Journal of Coordination Chemistry

ISSN: 0095-8972 (Print) 1029-0389 (Online) Journal homepage: http://www.tandfonline.com/loi/gcoo20

Synthesis of a cobalt-based photoluminescent

coordination complex to study quenching
mechanisms of nitro compounds

Saira Mansab, Uzaira Rafique & Muhammad Javed Akhtar

To cite this article: Saira Mansab, Uzaira Rafique & Muhammad Javed Akhtar (2018): Synthesis
of a cobalt-based photoluminescent coordination complex to study quenching mechanisms of nitro
compounds, Journal of Coordination Chemistry, DOI: 10.1080/00958972.2018.1473570

To link to this article: https://doi.org/10.1080/00958972.2018.1473570

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Publisher: Taylor & Francis
Journal: Journal of Coordination Chemistry
DOI: http://doi.org/10.1080/00958972.2018.1473570

Synthesis of a cobalt-based photoluminescent coordination complex to study

quenching mechanisms of nitro compounds
SAIRA MANSAB*†‡, UZAIRA RAFIQUE† and MUHAMMAD JAVED AKHTAR‡

†Department of Environmental Sciences, Fatima Jinnah Women University, The Mall, Rawalpindi, Pakistan
‡Physics Division, Pakistan Institute of Nuclear Science and Technology, P.O. Nilore, Islamabad

A cobalt metal coordination complex was synthesized using the bipyridyl spacer ligand along
with a dicarboxylate as secondary ligand. The coordination complex was characterized using
FTIR, 1H NMR, elemental analysis, thermogravimetric analysis and powder XRD. The structure
shown from single crystal XRD revealed that each Co(II) cation in the cluster can be described
as trigonal bipyramidal. Luminescence properties of the complex were investigated using
different solvents. The photoluminescence spectra depicted change in band gap for THF and
DCM. The complex was further investigated for ligand-based photoluminescence properties and
thus used for sensing of nitro compounds. The static and dynamic quenching mechanism of nitro
compounds was identified through the Stern-Volmer model.

Keywords: Coordination complex; Nitro compounds; Photoluminescence; Quenching

1. Introduction
Metal organic frameworks (MOF), or porous coordination polymers, consist of a central atom
(metal) surrounded with array of atoms or groups of atoms (ligands) [1]. These compounds
possess unique properties. One of the striking features is their low density, which provides them
with high surface area and porosities. Their rigid structure provides them high thermal stability
to be used for environmental applications for sensing of different compounds [2].
Dimensions and topology of the complex can be tuned by modifying the molecular
structure of the organic ligand or by affixing different substituents on the organic ligand and

*Corresponding author. Emails: saira.mansab90@gmail.com; mansab.saira@nus.edu.sg

1
hence new structures can be created [3]. One of the interesting structures of MOFs is pillared
layers that can be formed using a bipyridyl spacer ligand, dicarboxylate compound and metal
ions. Using a substituted carboxylic group such as isophthalic acid provides additional sites for
attracting the acidic guest molecules to be used for removal of different pollutants [4].
Long delocalized organic spacer ligands have been found to have considerable good
photoluminescence properties [5]. These properties can be enhanced by incorporating the metal
ions that create proton acceptor and donor environments which enhance their photoluminescence
properties and make the coordination complexes one of the promising materials for chemical
sensor applications [6].
Incorporation of metal ions with these ligands decreases the non-irradiative decay and
gives narrow PL bands [7]. Owing to this type of band and the porous nature of the coordination
polymers, these can be used for sensing of environmental pollutants such as nitro compounds.
These nitro compounds are not only toxic in nature but are extensively used as explosives [8].
The most dominant mechanism involved in sensing of these nitro compounds is quenching that
involves the electron transfer from the excited state of an electron-donating metal coordination
complex to an electron-withdrawing nitro compound [9]. These nitro compounds can be
involved in hydrogen bonding with the coordination complex or sometimes physically interact
with the complex, thus hindering the electron transfer from excited state to ground state of the
complex. This results in a decrease of fluorescence intensity [10].
The present study focuses on the synthesis of a porous coordination polymer
Co(bpeb)(isophthalic)]·DMA via a solvothermal method. The synthesized complex is further
used for photoluminescence sensing of nitro compounds.

