Anion-induced structural diversity of Zn and Cd coordination polymers based on bis-9,10-(pyridine-4-yl)-anthracene, their luminescent properties, and highly efficient sensing of nitro derivatives and herbicides

Supporting information

Anion-induced structural diversity of Zn and Cd coordination polymers based

on bis-9,10-(pyridine-4-yl)-anthracene, their luminescent properties and

highly efficient sensing of nitro derivatives and herbicides

Serhii I. Vasylevskyi,†*Dario M. Bassani,‡*

Katharina M. Fromm*†

†University of Fribourg, Chemin du Musee 9, Switzerland, 1700 Fribourg.

‡University of Bordeaux, ISM CNRS UMR 5255, 33400 Talence, France

Corresponding Authors:

[email protected]; [email protected];

Contents

1. Structure descriptions...S2 2. UV-Vis absorption ...S7 3. Solid-state steady state spectra ...S7 4. Lifetimes of the ligand and complexes...S8 5. Sensing of nitro explosives ...S11 6. Sensing gas-phase ...S16 7. Calculation of limit of the detection (LOD) and limit of quantification (LOQ) ...S18 8. Powder X-Ray diffraction of complexes ...S22 9. Thermal stability of the complexes ...S24 10. FT-IR spectra...S27 11. BET measurement for 4. ...S29 12. Crystallographic data ...S31

1. Structure descriptions

{[Zn(2-BA)(MeOH)2(p-Tos)2]}n (1). Coordination polymer 1 gives a structure of 1D coordination chain

formed by bridging coordination mode of BA to Zn2+ _{metal centres occupying axial position of}

octahedral geometry with the coordination bond at distance Zn1 – N1 = 2.110(3) Å. Equatorial positions are occupied by two coordinated MeOH and p-Tos through oxygen atoms in distance Zn1 – O1 = 2.158(3) Å and Zn1 – O2 = 2.115(3) Å (Fig. S1a). 1D polymers of Zn2+ _{self-assembled through weak}

hydrogen bonds forming graph-set of S1,1(6) with donation of a proton from coordinated methanol molecules in distance 2.144 Å. This proton also takes part in intermolecular interaction with another scaffold of 1D polymer in a,b-directions forming 2D polymer constructed by weak contacts (Fig. S1b). Additionally, 1D coordination chains are connected between each other through H-π interactions between proton from pyridine ring and benzene ring from tolyl-fragment of tosylate anion in distance of H4pyridine to the centroid of tosylate = 2.644 Å. General structure of the compound can be imagined

as a construction of “linear” 1D-polymers into 2D lattice assembled by weak hydrogen bonds and H-π interactions (Fig. S1b).

Figure S1. (a) Coordination geometry of Zn2+ _{in coordination polymer 1. (b) Formation of linear 1D}

polymers of Zn2+ _{formed by bridging coordination of BA, followed by self-assembly into 2D lattice of}

stacked 1D polymers by H- interactions.

{[Zn(2-BA)(MeOH)2(CF3CO2)2]}n. (2). Compound 2 crystalizes in monoclinic space group C2/c, Z=4.

Atoms of Zn have distorted octahedral coordination geometry (Fig. S2a). Equatorial positions are occupied by two coordinated N-atoms in distance Zn1 – N1 = 2.145(3) Å from pyridyl- of BA in syn-position and also coordinated CFCO- _{anion through O-atoms in distance Zn1 – O2 = 2.114(3) Å}

the formation of inter hydrogen bond between methanol proton and oxygen atom from TFA anion coordinated to the same Zn atom in distance of H1A – O3TFA=2.036 Å However, elongated coordinated

MeOH has intermolecular interaction with another 1D Zig-Zag chain to the oxygen atom of TFA in distance 2.201(3) Å (Fig. S2b). In comparison with previous coordination polymer 1, compound 2 has a “Zig-Zag” structure. Thus, mixed coordination behaviour of methanol stabilizes self-assembly of 2. Formation of “Zig-Zag” structure of 1D polymers is realised by syn-coordination of the BA to the Zn2+

atoms of tetrahedral geometry. It demonstrates a great linear rigidity of the ligand as an alternative self-assembly leading to the formation of Zig-Zag 1D coordination polymer of Zn2+_.

