction is cleaved (step 1) which brings S14b), the results showed that other metal ions do not
3
+
two adjacent molecules very close to each other from interfere with the intensity of H
3
L–Al system and
3
H L is
3+
approximately 5.642 Å to 2.806 Å but due to strong hindrance specific for Al (Fig. S14c). Moreover, to understand the mode
3
+ 1
between two bulkier naphthyl unit, one of the molecule of complexation between
vertically flipped to 180 . Thus, the two adjacent molecules been performed in DMSO
H
–
3
L
and Al , H NMR titration have
D6 ( ) and D O (Al(NO ·9H O)
strongly bonded to each other via strong O–H···O interactions solvents. On subsequent addition of Al to solution, the –
step 2) and subsequently each dimeric unit is stabilized by C OH peaks at 12.87, 10.87 and 9.36 ppm decrease and finally at
o
H
3
L
2
3
)
3
2
3
+
3
H L
(
–
1
3+
H···O interactions resulting in packing features of
discussed above. Further, the bending properties of
crystal was also explored which displayed same r value with S15). The stoichiometry of H
enhanced elastic property at a higher breaking strain of method and mass spectrum which shows 1:2(M:L) complex
3
H L as 0.8 equiv. of Al all three –OH peaks completely disappear
1
H
3
L
indicating the complex formation between
H
3
L
and Al3+ (Fig.
3+
c
3
L–Al was confirmed by Job’s
0
.001177 °/molecule as compared to
H
3
L
(Supplementary formation (Fig. S16 and S17). Furthermore, reversibility of the
chemosensor was also confirmed by the strong chelating agent
Video 5).
ethylene-diamine-tetra-acetic acid (EDTA). The enhanced
3+
fluorescence intensity of H
the EDTA, demonstrating the binding of
reversible in nature (Fig. 3b). The fluorescence quantum yield
3
L–Al was quenched after adding
with Al3+ is
3
H L
3
7
3+
and average life time of H
.182 and < τ > = 3.60 ns (Fig. S18 and Table S4). The
performance comparison of with other fluorescence
sensor for Al is shown in Supplementary Table S5.
3
L–Al was observed to be Φ =
0
3
H L
3+
1
Scheme 2. Proposed pathway for the transformation of H
After displaying excellent solid–state crystalline properties
and owing to its good solubility, we decided to
investigate the solution state properties. Aluminum is the third
most abundant element on the earth’s crust with a variety of
applications. The development of highly selective and sensitive
sensors for the detection of aluminum ions is of great
3 3
L to H L .
of
3
H L
Fig. 3 (a) Fluorescence spectra of H
intensity changes with respect to Al
Fluorescence Spectra of H L (20 µM) in the presence of 20 equiv. of
3
L, Inset: relative fluorescence
3+
concentration. (b)
3
3+
Al before and after treatment with excess EDTA (λex = 382 nm).
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 4 of 5
COMMUNICATION
Journal Name
In summary, we successfully demonstrated an elastic 16 S. Ghosh, M. K. Mishra, S. B. Kadambi, U. RamamViuewrtAyrtaicnledOnGlin. e
crystal by introducing a new functionality such as azine group. R. Desiraju, Angew. Chem. Int. Ed., 201
The elastic nature of crystals was found to be consistent in 17 A. C. Maahs, M. G. Ignacio, M. Ghazzali, D. V. Soldatov and K.
MeOH, EtOH and ACN solvents by producing long to very long E. Preuss, Cryst. Growth Des., 2017, 17, 1390.
length crystals. Photo-irradiation on results in a SCSC 18 O. S. Bushuyev, T. C. Corkery, C. J. Barrett and T. Friscic,
phase transformation by twisting of the molecule along a axis. Chem. Sci., 2014, , 3158.
Moreover, the mechanistic pathway of SCSC transformation of 19 (a) N. L. Toh, M. Nagarathinam and J. J. Vittal, Angew. Chem.
D
5
O
,
I
5
:
4
10
,
.
2
10
6
3
7
9
4
/C7CC04392A
.
3
H L
3
H L
5
1
H
3
L
to
H
3
L
has been explained. These findings in solid-state
Int. Ed., 2005, 44, 2237; (c) G. Liu, J. Liu, Y. Liu and X. Tao, J.