2. Materials and methods

All chemicals were purchased from commercial sources and used as received. All solvents used
are of reagent grade. Co(NO3)2·6H2O (99.99%) used was from Sigma Aldrich while isophthalic
acid (99%) and DMA (99%) were from Alfa Aesar. The 1,4-bis[2-(4-pyridyl)ethenyl]benzene
(bpeb) ligand was synthesized by the reported procedure [11]. CHNS elemental analysis was
carried out using an Elementar vario MICRO cube. A TA Instruments TGA-Q50
thermogravimetric analyser was used for weight loss study of prepared material. For this
purpose, a sample was heated at a constant rate of 5 °C min−1 from room temperature to 700 °C

2
in a continuous flow nitrogen atmosphere. The FT-IR spectrum was recorded using a FTS165
Bio-Rad FT-IR spectrometer as KBr pellets. NMR analysis was conducted using a Bruker A300
instrument after digesting the compound with trifluoroacetic acid in DMSO-d6 solvent. Powder
XRD of the synthesized coordination complex was determined using a Siemens D500
diffractometer with graphite monochromated Cu-Kα radiation (λ = 1.54056 Å) at room
temperature (23 C).

3. Experimental
3.1. Preparation of Co(bpeb)(isophthalic)]·1.5DMA
A mixture of bpeb (10 mg, 0.035 mmol), isophthalic acid (5.815 mg, 0.035 mmol) and
Co(NO3)2·6H2O (10.19 mg, 0.035 mmol) dissolved in DMA (3 mL) and H2O (1 mL) was placed
in a 5 mL glass tube. The tube was sealed and kept at 120 °C for 48 h, followed by cooling to
room temperature over 10 h. The pink cubic crystals obtained were washed with ethanol and
water and separated under an optical microscope. Yield: (15.33 mg) 73% (figure S1, Supporting
Information).

3.2. X-ray crystallographic structure determination

Single crystal X-ray diffraction (SCXRD) data for the compound was collected on a Bruker D8
Advance diffractometer (Bruker-AXS, Madison, WI, USA) with a Photon 100 CMOS area
detector and an IμS microfocus X-ray source (Bruker AXS) using Mo-Kα radiation. The crystal
was coated with Paratone oil (Hampton Research, Aliso Viejo, CA, USA) and cooled to 100 K
under a cold stream of nitrogen using an Oxford Cryostream cryostat (Oxford Cryosystems,
Oxford, UK). Unit cell determination, data collection, data reduction, and correction for
absorption were all conducted using the Apex3 software suite (Bruker AXS). The structure was
solved by an iterative dual space approach as implemented in SHELXT [12]. Non-hydrogen
atoms were located from the difference map and refined anisotropically. Hydrogen atoms bonded
to carbon atoms were placed in calculated positions. All hydrogen atom coordinates and thermal
parameters were constrained to ride on the carrier atoms. Anomalous thermal ellipsoids for some
of the N-dimethylacetamide (DMA) solvent molecules were found, possibly due to unresolvable
disorder. In addition, the disordered bpeb molecules were successfully modelled. Relevant

3
crystal data for this paper are shown in table 1 and available from Cambridge Crystallographic
Data Centre via CCDC 1585076.

3.3. Photoluminescence measurements

Photoluminescence properties of the complex were investigated using solid state dispersion in
different solvents under room temperature conditions. Dispersions were prepared by adding 3 mg
powdered samples of complex to 3 ml of the corresponding solvents. Sensing of nitro
compounds was studied using dispersions of complex in DMF which were ultrasonicated for 30
min to form stable emulsions. Different molar concentrations of analytes were added to the
dispersion and measurements were recorded using a Hitachi F-4500 fluorescence
spectrophotometer. Quenching efficiency (Q.E) was calculated using the following equation:

𝐼0 ‒ 𝐼
𝑄.𝐸 = 𝐼0
× 100 (1)

where I0 is the emission intensity without analyte and I is the emission intensity with analyte.