Figure S2. (a) Coordination node of [Zn(2-BA)(MeOH)2(CF3CO2)2] (2). (b) Projection of self-assembly

of “Zig-Zag” 1D coordination chains of 2 in a-direction.

{BA@[Zn(2-BA)(MeOH)2(H2O)2](CF3SO3)2}n (3). Coordination polymer 3 crystalizes in triclinic space

group P-1. Compound 3 has structure similar to the complex 1 which represents 1D polymer constructed by connection of Zn2+ _{atoms by bridging coordination BA. Zn}2+ _{atoms have distorted}

octahedral environment formed by four oxygen atoms from coordinated water molecules and methanol in equatorial positions in distances Zn1 – O1water = 2.106(2) Å and Zn1 – O2methanol = 2.168(2)

Å (Fig. S3a). Axial positions are occupied with N-atoms from coordinated BA in distance with Zn1 – N1 = 2.102(2) Å. Triflate anion remains uncoordinated and occupies position in the space between linear coordinated 1D ribbons and simultaneously takes part in intermolecular interaction with a proton of methanol in distance O3A – H2 = 1.825(2) Å with bond angle O3A – H2 – O2 = 169.924 and

(Fig. S3a). Interesting feature of the compound 3 is that it has encapsulated and remained uncoordinated BA which takes part also in intermolecular interaction with proton from coordinated water molecule in distance N2 – H1A = 1.932(2) Å. Such intermolecular interaction leads to the self-assembly of the 2D net formed by connecting of coordinated ribbons by hydrogen bonds involving uncoordinated BA linker, where uncoordinated triflate anions are logged (Fig. S3b).

Figure S3. (a) Coordination mode of Zn2+ _{centres in compound 3. (b) Self-assembly of 1D chains of 3}

with intercalation of uncoordinated BA (triflate and hydrogen atoms are omitted for clarity).

{[Cd(2-BA)2(ClO4)2]·n(DCM)}n (4). Compound 4 crystalizes in monoclinic space group C2/c, Z = 4. CdII

atoms have distorted coordination geometry occupied by four N-atoms from BA in distance Cd1 – N1 = 2.312(5) Å and Cd1 – N2 = 2.310(5) Å. Axial positions are occupied by oxygen atoms from coordinated perchlorate anions have disordered into two positions Cd1 – O1Apart1 = 2.460(6) Å and Cd1 – O1Bpart2 =

2.167(12) Å with a ratio of part 1:2 = 0.729:0.217 (Fig. S4a). Bridging coordination of BA leads to the self-assembly of 2D coordination polymer of Cd2+ _{with topology of the net 4,4 (Fig. S4b). The content}

that helps to self-assemble of the 4,4- topological nets together forming stack of the 2D nets, one on top of another, leading to the formation of the 3D supramolecular polymer of Cd2+_.

Figure S4. a) Coordination geometry around Cd(II) in compound 4, axial position occupied with coordinated perchlorate anion; b) formation of 2D polymeric net of 4 with topology of grids 4,4 with

cross-section of pores 11.2×11.2 Å including Van der Waals radii.

{[Cd(2-BA)(MeOH)2(Dioxane)(2-SiF6)]·mDioxane}n (5). Coordination polymer 5 crystalizes in

monoclinic space group in a P21/c space group, Z = 4. Metal centres of Cd2+ have pentagonal

bipyramidal coordination geometry forming of which proceeds due to axial coordination of BA in distance Cd1 – N1 = 2.261(3) Å (Fig. S5a). The pentagonal equatorial positions are formed by coordination of two methanol molecules Cd1 – O1 = 2.349(4) Å, Cd1 – O2 = 2.398(4) Å. Two bridging SiF62- anions in antisyn-coordinated Cd2+ with distances Cd1 – F1 =2.457(2) Å, Cd1 – F2 = 2.252(2) Å

