A novel dicationic ionic liquids encompassing pyridinium hydrazone-phenoxy conjugates as antimicrobial agents targeting diverse high resistant microbial strains

Article abstract of DOI:10.1016/j.molliq.2019.04.010

A focused library of new dicationic ionic liquids (DiILs) 6–41 appended pyridinium hydrazone and phenoxy side chain hybrids as counter cations were designed and synthesized, utilizing quaternization and metathesis reactions under both conventional and microwave irradiation. The novel DiILs 6–41 were fully characterized using different spectroscopic tools (¹H, ¹³C, ¹⁹F, ¹¹B, ³¹P NMR and mass spectra) and evaluated for their antimicrobial activity against diverse types of high resistant strains including two Gram-positive bacteria; methicillin-resistant Staphylococcus aureus (MRSA), Clostridium difficile, two Gram-negative bacteria; two Escherichia coli isolates, and Neisseria gonorrhea, and fungal strain; Candida albicans. The antibacterial screening was carried out by broth microdilution method and MIC values were reported as indicator of growth inhibition. They mostly exhibited antibacterial effect against MRSA and EC strains. The effect of the synthesized ILs on Gram-positive bacteria showed the phenoxy linker chain increases, the MIC values increases with more lethal effect due to the hydrophobicity parameter. This behavior was confirmed by the molecular dynamic simulation through the interaction with surface membrane as general mechanism of ILs. The dicationic ionic liquids are considered promising motifs for further investigations with focusing on the terminal hydrophobic adjuster.

Full text of DOI:10.1016/j.molliq.2019.04.010

Accepted Manuscript
A novel dicationic ionic liquids encompassing pyridinium
hydrazone-phenoxy conjugates as antimicrobial agents targeting
diverse high resistant microbial strains
Nadjet Rezki, Salsabeel A. Al-Sodies, Hany E.A. Ahmed, Saleh
Ihmaid, Mouslim Messali, Sahar Ahmed, Mohamed Reda Aouad
PII:
S0167-7322(19)31116-X
DOI:
https://doi.org/10.1016/j.molliq.2019.04.010
MOLLIQ 10733
Reference:
To appear in:
Journal of Molecular Liquids
Received date:
Revised date:
Accepted date:
25 February 2019
31 March 2019
2 April 2019
Please cite this article as: N. Rezki, S.A. Al-Sodies, H.E.A. Ahmed, et al., A novel
dicationic ionic liquids encompassing pyridinium hydrazone-phenoxy conjugates as
antimicrobial agents targeting diverse high resistant microbial strains, Journal of
Molecular Liquids, https://doi.org/10.1016/j.molliq.2019.04.010
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ACCEPTED MANUSCRIPT
A Novel Dicationic Ionic Liquids Encompassing Pyridinium Hydrazone-Phenoxy
Conjugates as Antimicrobial Agents Targeting Diverse High Resistant Microbial
Strains
a,b,
a
c,d
c
Nadjet Rezki, * Salsabeel A. Al-Sodies, Hany E. A. Ahmed, Saleh Ihmaid, Mouslim
a
c,e
a,
Messali, Sahar Ahmed, Mohamed Reda Aouad, *
a
Department of Chemistry, Faculty of Science, Taibah University, Al-Madinah Al-Munawarah 30002,
Saudi Arabia
b
Department of Chemistry, Faculty of Sciences, University of Sciences and Technology Mohamed Boudiaf,
Laboratoire de Chimie et Electrochimie des Complexes Metalliques (LCECM) USTO-MB, P.O. Box 1505,
El M‘nouar, Oran 31000, Algeria
c
Pharmacognosy and Pharmaceutical Chemistry Department, Pharmacy College, Taibah University, Al-
Madinah Al-Munawarah 41477, Saudi Arabia.
d
Department of Pharmaceutical Organic Chemistry, Faculty of Pharmacy, Al-Azhar University, Nasr City,
1
1754, Cairo, Egypt
e
Medicinal Chemistry Department, Faculty of Pharmacy, Assiut University, Assiut 71526, Egypt
*Corresponding authors
E-mail address: nadjetrezki@yahoo.fr (N. Rezki), aouadmohamedreda@yahoo.fr (M.R. Aouad)
ABSTRACT
A focused library of new dicationic ionic liquids (DiILs) 6-41 appended pyridinium
hydrazone and phenoxy side chain hybrids as counter cations were designed and
synthesized, utilizing quaternization and metathesis reactions under both conventional
and microwave irradiation. The novel DiILs 6-41 were fully characterized using different
1
13
19
11
31
spectroscopic tools ( H, C, F, B, P NMR and mass spectra) and evaluated for their
antimicrobial activity against diverse types of high resistant strains including two Gram-
positive bacteria; methicillin-resistant Staphylococcus aureus (MRSA), Clostridium
difficile, two Gram-negative bacteria; two Escherichia coli isolates, and Neisseria
gonorrhea, and fungal strain; Candida albicans. The antibacterial screening was carried
out by broth microdilution method and MIC values were reported as indicator of growth
inhibition. They mostly exhibited antibacterial effect against MRSA and EC strains. The
effect of the synthesized ILs on Gram-positive bacteria showed the phenoxy linker chain
increases, the MIC values increases with more lethal effect due to the hydrophobicity
parameter. This behavior was confirmed by the molecular dynamic simulation through
the interaction with surface membrane as general mechanism of ILs. The dicationc ionic

ACCEPTED MANUSCRIPT
liquids are considered promising motifs for further investigations with focusing on the
terminal hydrophobic adjuster.
Keywords: Dicationic ionic liquids; pyridinium hydrazone; antimicrobial activity; SAR;
docking.
1
. Introduction
Recently, the modern medicinal chemistry becomes intensively investigated to overcome
the challenge of drug design. Molecular hybridization involves the holistic design of
novel chemical scaffolds by combination of two or more bioactive entities to optimize
and increase the pharmacological properties of the targeted hybrid molecules (the
building block in drug discovery) [1-2]. The antibiotic resistance threatens to undermine
the entire structure of modern medicine which relies heavily on widespread use of
antibiotics to curb bacterial infections, particularly in healthcare settings. One particularly
problematic resistant pathogen is methicillin-resistant Staphylococcus aureus (MRSA).
Hydrazones are a kind of Schiff bases containing tunable azomethine linkage and are
widely used in drug design [3-4]. These classes have increasingly attracted attention
owing to their fascinating pharmacological activities such as anticancer [5], antimicrobial
[
6], anti-inflammatory [7] and antioxidant [8] properties.
Ionic liquids were originally defined as mixed metal anion and organic cation derived
from different nitrogen containing heterocycles. Pyridine derivatives are attractive
candidates in synthetic ionic liquids chemistry as convenient organic cations. Among
these, the functionalized pyridines are heterocycles that are suitable for ionic liquids
synthesis. This class of ILs is one of the most relevant motifs in organic chemistry with
many promising chemical, physical and biological properties [9-10] including
antibacterial [11], anti-inflammatory [12], antiproliferative [13] and antitubercular [14]
activity. Recently, dicationic ionic liquids (DiILs), a new category of ILs family, attracted
great concern as it represents an interesting variation of the cationic partner. DiILs consist
of two head groups (cations) linked by a rigid or flexible spacer and two anions. These
groups possess valuable advantages over monocationic ILs like higher thermal stability,
lower critical micelle concentration (CMC) values and larger d-spacing of crystal
structure [15-17]. Moreover, DiILs have been studied as lubricants, herbicides, magnetic
liquids or chiral salts [18-20]. Recently, we reported the synthesis of an array of

ACCEPTED MANUSCRIPT
dicationic ionic liquids tethering pyridinium hydrazone-phenacyl conjugates as promising
anticancer agents [21]. On the other hand, microwave assisted organic synthesis (MAOS)
provide ideal opportunities for the green chemistry in term of reaction times reduction
and yields improvement [22-25]. Based upon the results of such study, it was decided to
anticipate the conjunction of bis-pyridine hydrazones with some suitable substituted
phenoxyalkyl side chains as novel dicationic pyridinium ionic liquids under both classical
and microwave irradiation and subjecting of the novel compounds for testing of their
antimicrobial activity against the highly resistant strains.
2
. Results and Discussion
2
.1. Chemistry
The synthetic route investigated in the present work has been outlined in scheme
. The hydrazones 4 and/or 5 have been taken as starting materials in the synthesis of the
1
desired di-ionic liquids (DiILs) 6-41. These hydrazones in turn have been obtained by
thermal condensation of isonicotinaldehyde 1 and/or nicotinaldehyde 2 with
isonicotinohydrazide 3 in ethanol as solvent and a catalytic amount of hydrochloric acid
[
26, 27]. When the condensation was carried out under MWI, the hydrazones were
obtained in 96-98 % within 2-3 mins.

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Scheme 1. Synthesis of dicationic ionic liquids tethering pyridinium hydrazone-phenacyl
conjugates 6-41
As continuation of our previous work on the synthesis of ionic liquids [28-33] and
by taking the advantage of quaternization and metathesis reactions, we have adopted an
efficient and facile ecofriendly microwave assisted synthesis of a library of task specific
dipyridinium ionic liquids 6-41.
First, the quaternization of pyridine azomethine nitrogen atoms (=N-) of the
synthesized dipyridine hydrazones 4 and/or 5 with two equivalents of the appropriate
bromoalkoxybenzene derivatives (Scheme 1), in refluxing acetonitrile for 6-8 hours, gave
the corresponding halogenated di-cationic pyridinium ionic liquids (DiILs) appended
various phenoxy side chains 6-11 in 84-88% yields (Table 1). Much increase in reaction
yields (92-98%) and reduction in reaction time 3-4 mins were observed when the
quaternization was carried out under microwave irradiation (Table 1).
Second, the metathesis reaction has been performed through the exchange of the bromide
counter anion. Thus, thermal heating of the halogenated DiILs 6-11, in acetonitrile for 16
hours, with the appropriate metal salts (KPF , NaBF , CF COONa, NaSCN, NaN(CN) )
6
4
3
2

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gave the desired task-specific DiILs 12-41 in yield 80-89 %. The same DiILs were
obtained in yield 90-98 %, within 10 min, when the anion exchange was assisted by MWI
(Table 1).
Table 1
MAOS versus conventional synthesis of DiILs 6-41: times and yields.
Comp
No
n
3/4-
Pyridyl
Y
Conventional procedure
CP
Microwave irradiation
MWI
Time (h)
Yield (%)
Time (min) Yield (%)
6
7
8
9
2
3
4
2
3
4
2
2
2
2
2
3
3
3
3
3
4
4
4
4
4
2
2
2
2
2
3
3
3
3
3
4
4
4
4
4
4-Pyridyl
4-Pyridyl
4-Pyridyl
3-Pyridyl
3-Pyridyl
3-Pyridyl
4-Pyridyl
4-Pyridyl
4-Pyridyl
4-Pyridyl
4-Pyridyl
4-Pyridyl
4-Pyridyl
4-Pyridyl
4-Pyridyl
4-Pyridyl
4-Pyridyl
4-Pyridyl
4-Pyridyl
4-Pyridyl
4-Pyridyl
3-Pyridyl
3-Pyridyl
3-Pyridyl
3-Pyridyl
3-Pyridyl
3-Pyridyl
3-Pyridyl
3-Pyridyl
3-Pyridyl
3-Pyridyl
3-Pyridyl
3-Pyridyl
3-Pyridyl
3-Pyridyl
3-Pyridyl
I
I
I
I
I
I
PF
BF
6
6
7
6
8
8
86
84
3
3
4
4
4
4
94
96
96
98
94
92
92
98
90
94
93
92
98
92
92
98
94
94
94
96
92
98
96
98
92
94
92
92
90
90
92
94
96
96
95
98
88
88
86
86
82
80
84
88
85
87
88
88
86
88
89
88
87
82
88
89
84
88
89
86
88
88
87
84
86
88
85
87
88
86
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
6
4
COOCF
SCN
N(CN)
PF
BF
COOCF
SCN
N(CN)
PF
BF
COOCF
SCN
N(CN)
PF
BF
COOCF
SCN
N(CN)
PF
BF
COOCF
3
2
6
4
3
2
6
4
3
2
6
4
3
2
6
4
3
SCN
N(CN)
PF
BF
COOCF
2
6
4
3
SCN
N(CN)
2