4. Results and discussion

4.1. Characterization
4.1.1. NMR analysis. 1H NMR spectrum, , ppm: 8.82 (d, J = 6.6 Hz, 4H), 8.48 (s, 1H), 8.19 (d,
J = 6.8 Hz, 4H), 8.14 (d, J = 1.7 Hz, 1H), 8.11 (d, J = 1.7 Hz, 1H), 8.01 (s, 1H), 7.83 (s, 4H),
7.60 (d, J = 8.5 Hz, 2H), 7.55 (d, J = 7.7 Hz, 2H). 1H-NMR spectra has shown the presence of
both spacer ligand and carboxylate group indicating the successful synthesis of the framework
structure. The peaks present at 1.93 ppm, 2.77 ppm and 2.91 ppm are representative of DMA
solvent. Further, it was also found from the integration values that bpeb and isophthalic ligands
are coordinated to cobalt metal in 1:1, respectively, while DMA incorporation was found to be
1:1.5 compared to ligands (figure 1).

4.1.2. Elemental analysis. Elemental analysis calculated for C34H33.50CoN3.50O5.50: C, 64; H,

5.29; N, 7.68%. Found: C, 64.44; H, 6.18; N, 8.58%. The formula predicted as a result of
elemental analysis is [Co(bpeb)(isophthalic)]·1.5DMA.

4
4.1.3. TGA analysis. TGA results of the complex reveal the removal of DMA molecules below
200 C with a weight loss 19.003% that is quite similar to the theoretical weight loss i.e. 20.48%.
The framework starts decomposing at 425 C and its complete decomposition occurred above
650 C (figure 2).

4.1.4. FTIR analysis. 3400 cm-1 (OH stretching), 3068 cm-1 (CH stretching aromatic), 2924 cm-1
(CH stretching alkyl), 1604 cm-1 (C=O), 1549 cm-1 (CC stretching in aromatic ring), 1493 cm-1
(CN stretching), 1392 cm-1 (OH bending of carboxylic group), 1216, 1188, 1023, 958 cm-1 (CH
bending), 829, 737 cm-1 (CH out of plane bending) (figure 3).

4.1.5. Structural description. The compound crystallizes in triclinic space group P-1 with Z=2,
in which the asymmetric unit consists of one Co(II) cation, one coordinating isophthalate ligand,
one coordinating bpeb, and two free DMA solvates. The binuclear cluster in this structure act as
the node and it is linked to four isophthalate and four bpeb molecules. Each Co(II) cation in this
cluster can be best described as distorted trigonal bipyramidal, in which the Co(II) ion center is
bonded to four equatorial carboxylate oxygen ions from three different isophthalate ligands
(Co(II)-O bond distances range from 2.025(2)-2.258(2) Å), in which a chelate fashion (2) is
formed through one carboxylate. Additionally, two different carboxylate functionalities are
linked between two metal ion centers through the 2: 1-1 fashion, generating 1D coordination
polymers along the a-axis, as shown in figure 4. The distance between two adjacent Co(II) ions
was found to be 4.112 Å. Finally, two partially disordered bpeb ligands were found to be
disordered by flipping, the superposed structure around one of the ethylene groups and the
rotation of the aromatic rings; the molecule was successfully modelled and found to have the
occupancy of 69:31 (figure S2, Supporting Information). These bpeb ligands are located at the
axial positions (Co(II)-N bond lengths are 2.137(2) Å and 2.148(2) Å) and led to the formation
of 2D sheets (figure 5). Interestingly, the adjacent coordination sheets interact through -stacking
generated between the bpeb molecules with the shortest distance being 3.268(7) Å. Furthermore,
it was found that the ethylene C=C groups of the neighboring bpeb ligands surrounding the
cluster also stack via weaker -interactions with intermolecular distances of 3.663 Å and 3.826 Å
(figure 6). The two disordered DMA molecules are located in between the 2D sheets and engage
in weak van der Waals and hydrogen bonding intermolecular interactions with the framework.

5
According to the Cambridge Structural Database (CSD) there are 113 entries containing the
ligand bpeb, in which only 10 structures contain Co-based structures with a dicarboxylate
supporting ligand [13]. Vittal and co-workers described the formation of a pillared-layer
coordination polymer using cobalt salts and bpeb in the presence of the V-shaped 4,4′-
oxybisbenzoate [14]. In this structure, the use of larger secondary spacer led to an interpenetrated
framework, unlike the use of isophthalate ligand.