that additionally connects 1D chains of Cd2+ _{linked by BA into one 2D lattice (Fig. S5a). The pentagonal}

geometry completes with coordination of one more dioxane molecule through O-atom to Cd2+ _at

distance Cd1 – O3 = 2.439(3) Å (Fig. S5a). Methanol protons that are involved into coordination to the Cd2+ _{are forming intermolecular hydrogen bonds with F-atoms from SiF6}2- _{in moderate distance H1 –}

ribbons of Cd(2-BA) through bridging SiF62-. This leads to the formation of the sandwich structure of

anthracene moiety of BA which is filled with dioxane molecules (Fig. S5b), the disorder of which was not modelled due to the random distribution of electron density in Fourrier electron density difference map. Remaining residual electron density was assigned to dioxane molecules which is consistent with elemental analysis.

Figure S5. (a) Heptacoordinated Cd2+ _{ions in coordination polymer 5. (b) Formation of 2D network of}

2. UV-Vis absorption

200 300 400 500 600 700 800 0.0 0.2 0.4 0.6 0.8 1.0 N or m al iz ed in te ns ity /nm L 1 2 3 4 5

Figure S6. Solid-state UV-Vis absorption spectra of the ligand BA (L) and complexes (1-5).

3. Solid-state steady state spectra

350 400 450 500 550 600 650 700 0.0 0.2 0.4 0.6 0.8 1.0 

/nm

BA

1

2

3

4

5

4. Lifetimes of the ligand and complexes

0 100 200 300 400 500 600 0 2000 4000 6000 8000 10000 12000 0 100 200 300 400 500 600 -5 0 5 Channels C ou nt s C ou nt s Channels Prompt Decay Fitted T1 = 3.165891 ch 1.389692E-09 sec S.Dev = 3.735254E-11 sec T2 = 17.21525 ch 7.556761E-09 sec S.Dev = 9.51153E-11 sec T3 = 104.7022 ch 4.595983E-08 sec S.Dev = 9.824278E-10 sec

A = 0.8084088 S.Dev = 0.1543748 B1 = 0.4399164 [34.45 Rel.Ampl] S.Dev = 3.46166E-03 B2 = 0.1211536 [51.60 Rel.Ampl] S.Dev = 7.283877E-04 B3 = 5.385163E-03 [13.95 Rel.Ampl] S.Dev = 6.540211E-05 CHISQ = 1.264577 Residual

Figure S8. Lifetime of the ligand BA: black – response of the instrument; red – Emission decay; blue-fitted with triexponential decay. Green curve – residual data from fitting. Insertion: t1, t2, t3 –

values of lifetime, second insertion A, B1, B2, B3 – parameters of triexponential decay.

0 100 200 300 400 500 0 2000 4000 6000 8000 10000 0 100 200 300 400 500 600 -4 0 4 Channels C ou nt s C ou nt s Channels Prompt Decay Fitting T1 = 5.841788 ch 2.564297E-09 sec S.Dev = 9.290971E-11 sec T2 = 17.31323 ch 7.599774E-09 sec S.Dev = 1.012627E-10 sec T3 = 91.33381 ch 4.009166E-08 sec S.Dev = 1.2609E-09 sec A = 1.165564 S.Dev = 0.1552849 B1 = 0.3053067 [36.74 Rel.Ampl] S.Dev = 2.809494E-03 B2 = 0.1587042 [56.59 Rel.Ampl] S.Dev = 1.064363E-03 B3 = 3.545552E-03 [6.67 Rel.Ampl] S.Dev = 7.27389E-05 CHISQ = 1.201241 Residuals

Figure S9. Lifetime of the 1: black – response of the instrument; red – Emission decay; blue-fitted with triexponential decay. Green curve – residual data from fitting. Insertion: t1, t2, t3 – values of