ACCEPTED MANUSCRIPT
2
.2. Spectroscopic characterization
The construction of the target ionic liquids 6-41 was unambiguously confirmed by
their spectroscopic results.
2
.2.1. Quaternization reaction
The formation of the halogenated dipyridinium ILs 6-11 was confirmed by their
1
13
1
H and C NMR spectra. Their H NMR spectra exhibited two diagnostic triplets around
.03-5.18 ppm belonging to the NCH and OCH protons. Pyridinium ILs 7 and 10
4
2
2
bearing propyl linkage showed multiplets at 2.24-2.47 ppm assignable to the internal
methylene protons (CH CH CH ), which supported the proposed structures. On the other
2
2
2
hand, the presence of two butoxyphenyl side chains in the structures of ILs 8 and 11 was
clearly evidenced through the appearance of two distinct multiplets between 1.79 and
2
.16 ppm. In addition, the spectra of ILs 6-11 also revealed the presence of ten extra
protons in the aromatic area, which confirmed the success of the quaternization reaction
of the two pyridine rings with the appropriate phenyoxyalkyl bromide derivatives.
1
3
The success of the alkylation reaction was also confirmed by the C NMR results, which
were in agreement with the proposed structures. All spectra revealed the appearance of
new signals in the aliphatic region near 25.76-67.14 ppm characteristic of the alkoxy
carbons (NCH (CH ) CH OPh). Moreover, additional aromatic carbons were recorded at
2
2 n
2
1
14.92-149.22 ppm attributed to the two phenoxy rings.
2
.2.2. Metathesis reaction
All newly synthesized specific task-DiILs 12-41 have been elucidated using
1
13
19
31
11
H NMR, C NMR, F NMR, P NMR, B NMR and mass spectra. No change has
been observed in the protons and carbons assignment of the ILs 12-41 compared to their
corresponding halogenated ILs 6-11.
1
1
The significant peaks corresponding to the major anions were obvious in the B
31
19
NMR, P NMR and F NMR spectra. Thus, the success of the metathethical exchange
-
of the bromide anion with PF anion was deduced from the presence of a diagnostic
6
19
doublet at -71.08 to -71.03 ppm and a septet between -157.39 to -131.04 ppm in the F
31
NMR and P NMR spectra, respectively, which clearly indicated the presence of
hexafluorophosphate as counter anion in their structures.

ACCEPTED MANUSCRIPT
1
9
11
On the other hand, the F and B NMR spectra showed the presence of two
characteristic doublets around -148.39 to -148.12 ppm and a multiplet ranging between
-1.32 and -1.29 ppm, respectively. Such signals were in agreement with the structures of
-
dipyridinium ILs tethering tetrafluoroborate anion (BF ) as anionic head group.
4
1
9
Moreover, the F NMR analysis was also used to confirm the bromide exchange
-
with the trifluoroacetate anion (CF COO ). Thus, the appearance of a sharp singlet at -
3
-
7
3.87 to -73.47 ppm supported the structures of DiILs carrying the CF COO anion.
3
-
-
Since the dipyridinium ionic liquids carrying SCN and/or N(CN) anion head-
2
1
13
groups displayed similar H and C NMR spectra compared to their halogenated
precursors; the structural elucidation of these ionic liquids become more evident based on
their mass spectra (see experimental part).
2
.3. Antimicrobial testing results
In this study, the newly synthesized diionic liquids (DiILs) were tested for their
antimicrobial activity against human pathogenic strains; two Gram-positive bacteria
including; methicillin-resistant Staphylococcus aureus (MRSA), Clostridium difficile
(C.D), two Gram-negative bacteria including; two Escherichia coli isolates (E.C TM, E.C
WT), and Neisseria gonorrhea (N.G). The antifungal evaluation was determined against
Candida albicans (C.A). The data obtained are compared to control drugs (gentamicin,
linezolid, vancomycin, cefixime, fluconazole and 5-fluorocytosine (5-FC). The observed
minimum inhibitory concentration (MIC) antimicrobial data of the compounds and the
reference drugs are given in (Tables 2 and 3).
The results of the in vitro antimicrobial screening revealed that, the series of diionic
liquids with presences of 3-pyridyl moiety linked through the hydrazone part and ended
with substituted phenoxy ring exhibited promising antibacterial and antifungal inhibitory
effects against a wide range of microbial strains. Table 2 showed that the compounds 6,
1
8, 19, 20, 21, 23, 24, 25 and 26 has best activity towards Gram-negative bacteria (E.C
TM) with inhibition zone 32-64 µg/mL. The compounds 12, 13 and 23 showed high
activity against fungi (C.A) with inhibition zone 32-64 µg/mL. However, the compounds
2
8, 29, 33 and 35 showed high activity against Gram negative bacteria (E.C TM) with
inhibition range zone 32-64 µg/mL. The compounds 7, 8, 14, 15, 17 and 22 showed low
activity against Gram positive bacteria, negative bacteria (E.C TM) and fungi with

ACCEPTED MANUSCRIPT
inhibition range zone 128-150 µg/mL. Based on the obtained results for each of the
newly synthesized compounds, it is evident that compounds 23 and 29 have more potent
effect when compared to the others. Table 3 showed the compound 9 has best activity
towards Gram-negative bacteria with MIC 64 µg/mL and less potent towards Gram
positive bacteria and fungi as compared with the reference drugs. The compounds 27, 29,
3
5, 39 and 41 showed high activity against Gram positive bacteria (MRSA) with
inhibition range zone 16-64 µg/mL. The compounds 28, 29, 33 and 35 showed high
activity against Gram negative bacteria (E.C TM) with inhibition range zone 32-64
µg/mL. The compounds 10, 11, 30, 31, 32, 34, 36, 37, 38 and 40, showed low activity
against Gram positive bacteria, negative bacteria (E.C TM) and fungi with inhibition
range zone 128-150 µg/mL.
Table 2
MIC values for inhibition growth of bacteria (µg /mL).
MIC (µg/mL)
Gm-ve
E.C WT
Comp
No
R
Y
I
Gm+ve
MRSA C.D
Fungi
C.A
150
150
128
64
128
≥150
64
≥150
32
≥150
≥150
128
≥150
≥150
128
≥150
≥150
≥150
NT
E.C TM
64
N.G
128
128
150
128
6
7
8
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
)
)
)
)
)
)
)
)
)
)
)
)
)
)
)
)
)
)
2
3
4
2
3
4
2
3
4
2
3
4
2
3
4
2
3
4
OPh
OPh
OPh
OPh
OPh
OPh
OPh
OPh
OPh
OPh
150
150
64
≥150
128
128
150
≥150
≥150
150
150
150
150
150
150
150
150
150
150
150
150
150
150
150
NT
≥150
≥150
128
128
128
128
64
32
128
64
32
128
64
32
128
32
1
1
2
1
1
2
1
1
2
1
2
2
1
2
2
2
7
2
3
8
3
4
9
4
5
0
5
6
1
6
150
64
150
150
150
32
≥150
≥150
≥150
≥150
≥150
64
PF6
BF4
≥150
≥150
≥150
≥150
≥150
≥150
≥150
≥150
≥150
≥150
≥150
≥150
≥150
≥150
NT
150
150
128
150
150
128
150
150
128
1
≥150
≥150
128
≥150
≥150
128
OPh COOCF3
OPh
OPh
OPh
OPh
OPh
SCN
128
OPh N(CN)2
OPh
≥150
≥150
8
64
128
NT
Linezolid
1
NT
NT
2
NT
Vancomycin
Gentamicin
-Flurouracil
NT
NT
≤0.5
≤0.5
NT
0.5
NT
NT
NT
NT
5
NT
NT
NT: Not Tested

ACCEPTED MANUSCRIPT
Table 3
MIC values for inhibition growth of bacteria (µg /mL).
MIC (µg/mL)
Gm-ve
Comp
No
R
Y
I
Gm+ve
MRSA C.D
Fungi
C.A
128
≥150
≥150
128
≥150
≥150
≥150
≥150
≥150
64
≥150
≥150
≥150
≥150
≥150
≥150
≥150
64
E.C TM
E.C WT
N.G
128
≥150
≥150
128
9
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
(CH
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
)
)
)
)
)
)
)
)
)
)
)
)
)
)
)
)
)
)
2
3
4
2
3
4
2
3
4
2
3
4
2
3
4
2
3
4
OPh
OPh
OPh
OPh
OPh
OPh
OPh
OPh
OPh
OPh
150
150
150
64
150
150
150
150
150
16
≥150
≥150
≥150
≥150
≥150
≥150
128
≥150
≥150
64
64
128
128
64
128
128
64
32
≥150
32
150
150
150
150
150
150
150
150
150
64
1
1
2
3
3
2
3
3
2
3
3
3
3
4
3
3
4
0
1
7
2
7
8
3
8
9
4
9
0
5
0
1
6
1
PF6
BF4
≥150
≥150
≥150
≥150
≥150
≥150
≥150
≥150
≥150
≥150
≥150
≥150
≥150
≥150
NT
OPh COOCF3
150
64
≥150
128
128
128
128
32
≥150
128
≥150
128
128
NT
150
150
150
150
128
150
150
150
NT
OPh
OPh
OPh
OPh
OPh
150
64
128
128
SCN
128
150
150
32
≥150
128
≥150
≥150
8
OPh N(CN)2
OPh
Linezolid
1
NT
NT
1
NT
NT
2
Vancomycin
Gentamicin
-Flurouracil
NT
NT
≤0.5
≤0.5
NT
0.5
NT
NT
NT
NT
5
NT
NT
2
.4. Molecular Dynamics Simulations (MDs)
Molecular dynamics simulations (MDs) were performed to study the interaction
mechanism between the DiILs and cell membranes as mechanistic protocol for activity.
IL 23 was selected as model for the computational studies since they exhibit the worst
and best biological activity, respectively. Molecular dynamics (MD) simulations were
performed for the three-dimensional (3D) structures DOPC bilayer to study their
incorporation into the lipid phase using the MOE [34] (Molecular Operating
Environment) program and the MMFF94x force field as distributed in MOE (Chemical
Computing Group). According to the antibacterial screening and biological activity
determinations, DiILs with longer aliphatic chains are expected to be incorporated into
the lipid bilayer easily and quickly. This was done by immersion of the IL 23 in bulk

ACCEPTED MANUSCRIPT
water solvent at distance at 30 Å the distance between the ligand and the lipid center. IL
2
3 was incorporated into the bilayer and left for 10 ns for complete contact solvation with
the membrane as example of passive diffusion of the IL through the membrane surface.
The simulation analyses revealed that compound interact firstly with the membrane polar
surface through the twisted scaffold of polar pyridine moieties as polar-polar interaction
at 5 ps, (Fig.1). Once the touching to the surface occurs, the molecule applied full
twisting and incorporation of polar moieties to interact with upper layer after 25 ps the
structure orientation into the membrane. Following the simulation, the compound once
entered the upper layer showed changing in the orientation of hydrophobic side chain to
the lipophilic middle of membrane after 40 ps (Fig. 1). The calculated potential energy
for the incorporation effect of compounds 23 and 29 was reported at 50 ps (Fig. 2). In
general, the analysis of MD simulation proved the structural features effect, including the
pyridinium scaffold, linker hydrazide, and hydrophobic side chains, in the diffusion of
such compounds across the cell membrane and might be responsible for their
antibacterial effect.
Time; 15 ps
Time; 30 ps