4.1.6. Powder XRD analysis. The powder XRD measurements conducted on the bulk sample
show the crystalline nature of the product. The comparison of powder XRD data of the
synthesized complex with the simulated pattern from the single crystal structure is quite similar
which shows the phase purity and atmospheric stability of the synthesized compound (figure 7).

4.2. Photoluminescence studies

The excitation spectra of the bpeb ligand and complex were recorded and are centered at 360 nm
and 365 nm. Upon excitation at 360 nm, the emission band for the bpeb ligand is observed at
440 nm while for the complex it was blue shifted by 20 nm due to the change in band gap as a
result of a ligand centered transition and hence appeared at 420 nm along with the appearance of
shoulders at 395 nm and 437 nm (figure 8). These emission bands could be attributed to the
transition of metal ions due to metal-ligand charge transfer or ligand to metal charge transfer. It
has also been observed that the emission intensity of the complex is much higher compared to
the ligand due to quantitative polymerization of the ligand to form a rigid network structure with
the metal (figure 9). The PL spectra of the complex dispersed in DMF solution showed similar
peak behavior to that in the solid state with increased intensity which is due to exchange of
lattice solvent [8] (figure 10).

4.2.1. Effect of solvents. To investigate the effect of solvents on the luminescence behavior of
the complex different solvents were employed. Almost all solvents except THF and DCM
showed more or less the same emission intensity at 395 nm, 420 nm and 437 nm, which is
similar to the solid-state emission spectra. THF and DCM showed red shifted peaks at 409 nm,
433 nm and 455 nm. It was also observed that intensities decreased for all solvents except for
DMF (figure 11). This type of behavior can be explained through the nature of solvent. The

6
quenching results from protic alcoholic solvents may appear due to hydrogen bonding that
causes ground state charge transfer complex formation. This charge transfer complex formation
has decreased the excitation energy and thus fluorescence intensity decreases [15]. Further, the
presence of an oxygen quencher in alcoholic solvents enhances photo-induced energy transfer
processes that causes the non-radiative deactivation of the excited state [16]. Presence of a
bathochromic effect of a non-polar solvent i.e. DCM and less polar aprotic solvent i.e. THF can
appear due to structural changes and because of lattice vibrations upon host-guest interactions.
These vibrational motions change the band gap energies, which causes peak shifting [17, 18]. In
addition, it is noted that the complex has a nonpolar nature due to the unsubstituted aromatic
structure; the peak shifting is less prominent. Lakowicz explained various other factors that
affects the fluorescence behavior that includes solvent viscosity, solvent relaxation rate, internal
charge transfer and relative orientation of the charged group or polar solvent towards the
compound [19].

4.2.2. Sensing of nitro compounds. To investigate the sensing behavior of the complex, five
nitro compounds were selected and their quenching efficiency was calculated. It can be observed
that by increasing the concentration of nitro compounds the complex gradually undergoes
quenching with the appearance of broad band. This behavior is dominant in 2,4-
dinitrohydrazobenzene and nitroaniline with quenching percentages of 95% and 91% at 300 µM
concentration, respectively (figure 12). This can be attributed to hydrogen bonding of guest
molecules with the complex and the high electron deficiency of nitroaromatic compounds [20,
21]. 2,4-Dinitro phenol did not show any quenching behavior due to poor sensing response of
complex towards the mentioned analytes.(figure S3, Supporting Information). This type of
behavior was also observed by Park et al., in which a zinc-based bpeb coordination complex
showed less quenching behavior for nitrophenol compounds as compared to nitroaniline
compounds. They suggest that those compounds that show absorption maxima near the
excitation wavelength of the fluorophore do not show the quenching mechanism. Further, the
quenching mechanism can be attributed to the resonant energy transfer between the coordination
complex and the analytes due to proper matching of electronic bands of the fluorophore with the
analytes. This band matching can lead to fluorescence quenching along with other mechanisms
[17].