0 100 200 300 400 500 600 0 5000 10000 15000 20000 0 100 200 300 400 500 600 -4 0 4 Channels C ou nt s C ou nt s Channels Prompt Decay Fitting T1 = 7.990352 ch 3.507425E-09 sec S.Dev = 3.609012E-10 sec T2 = 22.7037 ch 9.965958E-09 sec S.Dev = 2.064129E-10 sec T3 = 107.5633 ch 4.721571E-08 sec S.Dev = 1.511138E-09 sec T4 = 1.488982 ch 6.535997E-10 sec S.Dev = 3.102172E-11 sec A = 0.7961147 S.Dev = 0.1679624 B1 = 7.418735E-02 [24.50 Rel.Ampl] S.Dev = 1.459008E-03 B2 = 5.241189E-02 [49.18 Rel.Ampl] S.Dev = 4.579635E-04 B3 = 2.14035E-03 [9.51 Rel.Ampl] S.Dev = 3.85215E-05 B4 = 0.273206 [16.81 Rel.Ampl] S.Dev = 4.776762E-03 CHISQ = 1.208554 Residuals

Figure S10. Lifetime of the 2: black – response of the instrument; red – Emission decay; blue-fitted with tetraexponential decay. Green curve – residual data from fitting. Insertion: t1, t2, t3 t4– values

of lifetime, second insertion A, B1, B2, B3 B4– parameters of tetraexponential decay.

0 100 200 300 400 500 600 0 2000 4000 6000 8000 10000 12000 0 100 200 300 400 500 600 -4 0 4 C ou nt s Channels C ou nt s Channels Prompt Decay Fitting A = 1.165564 S.Dev = 0.1552849 B1 = 0.3053067 [36.74 Rel.Ampl] S.Dev = 2.809494E-03 B2 = 0.1587042 [56.59 Rel.Ampl] S.Dev = 1.064363E-03 B3 = 3.545552E-03 [6.67 Rel.Ampl] S.Dev = 7.27389E-05 CHISQ = 1.201241 Residuals T1 = 5.841788 ch 2.564297E-09 sec S.Dev = 9.290971E-11 sec T2 = 17.31323 ch 7.599774E-09 sec S.Dev = 1.012627E-10 sec T3 = 91.33381 ch 4.009166E-08 sec S.Dev = 1.2609E-09 sec

Figure S11. Lifetime of the 3: black – response of the instrument; red – Emission decay; blue-fitted with triexponential decay. Green curve – residual data from fitting. Insertion: t1, t2, t3 – values of

0 100 200 300 400 500 600 0 2000 4000 6000 8000 10000 12000 14000 0 100 200 300 400 500 600 -4 0 4 _Channels C ou nt s C ou nt s Channels Prompt Decay Fitting T1 = 8.928375 ch 3.919177E-09 sec S.Dev = 3.109938E-10 sec T2 = 23.94492 ch 1.05108E-08 sec S.Dev = 2.279888E-10 sec T3 = 0.9723389 ch 4.268154E-10 sec S.Dev = 3.120762E-11 sec T4 = 126.3175 ch 5.544801E-08 sec S.Dev = 1.045813E-09 sec

A = 1.56334 S.Dev = 0.2045874 B1 = 0.1268507 [27.12 Rel.Ampl] S.Dev = 1.87287E-03 B2 = 0.0742778 [42.58 Rel.Ampl] S.Dev = 6.950916E-04 B3 = 0.6045961 [14.07 Rel.Ampl] S.Dev = 1.059032E-02 B4 = 5.365223E-03 [16.23 Rel.Ampl] S.Dev = 5.937317E-05 CHISQ = 1.135442 Residuals

Figure S12. Lifetime of the 4: black – response of the instrument; red – Emission decay; blue-fitted with tetraexponential decay. Green curve – residual data from fitting. Insertion: t1, t2, t3 t4– values

of lifetime, second insertion A, B1, B2, B3 B4– parameters of tetraexponential decay.