ACCEPTED MANUSCRIPT
Time; 40 ps
Time; 50 ps
Fig. 1. Incorporation of DiIL 23 into the DOPC membrane along with the 50 ns MDs.
Fig. 2. The calculated potential energy analysis for DiILs 23 and 18 with different linkers
as a function of 50 ns simulation time

ACCEPTED MANUSCRIPT
2
.5. ADME Properties
ADME properties were predicted for the most active broad antimicrobial DiILs
2
3 and 29 for their molecular and physical properties as an aid for understanding their
mechanism. The results suggested that there are no significant violations of Lipinski’s
rule since all calculated physicochemical descriptors and pharmacokinetics properties are
within the expected thresholds (molecular weight (g/mol) = 400-500; Log P = 3.72-5.28;
HB acceptors = 7 and HB donors = 1) (Table 4). Additionally, PSA and water solubility
(log S) parameters play an important role in the membrane penetration and so the IL 23
showed slight more hydrophobicity than the other with good permeability due to the
linker variations on the pyridinium cations.
Table 4
The in-silico ADME evaluation of active compounds.
Ligand
Mwt
LogP
HB-D
HB-A
TPSA
Logs
Vdw_SA
2
2
3
9
524
5.28
1
7
67.5
-5.25
570
468
3.72
1
7
67.8
-4.45
501
2
.6. Molecular docking analysis
In an attempt to understand the mechanism of such new dipyridinium ILs as
antimicrobial agents, docking experiments were conducted against the microbial target,
E. coli glucosamine-6-P synthase, which plays an important role of amination of glucose
to be converted into the amino sugars applied in constitution of the polysaccharides in the
cell membrane. The aim of such work is to study the binding modes of ILs inhibitors that
might be involved in the interference with the cellular membrane through this mechanism
[
35]. We have selected the most active DiIL 23 to be used in the analysis and the results
are depicted in (Fig. 3 and Table 5). We have used the validated docking protocol using
the high resolution of E. coli glucosamine-6-P synthase as the target protein. All
compounds are predicted to form stable hydrophobic and hydrogen bonding interactions.

ACCEPTED MANUSCRIPT
Fig. 3. Molecular docking pose of the most active DiIL 23 in the binding pocket of E.
coli glucosamine-6-P synthase with 2D and 3D analyses.
Table 5
The reported data for affinity and inhibition constant of ILs 23 and 29.
IL ID Affinity energy (Kcal/mol) Calculated GlcN-6-P inhibition constant,
Ki = μM (micromolar)
2
2
3
9
-10.4
-9.5
9.6
7.16
3
. Conclusion
Under green microwave conditions, some novel dicationic ionic liquids tethering
pyridinium hydrazone-phenoxy conjugates have been synthesized and evaluated for their
antibacterial activity against high resistant bacterial and fungal strains. The results are

ACCEPTED MANUSCRIPT
very promising and could inhibit the growth of the microorganisms by different MIC
values. Among these derivatives, the DiIL 23 displayed the highest inhibitory activity
against MRSA, E.C TM, C.A and C.D by (MIC = 32, 64, 32 and 32 µg/mL) respectively.
In addition, the DiIL 29 was more potent against MRSA (MIC 16 µg/mL) and E.C WT
(MIC 64 µg/mL). The SAR analyses proved that the linker n = 2 at the 3-position of
pyridinium scaffold have strong enhancement of the antimicrobial activities. While the
increase of the linker to n = 4 at 4-position will increase the activity against Gram
positive. The molecular dynamic simulation revealed the interaction behavior of the
target ILs to the cellular membranes surface showing a passive diffusion mechanism
towards the surface layer.
4
. Experimental Section
4
.1. General
Melting points were recorded on a Stuart Scientific SMP1 apparatus and are uncorrected.
1
13
19
31
11
The newly designed compounds were characterized by H, C, F, P, B-NMR
spectroscopy and HRMS. The NMR spectra were measured with a 400 MHz Bruker
NMR spectrometer. Chemical shifts (δ) were reported in ppm, with tetramethylsilane
(TMS) as an internal standard. High resolution mass spectroscopy (HRMS) was carried
out using a LC-MS/MS impact II. A controllable single-mode microwave reactor (CEM
Discovery) was used to carry out the microwave-assisted reactions. The microwave
reactor was equipped with a magnetic stirrer as well as pressure, temperature, and power
controls and a nitrogen cooling system. The maximum operating pressure of the reactor
6
was 2 x 10 Pa and the power was set to 300 W.
4
4
4
.2. Synthesis and characterization
.2.1. General procedures for the synthesis of dipyridine hydrazones 4 and/or 5
.2.1.1. Conventional procedure (CP)
A mixture of 3-pyridinecarboxaldehyde (1) and/or 4-pyridinecarboxaldehyde (2) (10
mmol) in ethanol (30 mL) and isonicotinic acid hydrazide (3) (10 mmol) with few drops
of hydrochloric acid was heated under reflux for 1 h. The solid obtained after the

ACCEPTED MANUSCRIPT
evaporation of the solvent under reduced pressure was recrystallized from ethanol to
furnish the desired Schiff bases 4 and/or 5.
4
.2.1.2. Microwave irradiation (MWI)
3
-Pyridinecarboxaldehyde (1) and/or 4-pyridinecarboxaldehyde (2) (1 mmol), ethanol (5
mL), isonicotinic acid hydrazide (3) (1 mmol) and few drops of hydrochloric acid were
placed in closed borosilicate glass vessel fitted with a silicone cap and exposed to
irradiation for 2-3 min using a microwave reactor. The reaction was processed as
described in the conventional procedure outlined earlier to give the same targets 4 and/or
5
4
4
.
.2.2. Characterization
.2.2.1. (E)-N′-(pyridin-4-ylmethylene)isonicotinohydrazide (4)
Yellow crystals, yields: 92 % (CP) and 96 % (MWI), mp: 223-224 ºC (Lit. mp: 224-225
1
ºC) [26, 27] H NMR (400 MHz, DMSO-d ): δ = 7.57 (d, 0.25H, J = 4 Hz, Ar-H), 7.71
6
H
(d, 0.25H, J = 4 Hz, Ar-H), 7.82 (d, 1.75H, J = 8 Hz, Ar-H), 7.90 (dd, 1.75H, J = 4 Hz, 8
Hz, Ar-H), 8.14 (s, 0.2H, H-C=N), 8.55 (s, 0.8H, H-C=N), 8.66 (d, 0.25H, J = 4 Hz, Ar-
H), 8.74 (d, 1.75H, J = 4 Hz, Ar-H), 8.79 (d, 0.25H, J = 4 Hz, Ar-H), 8.84 (dd, 1.75H, J
1
3
=
4 Hz, 8 Hz, Ar-H), 12.47 (s, 0.2H, CONH), 12.58 (s, 0.8H, CONH). C NMR (100
MHz, DMSO-d ): δ = 121.32, 121.62, 121.76, 123.28, 140.14, 142.58, 146.21, 149.21,
6
C
+
1
49.48, 150.38 (Ar-C), 162.08, 162.10 (C=N, C=O). HRMS (ESI) m/z = 226.1414 [M ].
.2.2.2. (E)-N′-(pyridin-3-ylmethylene)isonicotinohydrazide (5)
4
Yellow crystals, yields: 95 % (CM) and 98 % (MWI), mp: 230-231 ºC (Lit. mp: 230-233
1
ºC) [26, 27]. H NMR (400 MHz, DMSO-d ): δ = 7.43 (dd, 0.2 H, J = 6 Hz, Ar-H), 7.52
6
H
(dd, 0.8H, J = 4 Hz, 8 Hz, Ar-H), 7.68 (d, 0.2 H, J = 4 Hz, Ar-H), 7.84 (dd, 1.8 H, J = 4
Hz, 8 Hz, Ar-H), 7.89 (d, 0.2H, J = 4 Hz, Ar-H), 8.15 (s, 0.2 H, H-C=N), 8.18 (dd, 0.8 H,
J = 4 Hz, 8 Hz, Ar-H), 8.53 (s, 0.8H, H-C=N), 8.57 (d, 0.2H, J = 4 Hz, Ar-H), 8.65 (dd,
0
.8H, J = 4 Hz, 8 Hz, Ar-H), 8.72 (s, 0.2H, Ar-H), 8.75 (d, 0.2H, J = 4 Hz, Ar-H), 8.81
(dd, 1.8H, J = 4 Hz, 8 Hz, Ar-H), 8.89 (s, 0.8H, Ar-H), 12.20 (s, 0.2H, CONH), 12.25 (s,
1
3
0
1
1
.8H, CONH). C NMR (100 MHz, DMSO-d ): δ = 122.01, 123.58, 124.43, 124.53,
6 C
30.29, 130.42, 133.86, 134.10, 140.74, 141.96, 142.43, 146.79, 149.38, 149.40, 150.83,
+
51.74 (Ar-C), 162.23, 168.46 (C=N, C=O). HRMS (ESI) m/z = 226.1418 [M ].

ACCEPTED MANUSCRIPT
4
6
.2.3. General quaternization procedures for the synthesis of dipyridinium IL bromides
-11
4
.2.3.1. Conventional procedure (CP)
(2-Bromoethoxy)benzene, (3-bromopropoxy)benzene and/or (3-bromobutoxy)benzene
(10 mmol) was added with stirring to a solution of dipyridine Schiff base 4 and/or 5 (5
mmol) in acetonitrile (30 mL). Then, the reaction mixture was heated under reflux for 6-8
h, until the consumption of the starting material as indicated by TLC (silicagel, hexane-
ethyl acetate). The solvent was reduced by evaporation under reduce pressure; the
product formed was collected by filtration and/or extraction with chloroform to afford the
desired dicationic pyridinium bromides 6-11.
4
.2.3.2. Microwave irradiation (MWI)
Dipyridine Schiff base 4 and/or 5 (1 mmol), acetonitrile (5 mL), and the appropriate
bromoalkoxybenzene derivatives (2 mmol) were placed in closed borosilicate glass vessel
fitted with a silicone cap and exposed to irradiation for 3-4 min using a microwave
reactor. The reaction was processed as described in the conventional procedure outlined
earlier to give the same dicationic pyridinium bromides 6-11.
4
4
.2.4. Characterization
.2.4.1. 1-(2-Phenoxyethyl)-4-((2-(1-(2-phenoxyethyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium bromide (6)
1
Colorless crystals; mp: 82-83 ºC. H NMR (400 MHz, DMSO-d ): δ = 4.54 (t, 4H, J = 8
6
H
Hz, 2×NCH ), 5.18 (t, 4H, J = 8 Hz, 2×OCH ), 6.94-6.96 (m, 6H, Ar-H), 7.31 (dd, 4H, J
2
2
=
4 Hz, 8 Hz, Ar-H), 8.24 (d, 0.5H, J = 4 Hz, Ar-H), 8.33 (d, 0.5H, J = 4 Hz, Ar-H), 8.48
(
d, 1.5H, J = 4 Hz, Ar-H), 8.63 (d, 1.5H, J = 4 Hz, Ar-H), 8.71 (s, 0.75H, H-C=N), 8.84
s, 0.25H, H-C=N), 9.08 (d, 0.5H, J = 4 Hz, Ar-H), 9.22 (d, 1.5H, J = 4 Hz, Ar-H), 9.35
d, 0.5H, J = 4 Hz, Ar-H), 9.45 (d, 1.5H, J = 4 Hz, Ar-H), 12.89 (s, 0.25H, CONH),
(
(
1
3
1
6
1
3.28 (s, 0.75H, CONH). C NMR (100 MHz, DMSO-d ): δ = 60.22, 60.90 (2×NCH ),
6 C 2
6.43, 66.54 (2×OCH ), 115.11, 121.94, 125.19, 126.76, 130.08, 144.95, 146.38, 147.05,
2
+
47.51, 149.69 (Ar-C), 157.93, 160.34 (C=N, C=O). HRMS (ESI) m/z = 628.3540 [M ].
4
.2.4.2.
1-(3-Phenoxypropyl)-4-((2-(1-(3-phenoxypropyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium bromide (7)