7
 The Stern-Volmer quenching model has also been applied to study the quenching
mechanism. These quenching mechanisms can be dynamic, static or resonance energy transfer.
In dynamic quenching, the quencher guest molecule establishes contact with the fluorophore
during its excited state through a diffusion mechanism. This contact results in de-excitation of
the fluorophore without radiative emission and hence the luminescence intensity decreases. In
static quenching, a complex is formed before excitation between the quenching moiety and
fluorophore in their ground state that makes the compound non-fluorescent and hence the
fluorescence intensity decreases. The third type of mechanism involves the energy transfer
mechanism in which the excited state energy is transferred to the quenching guest molecule. This
molecule absorbs the energy without photon emission and thus fluorescence of the material is
reduced.
To study the dynamic behaviour of quenching, the linear Stern-Volmer equation is used:

𝐼0
𝐼
= 1 + 𝐾𝑠𝑣[𝑄] (2)

where I0 and I represent the fluroscence intensities without and with quencher, respectively, Ksv
is the Stern-Volmer constant that is obtained through the slope of I0/I versus [Q] linear plot and
[Q] is the concentration of quencher (figure 13) [22].
The S-V plot of the studied system shows linearity at initial concentrations (0-100 µM) of
quencher while at higher concentrations a positive deviation is observed. This positive deviation
suggests the association of luminophores with few molecules of quencher due to chemical
bonding while others diffuse through solution, collide with luminophores, and hence deactivate
the luminophore’s excited state. It causes the luminophore to return back to the ground state
without emission of a photon [23]. To analyze the possibility of ground state association, a
modified Stern-Volmer equation was used.

𝐼
[ ‒ 1]
0
𝐼

[𝑄]
= (𝐾𝑠𝑣 + 𝐾𝑔) + 𝐾𝑠𝑣𝐾𝑔[𝑄] (3)

Here, Ksv and Kg are the Stern-Volmer and ground state association constants, respectively, that
can be calculated from linear least square fit of a plot of [(I0/I)-1]/[Q] versus [Q] (figure S4,
Supporting Information) where Ksv + Kg is the intercept and KsvKg is the slope using a

8
quadratic equation (Eq. 4) [24]. The reported literature suggests that the higher value obtained
belongs to quenching constant Ksv while the lower value represents the instantaneous static
quenching mechanism [25].

2
𝐾𝑠𝑣 ‒ 𝐾𝑠𝑣(𝐼𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡) + 𝑆𝑙𝑜𝑝𝑒 = 0 (4)

If the Ksv obtained from the lower portion of the plot agrees well with the Ksv value obtained
from Eq. 3 then it insures the ground state complex formation. Contrarily, in the present case, the
Ksv values calculated from Eq. 2 and Eq. 3 do not match, hence ground state complexation
cannot be considered [26]. Further, ground state complex formation can also be identified from
the peak shifting in the fluroscence emission spectra due to a change in band gap energies [27].
But, in the studied system, no peak shifting was observed after addition of quencher which
confirms the non-existance of a ground state complex. So, it is predicted from the results that
quenching occurs through a collision mechanism as no complex formation is observed in the
ground state. Further, the positive deviation in the results at higher concentrations can be
explained, as the fluorophores in the excited state are present in close vicinity of the quencher
and thus a certain fraction of fluorophore molecules are quenched through a collision
mechanism. Also, there is possibility that some of the fraction is immediately deactivated due to
the presence of quencher at random positions within the proximity of fluorophore at the
excitation stage, which creates deviation in the intensities [28]. This instantaneous quenching is
considered to be static, and to study such a type of quenching mechanism the Stern-Volmer
equation was further modified by adding the certain fraction (1-W) for non-linear plots.

[1 ‒ ]
𝐼
𝐼

[𝑄]
𝑂
= 𝐾𝑠𝑣 ( ) + (1 ‒ 𝑊)[𝑄]
𝐼
𝐼0
(5)

From Eq. 5, the value of W is calculated from the intercept of (1-I/I0)/[Q] vs I/I0 plot (figure S5,
Supporting Information). It is reported that for a pure collisional quenching mechanism, the
collisional fraction W is equal to unity. The deviation in the present case is ascribed to
involvement of immediate quenching along with collisional quenching [29, 30]. Thus, the range
of W is further used to calculate instantaneous static quenching constant (V) by a least square fit
method using Eq. 6 through a W vs [Q] plot (figure S6, Supporting Information).