0 100 200 300 400 500 600 0 2000 4000 6000 8000 10000 12000 0 100 200 300 400 500 600 -4 0 4 C ou nt s Channels C ou nt s Channels Prompt Decay Fitting T1 = 3.266745 ch 1.433962E-09 sec S.Dev = T2 = 17.71803 ch 7.777461E-09 sec S.Dev = T3 = 90.14642 ch 3.957044E-08 sec S.Dev = A = 1.258483 S.Dev = 0.1607762 B1 = 0.3665825 [26.88 Rel.Ampl] S.Dev = 3.501024E-0 B2 = 0.1556008 [61.88 Rel.Ampl] S.Dev = 8.078113E-0 B3 = 5.552462E-03 [11.24 Rel.Ampl] S.Dev = 8.166841E-0 CHISQ = 1.301896 Residuals

Figure S13. Lifetime of the 5: black – response of the instrument; red – Emission decay; blue-fitted with triexponential decay. Green curve – residual data from fitting. Insertion: t1, t2, t3 – values of

5. Sensing of nitro explosives

400 450 500 550 600 650 700 0.0 5.0x105 1.0x106 1.5x106 2.0x106 2.5x106 3.0x106 3.5x106 A bs ol ut e in te ns ity /nm 0 20 40 60 80 120 160 NO2 NO2 Cl

Figure S14. Sensing of 1mM of 1-chloro-2-4-dinitrobenzene; legend: volume of added analyte in L to 1mg of complex 4 dispersed

in CH3CN (2.5 ml). 400 450 500 550 600 650 700 0.0 5.0x105 1.0x106 1.5x106 2.0x106 2.5x106 3.0x106 3.5x106 A bs ol ut e in te ns ilt y /nm 0 20 40 60 80 120 160 NO2 NO2 NH2 Figure S15. Sensing of 1mM of 2,4-dinitroaniline; legend: volume of added analyte in L to 1mg of complex 4 dispersed

in CH3CN (2.5 ml). 400 450 500 550 600 650 700 0.0 5.0x105 1.0x106 1.5x106 2.0x106 2.5x106 3.0x106 3.5x106 A bs ol ut e in te ns ilt y /nm 0 20 40 60 80 120 160 NH2 NO2 O2N Figure S16. Sensing of 1mM of 3,5-dinitroaniline; legend: volume of added analyte in L to 1mg of complex 4 dispersed in CH3CN (2.5 ml). 400 450 500 550 600 650 700 0.0 5.0x105 1.0x106 1.5x106 2.0x106 2.5x106 3.0x106 3.5x106 A bs ol ut e in te ns ity /nm 0 20 40 60 80 120 160 CH3 NO2 Figure S17. Sensing of 1mM of 3-nitrotoluene; legend: volume of added analyte in L to 1mg of complex 4 dispersed in CH3CN (2.5 ml). 400 450 500 550 600 650 700 0.0 5.0x105 1.0x106 1.5x106 2.0x106 2.5x106 3.0x106 3.5x106 4.0x106 A bs ol ut e in te ns ity /nm 0 20 40 60 80 120 160 NO2 NO2 CH3

Figure S18. Sensing of 1mM of 2,4-dinitrotoluene; legend volume of added analyte in L to 1mg of complex 4 dispersed in CH3CN (2.5 ml).

400 450 500 550 600 650 700 0.0 5.0x105 1.0x106 1.5x106 2.0x106 2.5x106 3.0x106 3.5x106 0 20 40 60 80 120 160 A bs ol ut e in te ns ity /nm Figure 19. Sensing of 1mM of 2,6-dinitrotoluene (2,6-DNT); legend: volume of added analyte in L to 1mg of complex 4 dispersed in CH3CN (2.5 ml) -1x10-5 _{0 1x10}-5 _2x10-5 _3x10-5 _4x10-5 _5x10-5 _6x10-5 _7x10-5 1 2 3 4 5 I0 /I M Equation y = a + b*x Weight No Weighting Residual Sum of Squares 0.0633 5 Pearson's r 0.9632 Adj. R-Squa 0.9949 Value Standard Er B Interce_{Slope 77814.46 4854.7920}1