ACCEPTED MANUSCRIPT
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 2.34-2.47 (m, 4H, 2×CH CH CH ), 4.12 (t,
6
H
2
2
2
4
H, J = 8 Hz, 2×NCH ), 4.84 (t, 4H, J = 8 Hz, 2×OCH ), 6.83 (dd, 4H, J = 4 Hz, 8 Hz,
2 2
Ar-H), 6.95 (dd, 2H, J = 4 Hz, 8 Hz, Ar-H), 7.27 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.16 (d,
0
8
0
9
.5H, J = 4 Hz, Ar-H), 8.33 (d, 0.5H, J = 4 Hz, Ar-H), 8.46 (d, 1.5H, J = 4 Hz, Ar-H),
.59 (d, 1.5H, J = 4 Hz, Ar-H), 8.71 (s, 0.75H, H-C=N), 8.84 (s, 0.25H, H-C=N), 9.05 (d,
.5H, J = 4 Hz, Ar-H), 9.21 (d, 1.5H, J = 4 Hz, Ar-H), 9.33 (d, 0.5H, J = 4 Hz, Ar-H),
1
3
.45 (d, 1.5H, J = 4 Hz, Ar-H), 13.25 (s, 1H, CONH). C NMR (100 MHz, DMSO-d ):
6
δ = 30.40, 30.43 (2×CH ), 59.12, 59.82 (2×NCH ), 65.20, 65.25 (2×OCH ), 114.78,
C
2
2
2
1
1
21.32, 125.27, 126.77, 129.98, 145.02, 146.01, 146.70, 147.03, 149.28 (Ar-C), 158.37,
+
60.28 (C=N, C=O). HRMS (ESI) m/z = 656.4087 [M ].
4
.2.4.3.
1-(4-Phenoxybutyl)-4-((2-(1-(4-phenoxybutyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium bromide (8)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 1.79 (bs, 4H, 2×CH CH N), 2.15 (bs, 4H,
6
H
2
2
2
6
8
×CH CH O), 4.03 (t, 4H, J = 4 Hz, 2×NCH ), 4.72 (t, 4H, J = 8 Hz, 2×OCH ), 6.93-
2 2 2 2
.96 (m, 6H, Ar-H), 7.29 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.20 (d, 0.5H, J = 4 Hz, Ar-H),
.32 (d, 0.5H, J = 4 Hz, Ar-H), 8.47 (d, 1.5H, J = 4 Hz, Ar-H), 8.59 (d, 1.5H, J = 4 Hz,
Ar-H), 8.67 (s, 0.75H, H-C=N), 8.72 (s, 0.25H, H-C=N), 9.06 (d, 0.5H, J = 4 Hz, Ar-H),
.19 (d, 1.5H, J = 4 Hz, Ar-H), 9.32 (d, 0.5H, J = 4 Hz, Ar-H), 9.41 (d, 1.5H, J = 4 Hz,
9
1
3
Ar-H), 13.20 (s, 1H, CONH). C NMR (100 MHz, DMSO-d ): δC = 25.76
6
(
2×CH CH N), 28.19 (2×CH CH O), 60.71, 61.39 (2×NCH ), 67.08 (2×OCH ), 114.92,
2 2 2 2 2 2
1
21.07, 125.48, 126.97, 129.97, 144.99, 145.71, 146.41, 149.23 (Ar-C), 158.87, 160.32
+
(
C=N, C=O). HRMS (ESI) m/z = 684.4619 [M ].
4
.2.4.4.
1-(2-Phenoxyethyl)-3-((2-(1-(2-phenoxyethyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium bromide (9)
1
Pale yellow crystals; mp: 90-91 ºC. H NMR (400 MHz, DMSO-d ): δ = 4.54 (t, 4H, J =
6
H
8
Hz, 2×NCH ), 5.18 (t, 4H, J = 8 Hz, 2×OCH ), 6.93-6.96 (m, 6H, Ar-H), 7.29 (dd, 4H,
2 2
J = 4 Hz, 8 Hz, Ar-H), 8.13 (dd, 0.25H, J = 4 Hz, 8 Hz, Ar-H), 8.27 (dd, 0.75H, J = 4 Hz,
8
0
Hz, Ar-H), 8.46 (d, 0.5H, J = 4 Hz, Ar-H), 8.59 (d, 1.5H, J = 4 Hz, Ar-H), 8.65 (s,
.2H, H-C=N), 8.68 (s, 0.8H, H-C=N), 8.95 (d, 0.75H, J = 8 Hz, Ar-H), 9.12 (d, 0.25H, J
=
4 Hz, Ar-H), 9.21 (d, 0.75H, J = 8 Hz, Ar-H), 9.31 (d, 0.5H, J = 4 Hz, Ar-H), 9.36 (s,
0
.25H, Ar-H), 9.42 (d, 1.5H, J = 4 Hz, Ar-H), 9.55 (s, 0.75H, Ar-H), 13.02 (s, 1H,

ACCEPTED MANUSCRIPT
1
3
CONH). C NMR (100 MHz, DMSO-d ): δ = 60.22, 60.90 (2×NCH ), 66.43, 66.54
6
C
2
(
2×OCH ), 114.92, 121.06, 126.91, 127.88, 129.97, 134.92, 144.34, 144.51, 145.79,
2
1
6
46.38, 147.22, 149.69 (Ar-C), 158.87, 159.93 (C=N, C=O). HRMS (ESI) m/z =
+
28.3555 [M ].
4
.2.4.5.
1-(3-Phenoxypropyl)-3-((2-(1-(3-phenoxypropyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium bromide (10)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 2.24-2.34 (m, 4H, 2×CH CH CH ), 4.13 (t,
6
H
2
2
2
4
H, J = 8 Hz, 2×NCH ), 4.92 (t, 4H, J = 8 Hz, 2×OCH ), 6.81 (dd, 4H, J = 4 Hz, 8 Hz,
2 2
Ar-H), 6.93 (dd, 2H, J = 4 Hz, 8 Hz, Ar-H), 7.27 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.09
dd, 0.25H, J = 4 Hz, 8 Hz, Ar-H), 8.26 (dd, 0.75H, J = 4 Hz, 8 Hz, Ar-H), 8.41 (d, 0.5H,
J = 4 Hz, Ar-H), 8.58 (d, 1.5H, J = 4 Hz, Ar-H), 8.62 (s, 0.2H, H-C=N), 8.64 (d, 0.25H, J
(
=
=
8 Hz, Ar-H), 8.67 (s, 0.8H, H-C=N), 8.97 (d, 0.75H, J = 8 Hz, Ar-H), 9.13 (d, 0.25H, J
4 Hz, Ar-H), 9.23 (d, 0.75H, J = 8 Hz, Ar-H), 9.32 (d, 0.5H, J = 4 Hz, Ar-H), 9.36 (s,
0
.25H, Ar-H), 9.44 (d, 1.5H, J = 4 Hz, Ar-H), 9.59 (s, 0.75H, Ar-H), 13.02 (s, 1H,
1
3
CONH). C NMR (100 MHz, DMSO-d ): δ = 30.41, 30.45 (2×CH ), 59.78, 59.80
6
C
2
(
2×NCH ), 65.18, 65.30 (2×OCH ), 114.79, 121.32, 126.70, 127.68, 129.98, 142.61,
2 2
1
45.98, 146.15, 146.66, 147.26, 149.32 (Ar-C), 158.38, 159.89 (C=N, C=O). HRMS
+
(
ESI) m/z = 656.4077 [M ].
4
.2.4.6.
1-(4-Phenoxybutyl)-3-((2-(1-(4-phenoxybutyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium bromide (11)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 1.81 (bs, 4H, 2×CH CH N), 2.16 (bs, 4H,
6
H
2
2
2
6
×CH CH O), 4.03 (t, 4H, J = 4 Hz, 2×NCH ), 4.81 (t, 4H, J = 8 Hz, 2×OCH ), 6.93-
2 2 2 2
.96 (m, 6H, Ar-H), 7.29 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.13 (dd, 0.25H, J = 4 Hz, 8
Hz, Ar-H), 8.27 (dd, 0.75H, J = 4 Hz, 8 Hz, Ar-H), 8.46 (d, 0.5H, J = 4 Hz, Ar-H), 8.59
d, 1.5H, J = 4 Hz, Ar-H), 8.65 (s, 0.2H, H-C=N), 8.68 (s, 0.8H, H-C=N), 8.95 (d, 0.75H,
J = 8 Hz, Ar-H), 9.12 (d, 0.25H, J = 4 Hz, Ar-H), 9.21 (d, 0.75H, J = 8 Hz, Ar-H), 9.31
(
(d, 0.5H, J = 4 Hz, Ar-H), 9.36 (s, 0.25H, Ar-H), 9.42 (d, 1.5H, J = 4 Hz, Ar-H), 9.55 (s,
13
0
.75H, Ar-H), 13.02 (s, 1H, CONH). C NMR (150 MHz, DMSO-d ): δ = 25.76, 25.79
6 C
(2×CH CH N), 28.21, 28.24 (2×CH CH O), 61.27, 61.34 (2×NCH ), 67.08, 67.14
2 2 2 2 2
(
2×OCH ), 114.92, 121.06, 126.91, 129.97, 144.34, 144.51, 145.79, 146.38, 149.22 (Ar-
2
+
C), 158.87, 159.93 (C=N, C=O). HRMS (ESI) m/z = 684.4602 [M ].

ACCEPTED MANUSCRIPT
4
4
.2.5. General metathesis procedures for the synthesis of dipyridinium ILs 12-41
.2.5.1. Conventional procedure (CP)
To the solution of dicationic pyridinium bromides 6-11 (1 mmol) in acetonitrile (20 mL),
was added with stirring the appropriate metal salts: potassium hexafluorophosphate,
sodium tetrafluoroborate, sodium trifluoroacetate, sodium thiocyanate, and/or sodium
dicyanamide (2.2 mmol) at room temperature, followed by heating under reflux for 16 h.
After cooling, the reaction mixture was filtered to remove solid metal halide. The
evaporation of acetonitrile leaded quantitatively to the targeted dicationic pyridinium ILs
1
2-41.
4
.2.5.2. Microwave irradiation (MWI)
Dicationic pyridinium bromides 6-11 (1 mmol), acetonitrile (5 mL), and the appropriate
metal salts (2.2 mmol) were placed in closed borosilicate glass vessel fitted with a
silicone cap and exposed to irradiation for 10 min using a microwave reactor. The
reaction was processed as described in the conventional procedure outlined earlier to give
the same dicationic pyridinium ILs 12-41.
4
4
.2.6. Characterization
.2.6.1. 1-(2-Phenoxyethyl)-4-((2-(1-(2-phenoxyethyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium hexafluorophosphate (12)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 4.54 (t, 4H, J = 8 Hz, 2×NCH ), 5.18 (t,
6
H
2
4
8
H, J = 8 Hz, 2×OCH ), 6.94-6.96 (m, 6H, Ar-H), 7.31 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H),
2
.24 (d, 0.5H, J = 4 Hz, Ar-H), 8.33 (d, 0.5H, J = 4 Hz, Ar-H), 8.48 (d, 1.5H, J = 4 Hz,
Ar-H), 8.63 (d, 1.5H, J = 4 Hz, Ar-H), 8.71 (s, 0.75H, H-C=N), 8.84 (s, 0.25H, H-C=N),
.08 (d, 0.5H, J = 4 Hz, Ar-H), 9.22 (d, 1.5H, J = 4 Hz, Ar-H), 9.35 (d, 0.5H, J = 4 Hz,
Ar-H), 9.45 (d, 1.5H, J = 4 Hz, Ar-H), 12.89 (s, 0.25H, CONH), 13.28 (s, 0.75H,
9
1
3
CONH). C NMR (100 MHz, DMSO-d ): δ = 60.22, 60.90 (2×NCH ), 66.43, 66.54
6
C
2
(
2×OCH ), 115.11, 121.94, 125.19, 126.76, 130.08, 144.95, 146.38, 147.05, 147.51,
2
3
1
1
49.69 (Ar-C), 157.93, 160.34 (C=N, C=O). P NMR (162 MHz, DMSO-d6):
1
9
δ = -157.39 to -131.04 (sept, 2P, 2×PF ). F NMR (377 MHz, DMSO-d ): δ = -69.17
P
6
6
F
+
(
d, 12F, 2×PF ). HRMS (ESI) m/z = 758.1438 [M ].
6

