Supporting Information

New Ni-Anthracene Complex for Selective and Sensitive Detection of

2,4,6-Trinitrophenol

Kumbam Lingeshwar Reddy, Anabathula Manoj Kumar,

Abhimanew Dhir* and Venkata Krishnan*

School of Basic Sciences and Advanced Materials Research Center, Indian Institute of

Technology Mandi, Mandi-175005, Himachal Pradesh, India.

E-mail: abhimanew@iitmandi.ac.in, vkn@iitmandi.ac.in

Page No. Content

S2 Calculations of fluorescence quantum yield and Stern-Volmer

constant

S3 1H NMR spectrum of A

S4 13C NMR spectrum of A

S5 Mass spectrum of B

S6 Energy dispersive x-ray spectrum (EDAX) of complex B.

S7 Detection limit of complex B for TNP sensing.

S8 Table S1. Detection limit comparison table

S9 Stern-Volmer plot of B

S10 References

S1

Calculation of fluorescence quantum yield:

The fluorescence quantum yield of the B was determined through optically matching

solutions of anthracene (ϕ = 0.65 in ethanol) as a standard at an excitation wavelength 342

nm, from a xenon lamp of spectrofluorophotometer. The quantum yield was calculated

using equation (1), where ΦS is quantum yield of the sample, ΦR is quantum yield of the

reference AR and AS are the absorbance of the reference and sample, respectively, DS, DR are

the area of the emission of sample and reference, nS and nR are the refractive indices of the

solvent with which sample and reference solutions were prepared.

ΦS = ΦR x (AR / AS) x (DS / DR) x [nS / nR]2 (1)

After substituting all the values in the above equation the quantum yield () of B is 0.57.

Calculation of Stern-Volmer constants:

The sensitivity of the B was determined using from its Stern-Volmer constant calculated

through the following equation:

Io /I = 1+ KSV [Q]

Herein, Io and I are the fluorescence intensities in the absence and presence of the TNP,

respectively and the Stern-Volmer plots were plotted as a function of TNP concentration

[Q].

S2

Figure S1. 1H NMR spectrum of A.

S3

Figure S2. 13C NMR spectrum of A.

S4

Figure S3. Mass spectrum of complex B.

S5

Figure S4. Energy dispersive x-ray spectrum (EDAX) of complex B.

S6

Figure S5. Change in fluorescence intensity of complex B at low concentrations of TNP.

S7

Table S1. Comparison of detection limit with different reported materials

S.No. Sample Explosive detected Detection limit Reference

1.Fabricated glassy carbon electrode-rGO/ZnO

2,4,6-TNP 16 μM [1]

2. Amine functionalized diatom frustules

TNT 1 μM [2]

3. Ag-Au nanoparticles

2,4-DNT 1 μM [3]

4. Zn based MOF TNP 5 μM [4]5. Eu based MOF TNP 5 μM [5]6. Nickel based

complexTNP 2.857 μM present work

S8

Figure S6. Stern-Volmer plot for the quenching of the fluorescence of B upon the addition of

120 μM of TNP.

S9

References:

[1] A. Mohammad, K. Ahmad, R. Rajak, S.M. Mobin, Binder Free Modification of Glassy

Carbon Electrode by Employing Reduced Graphene Oxide/ZnO Composite for Voltammetric

Determination of Certain Nitroaromatics, Electroanalysis, n/a-n/a.

[2] V. Selvaraj, N. Thomas, A.J. Anthuvan, P. Nagamony, V. Chinnuswamy, Amine-

functionalized diatom frustules: a platform for specific and sensitive detection of

nitroaromatic explosive derivative, Environmental Science and Pollution Research, (2017).

[3] C. Byram, V.R. Soma, 2,4-dinitrotoluene detected using portable Raman spectrometer

and femtosecond laser fabricated Au–Ag nanoparticles and nanostructures, Nano-Structures

& Nano-Objects, 12 (2017) 121-129.

[4] E.-L. Zhou, P. Huang, C. Qin, K.-Z. Shao, Z.-M. Su, A stable luminescent anionic porous

metal-organic framework for moderate adsorption of CO2 and selective detection of nitro

explosives, Journal of Materials Chemistry A, 3 (2015) 7224-7228.

[5] X.-Z. Song, S.-Y. Song, S.-N. Zhao, Z.-M. Hao, M. Zhu, X. Meng, L.-L. Wu, H.-J. Zhang,

Single-Crystal-to-Single-Crystal Transformation of a Europium(III) Metal–Organic Framework

Producing a Multi-responsive Luminescent Sensor, Advanced Functional Materials, 24

(2014) 4034-4041.

S10