--Figure S20. Stern-Volmer plot of quenching of 4 with 2,6-DNT with Ksv =

77814 M-1 400 450 500 550 600 650 700 0.0 5.0x105 1.0x106 1.5x106 2.0x106 2.5x106 3.0x106 3.5x106 A bs ol ut e in te ns ity /nm 0 L 20 L 40 L 60 L 80 L 120 L 160 L O2N NO2 NO2 Figure S21. Sensing of 1mM of

trinitrobenzene (TNB); legend: volume of added analyte in L to 1mg of complex 4 dispersed in CH3CN (2.5 ml) 0.0 5.0x10-6 _1.0x10-5 _1.5x10-5 _2.0x10-5 _2.5x10-5 1.0 1.2 1.4 1.6 1.8 2.0 I0 /I M Equation y = a + b*x Weight No Weighting Residual Sum of Squares 0.01896 Pearson's r 0.92327 Adj. R-Square 0.99706

Value Standard Erro B Intercept_{Slope 36855.2585}1 _2655.60075

--Figure S22. Stern-Volmer plot of quenching of 4 with TNB with Ksv =

36855 M-1 400 450 500 550 600 650 700 0 1x106 2x106 3x106 0.0 2.0x10-5 4.0x10-5 6.0x10-5 0 10 20 30 40 50 60 I0 /I M Equation y = a + b*x Weight No Weighting Residual Sum of Squares 1.1835 Pearson's r 0.97948 Adj. R-Square 0.95454

Value Standard Error

B Intercept 1 --Slope 139221.04088 20983.06282 Ksv = 139221 M -1 A bs ol ut e in te ns ity /nm 0 L 20 L 40 L 60 L 100 L 120 L 160 L OH O2N NO2 NO2 Figure S23. Sensing of 1mM of 0.0 2.0x10-5 _4.0x10-5 _6.0x10-5 0 10 20 30 40 50 60 I0 /I M Equation y = a + b*x Weight No Weighting Residual Sum of Squares 1.1835 Pearson's r 0.97948 Adj. R-Square 0.95454

Value Standard Error B Intercept_{Slope 139221.04088}1 _20983.06282

--K_sv = 139221 M-1

Sensing of Pesticides 400 500 600 700 0 1x106 2x106 3x106 4x106 0 10 20 40 60 80 120 160 Wavelength (nm) A bs ol ut e In te ns ity

Figure S25. Sensing of 2,4,6-trichloroanisole (TCA) by CP 4 the legend: the volume L of added analyte in mM concentration of TCA

400 450 500 550 600 650 700 0.0 5.0x105 1.0x106 1.5x106 2.0x106 2.5x106 3.0x106 3.5x106 A bs ol ut e in te ns ity /nm 0 20 40 60 80 120 160 N N N N H N H Cl

Figure S26. Sensing of Simazine by CP 4 the legend: the volume L of added analyte in mM

concentration of Simazine 0 1x10-5 2x10-5 3x10-5 4x10-5 1 2 3 4 5 6 7 8 Io /I M Equation y = a + b*x Weight No Weighting Residual Sum of Squares 0.04738 Pearson's r 0.97343 Adj. R-Squar 0.99813

Value Standard Err C Intercep_{Slope 90247.7580}1 _2625.30355

--Figure S27. Stern-Volmer plot of TCA sensing with compound 4, Ksv = 90247 M-1 -1x10-5 _{0 1x10}-5 _2x10-5 _3x10-5 _4x10-5 _5x10-5 _6x10-5 _7x10-5 1.0 1.5 2.0 2.5 3.0 I0 /I M Equation y = a + b*x Weight No Weighting Residual Sum of Squares 0.21896 Pearson's r 0.94289 Adj. R-Square 0.99236

Value Standard Error B Intercept_{Slope 36705.54902}1 _2094.3307

--Figure S28. Stern-Volmer plot of Simazine sensing with compound 4, Ksv = 40214 M-1