ACCEPTED MANUSCRIPT
4
.2.6.2.
1-(2-Phenoxyethyl)-4-((2-(1-(2-phenoxyethyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium tetrafluoroborate (13)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 4.54 (t, 4H, J = 8 Hz, 2×NCH ), 5.16 (t,
6
H
2
4
8
H, J = 8 Hz, 2×OCH ), 6.94-6.96 (m, 6H, Ar-H), 7.30 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H),
2
.20 (d, 0.5H, J = 4 Hz, Ar-H), 8.31 (d, 0.5H, J = 4 Hz, Ar-H), 8.48 (d, 1.5H, J = 4 Hz,
Ar-H), 8.60 (d, 1.5H, J = 4 Hz, Ar-H), 8.64 (s, 0.75H, H-C=N), 8.84 (s, 0.25H, H-C=N),
.08 (d, 0.5H, J = 4 Hz, Ar-H), 9.19 (d, 1.5H, J = 4 Hz, Ar-H), 9.32 (d, 0.5H, J = 4 Hz,
Ar-H), 9.42 (d, 1.5H, J = 4 Hz, Ar-H), 12.85 (s, 0.25H, CONH), 13.22 (s, 0.75H,
9
1
3
CONH). C NMR (100 MHz, DMSO-d ): δ = 60.24, 60.95 (2×NCH ), 66.41, 66.52
6
C
2
(
2×OCH ), 115.09, 121.96, 124.97, 125.21, 126.74, 127.65, 130.09, 144.96, 146.36,
2
1
1
1
47.05, 147.61, 149.71 (Ar-C), 157.88, 160.37 (C=N, C=O). B NMR (128 MHz,
1
9
DMSO-d ): δ = -1.32 to -1.30 (m, 2B, 2×BF ). F NMR (377 MHz, DMSO-d6):
6
B
4
+
δ = -148.28, -148.22 (2d, 8F, 2×BF ). HRMS (ESI) m/z = 642.2227 [M ].
F
4
4
.2.6.3.
1-(2-Phenoxyethyl)-4-((2-(1-(2-phenoxyethyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium trifluoroacetate (14)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 4.54 (t, 4H, J = 8 Hz, 2×NCH ), 5.16 (t,
6
H
2
4
8
H, J = 8 Hz, 2×OCH ), 6.94-6.96 (m, 6H, Ar-H), 7.32 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H),
2
.22 (d, 0.5H, J = 4 Hz, Ar-H), 8.32 (d, 0.5H, J = 4 Hz, Ar-H), 8.49 (d, 1.5H, J = 4 Hz,
Ar-H), 8.60 (d, 1.5H, J = 4 Hz, Ar-H), 8.66 (s, 0.75H, H-C=N), 8.84 (s, 0.25H, H-C=N),
.05 (d, 0.5H, J = 4 Hz, Ar-H), 9.20 (d, 1.5H, J = 4 Hz, Ar-H), 9.32 (d, 0.5H, J = 4 Hz,
Ar-H), 9.43 (d, 1.5H, J = 4 Hz, Ar-H), 12.86 (s, 0.25H, CONH), 13.24 (s, 0.75H,
9
1
3
CONH). C NMR (100 MHz, DMSO-d ): δ = 60.23, 60.93 (2×NCH ), 66.42, 66.53
6
C
2
(
2×OCH ), 115.10, 121.95, 125.20, 126.74, 127.62, 130.08, 144.96, 146.36, 147.05,
2
1
9
1
7
49.70 (Ar-C), 157.88, 160.36 (C=N, C=O). F NMR (377 MHz, DMSO-d ): δ = -
6 F
+
3.78 (s, 6F, 2×CF ). HRMS (ESI) m/z = 694.1867 [M ].
3
4
.2.6.4.
1-(2-Phenoxyethyl)-4-((2-(1-(2-phenoxyethyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium thiocyanate (15)
1
Colorless crystals; mp: 88-89 ºC. H NMR (400 MHz, DMSO-d ): δ = 4.57 (t, 4H, J = 8
6
H
Hz, 2×NCH ), 5.17 (t, 4H, J = 8 Hz, 2×OCH ), 6.94-6.96 (m, 6H, Ar-H), 7.30 (dd, 4H, J
2
2
=
4 Hz, 8 Hz, Ar-H), 8.21 (d, 0.5H, J = 4 Hz, Ar-H), 8.34 (d, 0.5H, J = 4 Hz, Ar-H), 8.47
(d, 1.5H, J = 4 Hz, Ar-H), 8.62 (d, 1.5H, J = 4 Hz, Ar-H), 8.69 (s, 0.75H, H-C=N), 8.83

ACCEPTED MANUSCRIPT
(s, 0.25H, H-C=N), 9.07 (d, 0.5H, J = 4 Hz, Ar-H), 9.21 (d, 1.5H, J = 4 Hz, Ar-H), 9.33
(d, 0.5H, J = 4 Hz, Ar-H), 9.43 (d, 1.5H, J = 4 Hz, Ar-H), 12.92 (s, 0.25H, CONH),
1
3
1
6
1
3.35 (s, 0.75H, CONH). C NMR (100 MHz, DMSO-d ): δ = 60.22, 60.91 (2×NCH ),
6 C 2
6.42, 66.53 (2×OCH ), 115.09, 121.94, 125.18, 126.73, 127.62, 130.08, 145.02, 146.39,
2
+
47.06, 149.71 (Ar-C), 157.93, 160.37 (C=N, C=O). HRMS (ESI) m/z = 584.1659 [M ].
4
.2.6.5.
1-(2-Phenoxyethyl)-4-((2-(1-(2-phenoxyethyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium dicyanamide (16)
1
Colorless crystals; mp: 93-94 ºC. H NMR (400 MHz, DMSO-d ): δ = 4.54 (t, 4H, J = 8
6
H
Hz, 2×NCH ), 5.17 (t, 4H, J = 8 Hz, 2×OCH ), 6.94-6.96 (m, 6H, Ar-H), 7.30 (dd, 4H, J
2
2
=
4 Hz, 8 Hz, Ar-H), 8.21 (d, 0.5H, J = 4 Hz, Ar-H), 8.32 (d, 0.5H, J = 4 Hz, Ar-H), 8.48
(
d, 1.5H, J = 4 Hz, Ar-H), 8.61 (d, 1.5H, J = 4 Hz, Ar-H), 8.67 (s, 0.75H, H-C=N), 8.84
s, 0.25H, H-C=N), 9.06 (d, 0.5H, J = 4 Hz, Ar-H), 9.20 (d, 1.5H, J = 4 Hz, Ar-H), 9.32
d, 0.5H, J = 4 Hz, Ar-H), 9.43 (d, 1.5H, J = 4 Hz, Ar-H), 12.87 (s, 0.25H, CONH),
(
(
1
3
1
6
1
3.25 (s, 0.75H, CONH). C NMR (100 MHz, DMSO-d ): δ = 60.23, 60.93 (2×NCH ),
6 C 2
6.43, 66.53 (2×OCH ), 115.10, 121.95, 126.75, 127.65, 130.09, 144.97, 146.37, 147.05,
2
+
49.71 (Ar-C), 157.93, 160.36 (C=N, C=O). HRMS (ESI) m/z = 600.2331 [M ].
4
.2.6.6.
1-(3-Phenoxypropyl)-4-((2-(1-(3-phenoxypropyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium hexafluorophosphate (17)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 2.34-2.47 (m, 4H, 2×CH CH CH ), 4.12 (t,
6
H
2
2
2
4
H, J = 8 Hz, 2×NCH ), 4.84 (t, 4H, J = 8 Hz, 2×OCH ), 6.83 (dd, 4H, J = 4 Hz, 8 Hz,
2 2
Ar-H), 6.95 (dd, 2H, J = 4 Hz, 8 Hz, Ar-H), 7.27 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.16 (d,
0
8
0
9
.5H, J = 4 Hz, Ar-H), 8.33 (d, 0.5H, J = 4 Hz, Ar-H), 8.46 (d, 1.5H, J = 4 Hz, Ar-H),
.59 (d, 1.5H, J = 4 Hz, Ar-H), 8.71 (s, 0.75H, H-C=N), 8.84 (s, 0.25H, H-C=N), 9.05 (d,
.5H, J = 4 Hz, Ar-H), 9.21 (d, 1.5H, J = 4 Hz, Ar-H), 9.33 (d, 0.5H, J = 4 Hz, Ar-H),
1
3
.45 (d, 1.5H, J = 4 Hz, Ar-H), 13.25 (s, 1H, CONH). C NMR (100 MHz, DMSO-d ):
6
δ = 30.40, 30.43 (2×CH ), 59.12, 59.82 (2×NCH ), 65.20, 65.25 (2×OCH ), 114.78,
C
2
2
2
1
1
2
=
21.32, 125.27, 126.77, 129.98, 145.02, 146.01, 146.70, 147.03, 149.28 (Ar-C), 158.37,
3
1
60.28 (C=N, C=O). P NMR (162 MHz, DMSO-d ): δ = -157.39 to -131.04 (sept, 2P,
6
P
1
9
×PF ). F NMR (377 MHz, DMSO-d ): δ = -69.18 (d, 12F, 2×PF ). HRMS (ESI) m/z
6
6
F
6
+
786.1755 [M ].