Am. Chem. Soc., 2014, 136, 590.
crystalline materials could be of vital importance in the fields
of crystal engineering and for the design of organic flexible 20 (a) H. Aggarwal, P. M. Bhatt, C. X. Bezuidenhout and L. J.
materials, flexible electronics devices and optics. Further, due
to excellent solubility, the solution state sensing behavior of
Barbour, J. Am. Chem. Soc., 2014, 136, 3776; (b) J. W. Brown,
B. L. Henderson, M. D. Kiesz, A. C. Whalley, W. Morris, S.
Grunder, H. Deng, H. Furukawa, J. I. Zink, J. F. Stoddart and
3 3
H L was explored. H L displays highly selective, sensitive and
3+
reversible sensing behavior towards Al with an LOD of 42
nM.
O. M. Yaghi, Chem. Sci., 2013,
4, 2858; (c) S. Shin, S. Jeong, D.
Kim and M. S. Lah, Cryst. Growth Des., 2017, 17, 2228.
We are grateful to the SIC, IIT Indore. S. M. M. thanks 21 (a) M. A. Sinnwell and L. R. MacGillivray, Angew. Chem. Int.
SERB-DST (Project No. EMR/2016/001113), New Delhi, for
financial support. We thank Prof. A. K. Singh, IIT Delhi for DSC
measurement. A. K. Saini and K. N. thank UGC and MHRD, New
Delhi, India, respectively, for research fellowships.
Ed., 2016, 55, 3477; (b) M. H. Mir, L. L. Koh, G. K. Tan and J. J.
Vittal, Angew. Chem. Int. Ed., 2010, 122, 400; (c) G. S.
Papaefstathiou, Z. Zhong, L. Geng and L. R. MacGillivray, J.
Am. Chem. Soc., 2014, 126, 9158.
2 T. Kim, L. Zhu, L. J. Mueller and C. J. Bardeen, J. Am. Chem.
Soc., 2014, 136, 6617.
3 (a) Y. Wang and N. Herron, J. Phys. Chem., 1991, 95, 525; (b)
M. Bendikov and F. Wudl, Chem. Rev., 2004, 104, 4891; (c) P.
K. Jain, X. Huang, I. H. El-Sayed, M, El-Sayed, Acc. Chem. Res.,
2
2
Notes and references
1
Q. Wei, K. Achazi, H. Liebe, A. Schulz, P.- L. M. Noeske, I.
Grunwald and R. Haag, Angew. Chem. Int. Ed., 2014, 53
1650.
,
2
008, 41, 1578; (d) S. Lv, D. M. Dudek, Y. Cao, M. M.
1
Balamurali, J. Gosline and H. Li, Nature 2010, 465, 69.
4 Y. Hong, J. W. Y. Lam and B. Z. Tang, Chem. Soc. Rev.,
2
3
4
5
Q. M. Zhang, H. Li, M. Poh, F. Xia, Z.Y. Cheng, H. Xu and C.
Huang, Nature 2002, 419, 284.
A. L. Briseno, R. J. Tseng, M. M. Ling, E. H. L. Falcao, Y. Yang,
F. Wudl and Z. Bao, Adv. Mater., 2006, 18, 2320.
Q. Tang, L. Li, Y. Song, Y. Liu, H. Li, W. Xu, Y. Liu, W. Hu and D.
Zhu, Adv. Mater., 2007, 19, 2624.
2
2
2
2
2
2
2
011, 40, 5361.
5 W. Z. Yuan, P. Lu, S. Chen, J. W. Y. Lam, Z. Wang, Y. Liu, H. S.
Kwok, Y. Ma and B. Z. Tang, Adv. Mater., 2010, 22, 2159.
6 K. P. Carter, A. M. Young and A. E. Palmer, Chem. Rev., 2014,
1
14, 4564.
7 S. Ghosh and C. M. Reddy, Angew. Chem. Int. Ed., 2012, 51
0319.
8 (a) D. B. Brown and M. Fatemi, J. Appl. Phys., 1980, 51, 2540;
b) D. L. Dorset, Acta. Cryst. A., 1980, 36, 592.
E. C. W. Ou, L. Hu, G. C. R. Raymond, O. K. Soo, J. Pan, Z.
Zheng, Y. Park, D. Hecht, G. Irvin, P. Drzaic and G. Gruner,
,
1
ACS Nano 2009,
J. A. Rogers, T. Someya and Y. Huang, Science 2010, 327
603.