400 450 500 550 600 650 700 0.0 5.0x105 1.0x106 1.5x106 2.0x106 2.5x106 3.0x106 3.5x106 0 20 40 60 80 120 160 A bs ol ut e in te ns ity Wavelength (nm)

Figure S29. Fluorescence sensing of Trinitrobenzene (TNB) by CP 4 in MeCN. Inset: plot of the quenching of 4 by TNB according to eq(2). *Volume of analyte added is in L of 1

mM concentration. 0.0 2.0x10-5 _4.0x10-5 _6.0x10-5 0.0 0.5 1.0 1.5 2.0 ln (Io /I ) [TNB] (M) Equation y = a + b*x Weight No Weighting Residual Sum of Squares 0.0352 2 Pearson's r 0.9947 Adj. R-Squar 0.9874

Value Standard Err

F Intercept_{Slope 33019.3110 1518.80473}-0.05256 0.05236

Figure S30. Plot of the quenching of 4 by TNB according to eq(2). With slope value = 33019.3

400 450 500 550 600 650 700 0.0 5.0x105 1.0x106 1.5x106 2.0x106 2.5x106 3.0x106 3.5x106 0 20 40 60 80 120 160 A bs ol ut e in te ns ity /nm

Figure S31. Fluorescence sensing of 2,6-Dinitrotoluene (2,6-DNT) by CP 4 in MeCN.

Inset: plot of the quenching of 4 by DNT according to eq(2). *Volume added of analyte is

in L 0.0 2.0x10-5 _4.0x10-5 _6.0x10-5 0.0 0.5 1.0 1.5 ln (Io /I ) [DNT] (M) Equation y = a + b*x Weight No Weighting Residual Sum of Squares 3.4548E-4 Pearson's r 0.99974 Adj. R-Square 0.99923

Value Standard Error ?$OP:A=1 Intercept_{Slope 45743.2889}0.00988 _734.71920.011

Figure S32. Plot of the quenching of 4 by DNT according to eq(2). With slope value = 45743.2

0 1x10-5 _2x10-5 _3x10-5 _4x10-5 _5x10-5 _6x10-5 _7x10-5 0 1 2 3 4 ln (I0 /I) M Equation y = a + b*x Weight No Weighting Residual Sum of Squares 0.1675 6 Pearson's 0.9939 Adj. R-Squ 0.9854 Value Standard B Interce_{Slope 66797.52 3312.7033}-0.00357 0.11421

Figure S33. Plot of the quenching of 4 by TNP according to eq(2). With slope value = 66797.5

400 500 600 700 0 200000 400000 600000 0L 10L 30L 60L 90L 160L 200L 240L Wavelength (nm) In te ns ity (C P S / M ic ro A m ps )

Figure S35. Fluorescent quenching of 4 in water with TNP (1mM concentration) with em is 450

nm (ex is 375 nm). 0 1x10-5 _2x10-5 _3x10-5 _4x10-5 0.0 0.5 1.0 1.5 2.0 ln (I0 /I) M Equation y = a + b*x Weight No Weighting Residual Sum of Squares 0.0347 Pearson's r 0.99444 Adj. R-Square 0.98705

Value Standard Erro B Intercept 0.00183 0.04909 Slope 54263.43863 2346.87479

Figure S34. Plot of the quenching of 4 by TCA according to eq(2). With slope value = 54260.4

0.0E+0 1.0E-4 2.0E-4 1 1.01 1.02 1.03 1.04 1.05







[TNP] (M)

Figure S36. Stern-Volmer plot of the intermolecular quenching of BA by TNP in acetonitrile. ex = 370 nm, em = 450 nm. Line

400 450 500 550 600 0 200000 400000 600000 800000 C ou nt s Wavelength/nm 0 L 20 L 40 L 60 L 80 L 100 L 120 L 140 L 180 L

Figure S37. Detection of TNP (1mM concentration) by 4 in CH3CN in the presence of 1mM solution of

each NAC: 1-chloro-2-4-dinitrobenzene, 3,5-dinitroaniline, 2,4-dinitrotoluene, 2,4-dinitroaniline.