ACCEPTED MANUSCRIPT
4
.2.6.7.
1-(3-Phenoxypropyl)-4-((2-(1-(3-phenoxypropyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium tetrafluoroborate (18)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 2.34-2.40 (m, 4H, 2×CH CH CH ), 4.12 (t,
6
H
2
2
2
4
H, J = 8 Hz, 2×NCH ), 4.83 (t, 4H, J = 8 Hz, 2×OCH ), 6.83 (dd, 4H, J = 4 Hz, 8 Hz,
2 2
Ar-H), 6.94 (dd, 2H, J = 4 Hz, 8 Hz, Ar-H), 7.28 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.14 (d,
0
8
0
9
.5H, J = 4 Hz, Ar-H), 8.32 (d, 0.5H, J = 4 Hz, Ar-H), 8.46 (d, 1.5H, J = 4 Hz, Ar-H),
.57 (d, 1.5H, J = 4 Hz, Ar-H), 8.66 (s, 0.75H, H-C=N), 8.72 (s, 0.25H, H-C=N), 9.02 (d,
.5H, J = 4 Hz, Ar-H), 9.19 (d, 1.5H, J = 4 Hz, Ar-H), 9.31 (d, 0.5H, J = 4 Hz, Ar-H),
1
3
.42 (d, 1.5H, J = 4 Hz, Ar-H), 13.21 (s, 1H, CONH). C NMR (100 MHz, DMSO-d ):
6
δ = 30.38, 30.41 (2×CH ), 59.15, 59.87 (2×NCH ), 65.19, 65.23 (2×OCH ), 114.76,
C
2
2
2
1
1
21.32, 125.27, 126.76, 127.61, 129.98, 145.01, 145.98, 146.69, 149.31 (Ar-C), 158.37,
1
1
60.29 (C=N, C=O). B NMR (128 MHz, DMSO-d ): δ = -1.30 to -1.29 (m, 2B, 2 ×
6
B
1
9
BF ). F NMR (377 MHz, DMSO-d ): δ = -148.39, -148.32 (2d, 8F, 2 × BF ). HRMS
4
6
F
4
+
(
ESI) m/z = 670.2527 [M ].
4
.2.6.8.
1-(3-Phenoxypropyl)-4-((2-(1-(3-phenoxypropyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium trifluoroacetate (19)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 2.34-2.39 (m, 4H, 2×CH CH CH ), 4.12 (t,
6
H
2
2
2
4
H, J = 8 Hz, 2×NCH ), 4.83 (t, 4H, J = 8 Hz, 2×OCH ), 6.82 (dd, 4H, J = 4 Hz, 8 Hz,
2 2
Ar-H), 6.93 (dd, 2H, J = 4 Hz, 8 Hz, Ar-H), 7.27 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.14 (d,
0
8
0
9
.5H, J = 4 Hz, Ar-H), 8.33 (d, 0.5H, J = 4 Hz, Ar-H), 8.44 (d, 1.5H, J = 4 Hz, Ar-H),
.58 (d, 1.5H, J = 4 Hz, Ar-H), 8.70 (s, 0.75H, H-C=N), 8.72 (s, 0.25H, H-C=N), 9.02 (d,
.5H, J = 4 Hz, Ar-H), 9.18 (d, 1.5H, J = 4 Hz, Ar-H), 9.31 (d, 0.5H, J = 4 Hz, Ar-H),
1
3
.41 (d, 1.5H, J = 4 Hz, Ar-H), 13.24 (s, 1H, CONH). C NMR (100 MHz, DMSO-d ):
6
δ = 30.38, 30.41 (2×CH ), 59.13, 59.83 (2×NCH ), 65.19, 65.23 (2×OCH ), 114.77,
C
2
2
2
1
1
21.31, 125.25, 126.76, 127.61, 129.97, 145.01, 145.99, 146.68, 149.31 (Ar-C), 158.37,
1
9
60.29 (C=N, C=O). F NMR (377 MHz, DMSO-d ): δ = -73.78 (s, 6F, 2×CF ).
6
F
3
+
HRMS (ESI) m/z = 722.2170 [M ].
.2.6.8. 1-(3-Phenoxypropyl)-4-((2-(1-(3-phenoxypropyl)pyridin-1-ium-4-carbonyl)-
4
hydrazono)methyl)pyridin-1-ium thiocyanate (20)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 2.34-2.40 (m, 4H, 2×CH CH CH ), 4.12 (t,
6
H
2
2
2
4
H, J = 8 Hz, 2×NCH ), 4.84 (t, 4H, J = 8 Hz, 2×OCH ), 6.83 (dd, 4H, J = 4 Hz, 8 Hz,
2 2

ACCEPTED MANUSCRIPT
Ar-H), 6.94 (dd, 2H, J = 4 Hz, 8 Hz, Ar-H), 7.27 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.16 (d,
0
8
0
9
.5H, J = 4 Hz, Ar-H), 8.34 (d, 0.5H, J = 4 Hz, Ar-H), 8.46 (d, 1.5H, J = 4 Hz, Ar-H),
.59 (d, 1.5H, J = 4 Hz, Ar-H), 8.71 (s, 0.75H, H-C=N), 8.75 (s, 0.25H, H-C=N), 9.05 (d,
.5H, J = 4 Hz, Ar-H), 9.22 (d, 1.5H, J = 8 Hz, Ar-H), 9.33 (d, 0.5H, J = 4 Hz, Ar-H),
1
3
.45 (d, 1.5H, J = 4 Hz, Ar-H), 13.30 (s, 1H, CONH). C NMR (100 MHz, DMSO-d ):
6
δ = 30.40, 30.44 (2×CH ), 59.12, 59.81 (2×NCH ), 65.14, 65.20 (2×OCH ), 114.77,
C
2
2
2
1
1
21.31, 125.26, 126.76, 127.85, 129.97, 145.05, 145.64, 146.70, 149.29 (Ar-C), 158.38,
+
60.28 (C=N, C=O). HRMS (ESI) m/z = 612.1981 [M ].
4
.2.6.9.
1-(3-Phenoxypropyl)-4-((2-(1-(3-phenoxypropyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium dicyanamide (21)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 2.34-2.40 (m, 4H, 2×CH CH CH ), 4.12 (t,
6
H
2
2
2
4
H, J = 8 Hz, 2×NCH ), 4.84 (t, 4H, J = 8 Hz, 2×OCH ), 6.83 (dd, 4H, J = 4 Hz, 8 Hz,
2 2
Ar-H), 6.93 (dd, 2H, J = 4 Hz, 8 Hz, Ar-H), 7.27 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.14 (d,
0
8
0
9
.5H, J = 4 Hz, Ar-H), 8.33 (d, 0.5H, J = 4 Hz, Ar-H), 8.45 (d, 1.5H, J = 4 Hz, Ar-H),
.58 (d, 1.5H, J = 4 Hz, Ar-H), 8.69 (s, 0.75H, H-C=N), 8.75 (s, 0.25H, H-C=N), 9.04 (d,
.5H, J = 4 Hz, Ar-H), 9.20 (d, 1.5H, J = 4 Hz, Ar-H), 9.32 (d, 0.5H, J = 4 Hz, Ar-H),
1
3
.43 (d, 1.5H, J = 4 Hz, Ar-H), 13.24 (s, 1H, CONH). C NMR (100 MHz, DMSO-d ):
6
δ = 30.40, 30.43 (2×CH ), 59.13, 59.84 (2×NCH ), 65.19, 65.23 (2×OCH ), 114.78,
C
2
2
2
1
1
21.31, 125.27, 126.77, 127.60, 129.98, 145.04, 145.59, 146.68, 149.29 (Ar-C), 158.37,
+
60.28 (C=N, C=O). HRMS (ESI) m/z = 628.2648 [M ].
4
.2.6.10.
1-(4-Phenoxybutyl)-4-((2-(1-(4-phenoxybutyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium hexafluorophosphate (22)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 1.79 (bs, 4H, 2×CH CH N), 2.15 (bs, 4H,
6
H
2
2
2
6
×CH CH O), 4.03 (t, 4H, J = 4 Hz, 2×NCH ), 4.72 (t, 4H, J = 8 Hz, 2×OCH ), 6.93-
2 2 2 2
.96 (m, 6H, Ar-H), 7.29 (dd, 4H, J = 8 Hz, Ar-H), 8.20 (d, 0.5H, J = 4 Hz, Ar-H), 8.32
(d, 0.5H, J = 4 Hz, Ar-H), 8.47 (d, 1.5H, J = 4 Hz, Ar-H), 8.59 (d, 1.5H, J = 4 Hz, Ar-H),
8
1
1
2
1
.67 (s, 0.75H, H-C=N), 8.72 (s, 0.25H, H-C=N), 9.06 (d, 0.5H, J = 4 Hz, Ar-H), 9.19 (d,
.5H, J = 4 Hz, Ar-H), 9.32 (d, 0.5H, J = 4 Hz, Ar-H), 9.41 (d, 1.5H, J = 4 Hz, Ar-H),
1
3
3.20 (s, 1H, CONH). C NMR (100 MHz, DMSO-d ): δ = 25.76 (2×CH CH N),
6
C
2
2
8.19 (2×CH CH O), 60.71, 61.39 (2×NCH ), 67.08 (2×OCH ), 114.92, 121.07, 125.48,
2
2
2
2
3
1
26.97, 129.97, 144.99, 145.71, 146.41, 149.23 (Ar-C), 158.87, 160.32 (C=N, C=O). P

ACCEPTED MANUSCRIPT
19
NMR (162 MHz, DMSO-d ): δ = -157.39 to -131.04 (sept, 2P, 2×PF ). F NMR (377
6
P
6
+
MHz, DMSO-d ): δ = -69.19 (d, 12F, 2×PF ). HRMS (ESI) m/z = 814.2065 [M ].
6
F
6
4
.2.6.11.
1-(4-Phenoxybutyl)-4-((2-(1-(4-phenoxybutyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium tetrafluoroborate (23)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 1.79 (bs, 4H, 2×CH CH N), 2.15 (bs, 4H,
6
H
2
2
2
6
8
×CH CH O), 4.03 (t, 4H, J = 4 Hz, 2×NCH ), 4.71 (t, 4H, J = 4 Hz, 2×OCH ), 6.93-
2 2 2 2
.95 (m, 6H, Ar-H), 7.29 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.19 (d, 0.5H, J = 4 Hz, Ar-H),
.31 (d, 0.5H, J = 4 Hz, Ar-H), 8.46 (d, 1.5H, J = 4 Hz, Ar-H), 8.58 (d, 1.5H, J = 4 Hz,
Ar-H), 8.65 (s, 0.75H, H-C=N), 8.72 (s, 0.25H, H-C=N), 9.03 (d, 0.5H, J = 4 Hz, Ar-H),
.16 (d, 1.5H, J = 4 Hz, Ar-H), 9.29 (d, 0.5H, J = 4 Hz, Ar-H), 9.38 (d, 1.5H, J = 4 Hz,
9
1
3
Ar-H), 13.19 (s, 1H, CONH). C NMR (100 MHz, DMSO-d ): δC = 25.77
6
(
2×CH CH N), 28.21 (2×CH CH O), 60.73, 61.41 (2×NCH ), 67.07 (2×OCH ), 114.91,
2 2 2 2 2 2
1
1
2
21.06, 121.07, 125.48, 126.97, 129.97, 145.69, 146.39, 147.08, 149.25 (Ar-C), 158.87,
1
1
60.32 (C=N, C=O). B NMR (128 MHz, DMSO-d ): δ = -1.31 to -1.29 (m, 2B,
6
B
1
9
×BF ). F NMR (377 MHz, DMSO-d ): δ = -148.28, -148.21 (2d, 8F, 2×BF ). HRMS
4
6
F
4
+
(
ESI) m/z = 698.2850 [M ].
4
.2.6.12.
1-(4-Phenoxybutyl)-4-((2-(1-(4-phenoxybutyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium trifluoroacetate (24)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 1.79 (bs, 4H, 2×CH CH N), 2.15 (bs, 4H,
6
H
2
2
2
6
8
×CH CH O), 4.03 (t, 4H, J = 4 Hz, 2×NCH ), 4.71 (t, 4H, J = 8 Hz, 2×OCH ), 6.93-
2 2 2 2
.95 (m, 6H, Ar-H), 7.29 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.19 (d, 0.5H, J = 4 Hz, Ar-H),
.31 (d, 0.5H, J = 4 Hz, Ar-H), 8.47 (d, 1.5H, J = 4 Hz, Ar-H), 8.59 (d, 1.5H, J = 4 Hz,
Ar-H), 8.65 (s, 0.75H, H-C=N), 8.73 (s, 0.25H, H-C=N), 9.04 (d, 0.5H, J = 4 Hz, Ar-H),
.18 (d, 1.5H, J = 4 Hz, Ar-H), 9.30 (d, 0.5H, J = 4 Hz, Ar-H), 9.40 (d, 1.5H, J = 4 Hz,
9
1
3
Ar-H), 13.19 (s, 1H, CONH). C NMR (100 MHz, DMSO-d ): δC = 25.77
6
(
2×CH CH N), 28.21 (2×CH CH O), 60.72, 61.41 (2×NCH ), 67.08 (2×OCH ), 114.91,
2 2 2 2 2 2
1
1
21.06, 121.08, 125.49, 126.97, 129.97, 145.00, 145.71, 146.41, 149.23 (Ar-C), 158.87,
1
9
60.30 (C=N, C=O). F NMR (377 MHz, DMSO-d ): δ = -73.78 (s, 6F, 2×CF ).
6
F
3
+
HRMS (ESI) m/z = 750.2478 [M ].