(a) M. Owczarek, K. A. Hujsak, D. P. Ferris, A. Prokofjevs, I.
Majerz, P. Szklarz, H. Zhang, A. A. Sarjeant, C. L. Stern, R.
Jakubas, S. Hong, V. P. Dravid and J. F. Stoddart, Nat.
3, 2258.
6
7
,
(
1
9 (a) B. I. Yakobson, C. J. Brabec and J. Bernholc, Phys. Rev.
Lett., 1996, 76, 2511; (b) R. Martel, H. R. Saha and P. Avouris,
J. Phys. Chem. B., 1999, 103, 7551.
0 D. J. Barber and R. London, An Introduction to the Properties
of Condensed Matter, Cambridge University Press,
Cambridge, 1989.
3
3
Commun., 2016, 7, 13108; (b) L. Wen, L. Zhou, B. Zhang, X.
Meng, H. Xu and D. Li, J. Mater. Chem., 2012, 22, 22603.
G. R. Krishna, R. Devarapalli, G. Lal and C. M. Reddy, J. Am.
Chem. Soc., 2016, 138, 13561.
8
9
1 (a) V. A. Atrazhev, S. F. Burlatsky, D. V. Dmitriev and V. I.
Sultanov, J. Stat. Mech., 2013, 13, 2004; (b) S. M. Notley, B.
(a) S. Takamizawa and Y. Miyamoto, Angew. Chem. Int. Ed.,
Pettersson and L. Wagberg, J. Am. Chem. Soc., 2004, 126
3930.
2 O. S. Bushuyev, A. Tomberg, T. Frisci
Chem. Soc., 2013, 135, 12556.
3 S. Jacimovski and D. Rakovic, Acta Phys. Pol. Acta., 2011,
20, 231.
4 A. K. Saini, V. Sharma, P. Mathur and M. M. Shaikh, Sci. Rep.,
016, , 34807.
5 S. Kim, J. Y. Noh, K. Y. Kim, J. H. Kim, H. K. Kang, S.-W. Nam, S.
H. Kim, S. Park, C. Kim and J. Kim, Inorg. Chem., 2012, 51
597.
6 Y. Lu, S. Huang, Y. Liu, S. He, L. Zhao and X. Zeng, Org. Lett.,
011, 13, 5274.
,
2
014, 53, 6970; (b) S. Takamizawa and Y. Takasaki, Angew.
1
Chem. Int. Ed., 2015, 54, 4815.
3
3
3
3
̌
c
̌
and C. J. Barrett, J. Am.
1
1
1
1
0 S. Saha and G. R. Desiraju, Chem. Commun., 2016, 52, 7676.
1 P. Fratzl and F. G. Barth, Nature 2009, 462, 442.
2 Y. Cao and H. Li, Nat. Nanotechnol., 2008, 3, 512.
1
3 (a) M. K. Panda, S. Ghosh, N. Yasuda, T. Moriwaki, G. D.
Mukherjee, C. M. Reddy and P. Naumov, Nat. Chem., 2015,
2
6
7
, 65; (b) L. Pejov, M. K. Panda, T. Moriwaki and P. Naumov,
J. Am. Chem. Soc., 2017, 139, 2318; (c) D. P. Karothu, J.
Weston, I. T. Desta and P. Naumov, J. Am. Chem. Soc., 2016,
,
3
1
38, 13298.
3
3
1
1
4 C. M. Reddy, M. T. Kirchner, R. C. Gundakaram, K. A.
2
Padmanabhan and G. R. Desiraju, Chem.–Eur. J., 2006, 12
222.
5 S. Saha and G. R. Desiraju, J. Am. Chem. Soc., 2017, 139
975.
,
7 E. Heyer, P. Lory, J. Leprince, M. Moreau, A. Romieu, M.
Guardigli, A. Roda and R. Ziessel, Angew. Chem. Int. Ed.,
2
,
2
015, 54, 2995.
1
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 5
ChemComm
View Article Online
DOI: 10.1039/C7CC04392A
Multifunctional azine ligand with elastic bending with full phase retention, photoinduced SCSC
3+
transformation and sensitive Al detection