9
 ‒ 𝑉[𝑄]
𝑊=𝑒 (6)

It is observed that the range of W is close to unity for 2,4-dinitroaniline and 4-nitrophenyl
hydrazine indicating less participation of instantaneous quenching while dinitrohydrazobenzene
and nitroaniline have shown more deviation from unity, which is attributed to relatively high
prompt static quenching. It is found from these results that the collisional quenching mechanism
is dominating the instantaneous static quenching as the value of static quenching model is lower
than the dynamic quenching model for all studied quenchers except 2,4-dinitrophenol which has
a negative quenching constant (table 2) [23].

5. Conclusion
A high intensity blue light emitting Co(bpeb)(isophthalic)]·1.5DMA coordination complex was
synthesized under solvothermal conditions. Its structure has also been verified through different
characterization techniques. Single crystal XRD has shown the formation of 2D sheets due to
axial positions of the ligands. The photoluminescence sensing of nitro compounds has shown
high quenching efficiency due to donor-acceptor electron transfer mechanism. The Stern-Volmer
model revealed the collision mechanism as a dominant factor for quenching of synthesized
coordination complex by nitro-compounds. This coordination complex can be further used to
investigate the nitro explosives compounds.

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Figure captions

Figure 1. 1H NMR spectra of complex in DMSO-d6 with a small drop of trifluoroacetic acid to
dissolve the crystals.

Figure 2. TGA curve of complex under air flow with heating rate of 5 °C·min-1.

Figure 3. FTIR spectral of cobalt coordination complex.

Figure 4. Perspective view of cobalt binding with ligands.

Figure 5. Orientation of ligands and cobalt binding with in cell.

Figure 6. Slip stacked structure of bpeb ligand.

Figure 7. PXRD patterns of complex and simulated from the single crystal XRD.

Figure 8. Solid state excitation and emission spectra of complex and ligand.

Figure 9. Solid state emission spectra of complex and ligand at 360 nm excitation.

Figure 10. PL spectra of complex in solid state and liquid dispersion in DMF solvent.

Figure 11. Emission spectra of complex in different solvents at 360 nm excitation.

Figure 12. Quenching efficiency of selected nitrocompounds.

Figure 13. Stern-Volmer plot for quenching mechanism of nitro compounds a) 2,4-
dinitrohydrazobenzene, b) nitroaniline, c) 2,4-dinitroaniline, d) 4-nitrophenyl hydrazine, e) 2,4-
dinitrophenol.

12
13
14
15
16
17
18
19
Table 1. Crystal data and structure refinement.
Identification code Co(bpeb)(isophthalic)]·1.5DMA
Empirical formula C34H33.50CoN3.50O5.50
Formula weight 638.07
Temperature 100(2) K
Wavelength 0.71073 Å
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 10.0544(4) Å α = 104.824(2)°
b = 11.4138(5) Å  = 92.795(2)°
c = 14.1215(6) Å γ = 104.678(2)°
Volume 1504.28(11) Å3
Z 2
Density (calculated) 1.409 Mg/m3
Absorption coefficient 0.621 mm-1
F(000) 666
Crystal size 0.195 × 0.153 × 0.135 mm3
Theta range for data collection 2.084 to 28.310°
Index ranges -13<=h<=13, -15<=k<=15, -18<=l<=18
Reflections collected 38629
Independent reflections 7487 [R(int) = 0.0256]
Completeness to theta = 25.242° 99.9%
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 0.7461 and 0.6845
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 7487 / 828 / 627
Goodness-of-fit on F2 1.027
Final R indices [I>2sigma(I)] R1 = 0.0619, wR2 = 0.1656
R indices (all data) R1 = 0.0682, wR2 = 0.1757
Extinction coefficient n/a
Largest diff. peak and hole 1.975 and -0.934 e.Å-3

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Table 2. Stern-Volmer constants for studying quenching mechanism.

Ksv × 103 (M-1) Ksv × 103 (M-1)

Quencher Range of W V × 103 (M-1)
from Eq. 2 from Eq. 3
Dinitrohydrozobenzene 15.3 21.7 0.001-0.92 7.08
Nitroaniline 6.2 9.9 0.03-0.9 5.8
2,4-Dinitroaniline 2.7 3.8 0.71-0.98 1.49
4-Nitrophenylhydrazine 1.5 1.7 0.61-0.97 1.08
2,4-Dinitrophenol -0.30 -1.9 -19.5-₋0.3 -10.63

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