ACCEPTED MANUSCRIPT
4
.2.6.13.
1-(4-Phenoxybutyl)-4-((2-(1-(4-phenoxybutyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium thiocyanate (25)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 1.78 (bs, 4H, 2×CH CH N), 2.14 (bs, 4H,
6
H
2
2
2
6
8
×CH CH O), 4.03 (t, 4H, J = 4 Hz, 2×NCH ), 4.72 (t, 4H, J = 8 Hz, 2×OCH ), 6.93-
2 2 2 2
.95 (m, 6H, Ar-H), 7.29 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.20 (d, 0.5H, J = 4 Hz, Ar-H),
.32 (d, 0.5H, J = 4 Hz, Ar-H), 8.47 (d, 1.5H, J = 4 Hz, Ar-H), 8.59 (d, 1.5H, J = 4 Hz,
Ar-H), 8.67 (s, 0.75H, H-C=N), 8.73 (s, 0.25H, H-C=N), 9.06 (d, 0.5H, J = 4 Hz, Ar-H),
.19 (d, 1.5H, J = 4 Hz, Ar-H), 9.32 (d, 0.5H, J = 4 Hz, Ar-H), 9.42 (d, 1.5H, J = 4 Hz,
9
1
3
Ar-H), 13.23 (s, 1H, CONH). C NMR (100 MHz, DMSO-d ): δC = 25.76
6
(
2×CH CH N), 28.19 (2×CH CH O), 60.73, 61.38 (2×NCH ), 67.08 (2×OCH ), 114.91,
2 2 2 2 2 2
1
1
21.06, 121.08, 125.48, 126.96, 127.80, 129.97, 145.02, 145.71, 146.41, 149.23 (Ar-C),
+
58.86, 160.31 (C=N, C=O). HRMS (ESI) m/z = 640.2285 [M ].
4
.2.6.14.
1-(4-Phenoxybutyl)-4-((2-(1-(4-phenoxybutyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium dicyanamide (26)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 1.79 (bs, 4H, 2×CH CH N), 2.15 (bs, 2H,
6
H
2
2
4
6
8
×CH CH O), 4.03 (t, 4H, J = 4 Hz, 2×NCH ), 4.71 (t, 4H, J = 8 Hz, 2×OCH ), 6.93-
2 2 2 2
.95 (m, 6H, Ar-H), 7.29 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.19 (d, 0.5H, J = 4 Hz, Ar-H),
.31 (d, 0.5H, J = 4 Hz, Ar-H), 8.47 (d, 1.5H, J = 4 Hz, Ar-H), 8.58 (d, 1.5H, J = 4 Hz,
Ar-H), 8.65 (s, 0.75H, H-C=N), 8.73 (s, 0.25H, H-C=N), 9.04 (d, 0.5H, J = 4 Hz, Ar-H),
.18 (d, 1.5H, J = 4 Hz, Ar-H), 9.29 (d, 0.5H, J = 4 Hz, Ar-H), 9.40 (d, 1.5H, J = 4 Hz,
9
1
3
Ar-H), 13.19 (s, 1H, CONH). C NMR (100 MHz, DMSO-d ): δC = 25.78
6
(
2×CH CH N), 28.21 (2×CH CH O), 60.74, 61.42 (2×NCH ), 67.08 (2×OCH ), 114.91,
2 2 2 2 2 2
1
1
21.06, 121.07, 125.48, 126.96, 129.97, 145.00, 145.71, 146.40, 149.24 (Ar-C), 158.87,
+
60.32 (C=N, C=O). HRMS (ESI) m/z = 656.2971 [M ].
4
.2.6.15.
1-(2-Phenoxyethyl)-3-((2-(1-(2-phenoxyethyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium hexafluorophosphate (27)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 4.54 (t, 4H, J = 8 Hz, 2×NCH ), 5.18 (t,
6
H
2
4
8
0
0
H, J = 8 Hz, 2×OCH ), 6.93-6.96 (m, 6H, Ar-H), 7.29 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H),
2
.13 (dd, 0.25H, J = 4 Hz, 8 Hz, Ar-H), 8.27 (dd, 0.75H, J = 4 Hz, 8 Hz, Ar-H), 8.46 (d,
.5H, J = 4 Hz, Ar-H), 8.59 (d, 1.5H, J = 4 Hz, Ar-H), 8.65 (s, 0.2H, H-C=N), 8.68 (s,
.8H, H-C=N), 8.95 (d, 0.75H, J = 8 Hz, Ar-H), 9.12 (d, 0.25H, J = 4 Hz, Ar-H), 9.21 (d,

ACCEPTED MANUSCRIPT
0
1
.75H, J = 8 Hz, Ar-H), 9.31 (d, 0.5H, J = 4 Hz, Ar-H), 9.36 (s, 0.25H, Ar-H), 9.42 (d,
1
3
.5H, J = 4 Hz, Ar-H), 9.55 (s, 0.75H, Ar-H), 13.02 (s, 1H, CONH). C NMR (100
MHz, DMSO-d ): δ = 60.22, 60.90 (2×NCH ), 66.43, 66.54 (2×OCH ), 114.92, 121.06,
6
C
2
2
1
1
26.91, 127.88, 129.97, 134.92, 144.34, 144.51, 145.79, 146.38, 147.22, 149.69 (Ar-C),
3
1
58.87, 159.93 (C=N, C=O). P NMR (162 MHz, DMSO-d ): δ = -157.39 to -131.04
6
P
1
9
(
sept, 2P, 2×PF ). F NMR (377 MHz, DMSO-d ): δ = -69.14 (d, 12F, 2×PF ). HRMS
6 6 F 6
+
(
ESI) m/z = 758.1449 [M ].
4
.2.6.16. 1-(2-Phenoxyethyl)-3-((2-(1-(2-phenoxyethyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium tetrafluoroborate (28)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 4.54 (t, 4H, J = 8 Hz, 2×NCH ), 5.18 (t,
6
H
2
4
8
0
0
0
1
H, J = 8 Hz, 2×OCH ), 6.93-6.96 (m, 6H, Ar-H), 7.29 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H),
2
.13 (dd, 0.25H, J = 4 Hz, 8 Hz, Ar-H), 8.27 (dd, 0.75H, J = 4 Hz, 8 Hz, Ar-H), 8.46 (d,
.5H, J = 4 Hz, Ar-H), 8.59 (d, 1.5H, J = 4 Hz, Ar-H), 8.65 (s, 0.2H, H-C=N), 8.68 (s,
.8H, H-C=N), 8.95 (d, 0.75H, J = 8 Hz, Ar-H), 9.12 (d, 0.25H, J = 4 Hz, Ar-H), 9.21 (d,
.75H, J = 8 Hz, Ar-H), 9.31 (d, 0.5H, J = 4 Hz, Ar-H), 9.36 (s, 0.25H, Ar-H), 9.42 (d,
1
3
.5H, J = 4 Hz, Ar-H), 9.55 (s, 0.75H, Ar-H), 13.02 (s, 1H, CONH). C NMR (100
MHz, DMSO-d ): δ = 60.22, 60.90 (2×NCH ), 66.43, 66.54 (2×OCH ), 114.92, 121.06,
6
C
2
2
1
1
2
26.91, 127.88, 129.97, 134.92, 144.34, 144.51, 145.79, 146.38, 147.22, 149.69 (Ar-C),
1
1
58.87, 159.93 (C=N, C=O). B NMR (128 MHz, DMSO-d ): δ = -1.30 to -1.29 (s, 2B,
6
B
1
9
×BF ). F NMR (377 MHz, DMSO-d ): δ = -148.17, -148.12 (2d, 8F, 2×BF ). HRMS
4
6
F
4
+
(
ESI) m/z = 642.2227 [M ].
4
.2.6.17.
1-(2-Phenoxyethyl)-3-((2-(1-(2-phenoxyethyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium trifluoroacetate (29)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 4.54 (t, 4H, J = 8 Hz, 2×NCH ), 5.18 (t,
6
H
2
4
8
0
0
0
1
H, J = 8 Hz, 2×OCH ), 6.93-6.96 (m, 6H, Ar-H), 7.29 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H),
2
.13 (dd, 0.25H, J = 4 Hz, 8 Hz, Ar-H), 8.27 (dd, 0.75H, J = 4 Hz, 8 Hz, Ar-H), 8.46 (d,
.5H, J = 4 Hz, Ar-H), 8.59 (d, 1.5H, J = 4 Hz, Ar-H), 8.65 (s, 0.2H, H-C=N), 8.68 (s,
.8H, H-C=N), 8.95 (d, 0.75H, J = 8 Hz, Ar-H), 9.12 (d, 0.25H, J = 4 Hz, Ar-H), 9.21 (d,
.75H, J = 8 Hz, Ar-H), 9.31 (d, 0.5H, J = 4 Hz, Ar-H), 9.36 (s, 0.25H, Ar-H), 9.42 (d,
1
3
.5H, J = 4 Hz, Ar-H), 9.55 (s, 0.75H, Ar-H), 13.02 (s, 1H, CONH). C NMR (100
MHz, DMSO-d ): δ = 60.22, 60.90 (2×NCH ), 66.43, 66.54 (2×OCH ), 114.92, 121.06,
6
C
2
2

ACCEPTED MANUSCRIPT
1
1
2
26.91, 127.88, 129.97, 134.92, 144.34, 144.51, 145.79, 146.38, 147.22, 149.69 (Ar-C),
1
9
58.87, 159.93 (C=N, C=O). F NMR (377 MHz, DMSO-d ): δ = -73.87 (s, 6F,
6
F
+
×CF ). HRMS (ESI) m/z = 694.1869 [M ].
3
4
.2.6.18.
1-(2-Phenoxyethyl)-3-((2-(1-(2-phenoxyethyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium thiocyanate (30)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 4.54 (t, 4H, J = 8 Hz, 2×NCH ), 5.18 (t,
6
H
2
4
8
0
0
0
1
H, J = 8 Hz, 2×OCH ), 6.93-6.96 (m, 6H, Ar-H), 7.29 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H),
2
.13 (dd, 0.25H, J = 4 Hz, 8 Hz, Ar-H), 8.27 (dd, 0.75H, J = 4 Hz, 8 Hz, Ar-H), 8.46 (d,
.5H, J = 4 Hz, Ar-H), 8.59 (d, 1.5H, J = 4 Hz, Ar-H), 8.65 (s, 0.2H, H-C=N), 8.68 (s,
.8H, H-C=N), 8.95 (d, 0.75H, J = 8 Hz, Ar-H), 9.12 (d, 0.25H, J = 4 Hz, Ar-H), 9.21 (d,
.75H, J = 8 Hz, Ar-H), 9.31 (d, 0.5H, J = 4 Hz, Ar-H), 9.36 (s, 0.25H, Ar-H), 9.42 (d,
1
3
.5H, J = 4 Hz, Ar-H), 9.55 (s, 0.75H, Ar-H), 13.02 (s, 1H, CONH). C NMR (100
MHz, DMSO-d ): δ = 60.22, 60.90 (2×NCH ), 66.43, 66.54 (2×OCH ), 114.92, 121.06,
6
C
2
2
1
1
26.91, 127.88, 129.97, 134.92, 144.34, 144.51, 145.79, 146.38, 147.22, 149.69 (Ar-C),
+
58.87, 159.93 (C=N, C=O). HRMS (ESI) m/z = 584.1659 [M ].
4
.2.6.19.
1-(2-Phenoxyethyl)-3-((2-(1-(2-phenoxyethyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium dicyanamide (31)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 4.54 (t, 4H, J = 8 Hz, 2×NCH ), 5.18 (t,
6
H
2
4
8
0
0
0
1
H, J = 8 Hz, 2×OCH ), 6.93-6.96 (m, 6H, Ar-H), 7.29 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H),
2
.13 (dd, 0.25H, J = 4 Hz, 8 Hz, Ar-H), 8.27 (dd, 0.75H, J = 4 Hz, 8 Hz, Ar-H), 8.46 (d,
.5H, J = 4 Hz, Ar-H), 8.59 (d, 1.5H, J = 4 Hz, Ar-H), 8.65 (s, 0.2H, H-C=N), 8.68 (s,
.8H, H-C=N), 8.95 (d, 0.75H, J = 8 Hz, Ar-H), 9.12 (d, 0.25H, J = 4 Hz, Ar-H), 9.21 (d,
.75H, J = 8 Hz, Ar-H), 9.31 (d, 0.5H, J = 4 Hz, Ar-H), 9.36 (s, 0.25H, Ar-H), 9.42 (d,
1
3
.5H, J = 4 Hz, Ar-H), 9.55 (s, 0.75H, Ar-H), 13.02 (s, 1H, CONH). C NMR (100
MHz, DMSO-d ): δ = 60.22, 60.90 (2×NCH ), 66.43, 66.54 (2×OCH ), 114.92, 121.06,
6
C
2
2
1
1
26.91, 127.88, 129.97, 134.92, 144.34, 144.51, 145.79, 146.38, 147.22, 149.69 (Ar-C),
+
58.87, 159.93 (C=N, C=O). HRMS (ESI) m/z = 600.2341 [M ].
4
.2.6.20. 1-(3-Phenoxypropyl)-3-((2-(1-(3-phenoxypropyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium hexafluorophosphate (32)

ACCEPTED MANUSCRIPT
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 2.24-2.34 (m, 4H, 2×CH CH CH ), 4.13 (t,
6
H
2
2
2
4
H, J = 8 Hz, 2×NCH ), 4.92 (t, 4H, J = 8 Hz, 2×OCH ), 6.81 (dd, 4H, J = 4 Hz, 8 Hz,
2 2
Ar-H), 6.93 (dd, 2H, J = 4 Hz, 8 Hz, Ar-H), 7.27 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.09
dd, 0.25H, J = 4 Hz, 8 Hz, Ar-H), 8.26 (dd, 0.75H, J = 4 Hz, 8 Hz, Ar-H), 8.41 (d, 0.5H,
J = 4 Hz, Ar-H), 8.58 (d, 1.5H, J = 4 Hz, Ar-H), 8.62 (s, 0.2H, H-C=N), 8.64 (d, 0.25H, J
(
=
=
8 Hz, Ar-H), 8.67 (s, 0.8H, H-C=N), 8.97 (d, 0.75H, J = 8 Hz, Ar-H), 9.13 (d, 0.25H, J
4 Hz, Ar-H), 9.23 (d, 0.75H, J = 8 Hz, Ar-H), 9.32 (d, 0.5H, J = 4 Hz, Ar-H), 9.36 (s,
0
.25H, Ar-H), 9.44 (d, 1.5H, J = 4 Hz, Ar-H), 9.59 (s, 0.75H, Ar-H), 13.02 (s, 1H,
1
3
CONH). C NMR (100 MHz, DMSO-d ): δ = 30.41, 30.45 (2×CH ), 59.78, 59.80
6
C
2
(
2×NCH ), 65.18, 65.30 (2×OCH ), 114.79, 121.32, 126.70, 127.68, 129.98, 142.61,
2 2
3
1
1
45.98, 146.15, 146.66, 147.26, 149.32 (Ar-C), 158.38, 159.89 (C=N, C=O). P NMR
1
9
(
162 MHz, DMSO-d ): δ = -157.39 to -131.04 (sept, 2P, 2×PF ). F NMR (377 MHz,
6 P 6
+
DMSO-d ): δ = -69.14 (d, 12F, 2×PF ). HRMS (ESI) m/z = 786.1750 [M ].
6
F
6
4
.2.6.21. 1-(3-Phenoxypropyl)-3-((2-(1-(3-phenoxypropyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium tetrafluoroborate (33)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 2.24-2.34 (m, 4H, 2×CH CH CH ), 4.13 (t,
6
H
2
2
2
4
H, J = 8 Hz, 2×NCH ), 4.92 (t, 4H, J = 8 Hz, 2×OCH ), 6.81 (dd, 4H, J = 4 Hz, 8 Hz,
2 2
Ar-H), 6.93 (dd, 2H, J = 4 Hz, 8 Hz, Ar-H), 7.27 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.09
dd, 0.25H, J = 4 Hz, 8 Hz, Ar-H), 8.26 (dd, 0.75H, J = 4 Hz, 8 Hz, Ar-H), 8.41 (d, 0.5H,
J = 4 Hz, Ar-H), 8.58 (d, 1.5H, J = 4 Hz, Ar-H), 8.62 (s, 0.2H, H-C=N), 8.64 (d, 0.25H, J
(
=
=
8 Hz, Ar-H), 8.67 (s, 0.8H, H-C=N), 8.97 (d, 0.75H, J = 8 Hz, Ar-H), 9.13 (d, 0.25H, J
4 Hz, Ar-H), 9.23 (d, 0.75H, J = 8 Hz, Ar-H), 9.32 (d, 0.5H, J = 4 Hz, Ar-H), 9.36 (s,
0
.25H, Ar-H), 9.44 (d, 1.5H, J = 4 Hz, Ar-H), 9.59 (s, 0.75H, Ar-H), 13.02 (s, 1H,
1
3
CONH). C NMR (100 MHz, DMSO-d ): δ = 30.41, 30.45 (2×CH ), 59.78, 59.80
6
C
2
(
2×NCH ), 65.18, 65.30 (2×OCH ), 114.79, 121.32, 126.70, 127.68, 129.98, 142.61,
2 2
1
1
1
45.98, 146.15, 146.66, 147.26, 149.32 (Ar-C), 158.38, 159.89 (C=N, C=O). B NMR
19
(
128 MHz, DMSO-d ): δ = -1.31 to -1.29 (m, 2B, 2×BF ). F NMR (377 MHz, DMSO-
6 B 4
+
d ): δ = -148.17, -148.12 (2d, 8F, 2×BF ). HRMS (ESI) m/z = 670.2540 [M ].
6
F
4
4
.2.6.22.
1-(2-Phenoxyethyl)-3-((2-(1-(2-phenoxyethyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium trifluoroacetate (34)

ACCEPTED MANUSCRIPT
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 2.24-2.34 (m, 4H, 2×CH CH CH ), 4.13 (t,
6
H
2
2
2
4
H, J = 8 Hz, 2×NCH ), 4.92 (t, 4H, J = 8 Hz, 2×OCH ), 6.81 (dd, 4H, J = 4 Hz, 8 Hz,
2 2
Ar-H), 6.93 (dd, 2H, J = 4 Hz, 8 Hz, Ar-H), 7.27 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.09
dd, 0.25H, J = 4 Hz, 8 Hz, Ar-H), 8.26 (dd, 0.75H, J = 4 Hz, 8 Hz, Ar-H), 8.41 (d, 0.5H,
J = 4 Hz, Ar-H), 8.58 (d, 1.5H, J = 4 Hz, Ar-H), 8.62 (s, 0.2H, H-C=N), 8.64 (d, 0.25H, J
(
=
=
8 Hz, Ar-H), 8.67 (s, 0.8H, H-C=N), 8.97 (d, 0.75H, J = 8 Hz, Ar-H), 9.13 (d, 0.25H, J
4 Hz, Ar-H), 9.23 (d, 0.75H, J = 8 Hz, Ar-H), 9.32 (d, 0.5H, J = 4 Hz, Ar-H), 9.36 (s,
0
.25H, Ar-H), 9.44 (d, 1.5H, J = 4 Hz, Ar-H), 9.59 (s, 0.75H, Ar-H), 13.02 (s, 1H,
1
3
CONH). C NMR (100 MHz, DMSO-d ): δ = 30.41, 30.45 (2×CH ), 59.78, 59.80
6
C
2
(
2×NCH ), 65.18, 65.30 (2×OCH ), 114.79, 121.32, 126.70, 127.68, 129.98, 142.61,
2 2
1
9
1
45.98, 146.15, 146.66, 147.26, 149.32 (Ar-C), 158.38, 159.89 (C=N, C=O). F NMR
+
(
377 MHz, DMSO-d ): δ = -73.87 (s, 6F, 2×CF ). HRMS (ESI) m/z = 722.2170 [M ].
6
F
3
4
.2.6.23. 1-(3-Phenoxypropyl)-3-((2-(1-(3-phenoxypropyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium thiocyanate (35)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 2.24-2.34 (m, 4H, 2×CH CH CH ), 4.13 (t,
6
H
2
2
2
4
H, J = 8 Hz, 2×NCH ), 4.92 (t, 4H, J = 8 Hz, 2×OCH ), 6.81 (dd, 4H, J = 4 Hz, 8 Hz,
2 2
Ar-H), 6.93 (dd, 2H, J = 4 Hz, 8 Hz, Ar-H), 7.27 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.09
dd, 0.25H, J = 4 Hz, 8 Hz, Ar-H), 8.26 (dd, 0.75H, J = 4 Hz, 8 Hz, Ar-H), 8.41 (d, 0.5H,
J = 4 Hz, Ar-H), 8.58 (d, 1.5H, J = 4 Hz, Ar-H), 8.62 (s, 0.2H, H-C=N), 8.64 (d, 0.25H, J
(
=
=
8 Hz, Ar-H), 8.67 (s, 0.8H, H-C=N), 8.97 (d, 0.75H, J = 8 Hz, Ar-H), 9.13 (d, 0.25H, J
4 Hz, Ar-H), 9.23 (d, 0.75H, J = 8 Hz, Ar-H), 9.32 (d, 0.5H, J = 4 Hz, Ar-H), 9.36 (s,
0
.25H, Ar-H), 9.44 (d, 1.5H, J = 4 Hz, Ar-H), 9.59 (s, 0.75H, Ar-H), 13.02 (s, 1H,
1
3
CONH). C NMR (100 MHz, DMSO-d ): δ = 30.41, 30.45 (2×CH ), 59.78, 59.80
6
C
2
(
2×NCH ), 65.18, 65.30 (2×OCH ), 114.79, 121.32, 126.70, 127.68, 129.98, 142.61,
2 2
1
45.98, 146.15, 146.66, 147.26, 149.32 (Ar-C), 158.38, 159.89 (C=N, C=O). HRMS
+
(
ESI) m/z = 612.1982 [M ].
4
.2.6.24. 1-(3-Phenoxypropyl)-3-((2-(1-(3-phenoxypropyl)pyridin-1-ium-4-carbonyl)-
hydrazono)methyl)pyridin-1-ium dicyanamide (36)
1
Syrup. H NMR (400 MHz, DMSO-d ): δ = 2.24-2.34 (m, 4H, 2×CH CH CH ), 4.13 (t,
6
H
2
2
2
4
H, J = 8 Hz, 2×NCH ), 4.92 (t, 4H, J = 8 Hz, 2×OCH ), 6.81 (dd, 4H, J = 4 Hz, 8 Hz,
2 2
Ar-H), 6.93 (dd, 2H, J = 4 Hz, 8 Hz, Ar-H), 7.27 (dd, 4H, J = 4 Hz, 8 Hz, Ar-H), 8.09