400 450 500 550 600 -100000 0 100000 200000 300000 400000 500000 600000 700000 800000 900000 1000000 C o u n ts Wavelength/nm 0 L 20 L of TNP 200 L 1Cl-2,4-DNB

Figure S38. Response of sensor 4 after adding 20 L of TNP and sequential addition of 200 L 1-chloro-2,4-dinitrobenzene. Stock solutions of TNP

and 1-Cl-2,4-DNB are 1mM. 400 450 500 550 600 0 200000 400000 600000 800000 1000000 C ou nt s Wavelength/nm 0 L 20 L of TNP 200 L of 2,4-DNT

Figure S39. Response of sensor 4 after adding 20 L of TNP and sequential addition of 200 L 2,4-dinitrotoluene (2,4-DNT). Stock solutions of TNP and

2,4-DNT are 1mM. 400 450 500 550 600 0 200000 400000 600000 800000 1000000 C ou nt s Wavelength/nm 0 L 20 L of TNP 200 L of 2,4-DNA

Figure S40. Response of sensor 4 after adding 20 L of TNP and sequential addition of 200 L

2,4-dinitroaniline (2,4-DNA). Stock solutions of TNP and 2,4-DNA are 1mM.

400 450 500 550 600 0 200000 400000 600000 800000 1000000 C ou nt s Wavelength/nm 0 L 20 L of TNP 200 L of 2,6-DNA

Figure S41. Response of sensor 4 after adding 20 L of TNP and sequential addition of 200 L 2.6-dinitroaniline (2,6-DNA). Stock solutions of TNP and

400 450 500 550 600 0 20000 40000 60000 80000 100000 120000 140000 C ou nt s Wavelength/nm 0 L 5 L 20 L 45 L 65 L 90 L 120 L 160 L

Figure S42. TNP detection by 4, 4 is dispersed in water containing 1mM solution of each cation: Na+_,

K+_{, Ca}2+_{, Mg}2+ _{and anions: Cl}-_{, SO4}2-_{, NO3}-_{, CH3CO2}-_{. (TNP concentration in water is 1mM).}

6. Sensing gas-phase

400 500 600 700 0.0 5.0x105 1.0x106 1.5x106 2.0x106 2.5x106 3.0x106 3.5x106 4.0x106 _{0 min} 15 min 30 min 45 min 1h nm C ou nt s

Figure S43. Sensing of 2,4,6-trichloroanisole (TCA) from the gas-phase with 4. The experiment performed with a neat vapour pressure at 25 o_{C of TCA.}

400 450 500 550 600 650 700 0.0 5.0x105 1.0x106 1.5x106 2.0x106 2.5x106 3.0x106 3.5x106 4.0x106 C ou nt s /nm 0 min 1 h 2 h 3 h 4 h 6 h 10 h 12 h

Figure S44. Sensing of 1,3,5-trinitrobenzene (TNB) from the gas-phase with 4 deposited in glass substrate. The experiment performed with a neat vapour pressure at 25 o_{C of TNB.}

400 450 500 550 600 650 700 0 1000000 2000000 3000000 4000000 5000000 6000000 7000000 8000000 In te ns ity (C P S / M ic ro A m ps ) Wavelength (nm)

Figure S45. Reusability of the sensor 4 in sensing of TCA. A drop-cast film of 4 was exposed for 30 min to vapours of TCA (30 min, green line). After exposure to ambient for 3 hours, the fluorescence

400 500 600 700 0 1000000 2000000 3000000 0 2h 3h 12h 18h Wavelength (nm) In te ns ity (C P S / M ic ro A m ps )

Figure S46. Sensing of 2,6-dinitrotoluene (2,6-DNT) from the gas-phase with 4 deposited in glass substrate. The experiment performed with a neat vapour pressure at 25 o_{C of 2,6-DNT.}

7. Calculation of limit of the detection (LOD) and limit of quantification (LOQ)

Table S1. Standard deviation () determined as a three times response of the blank in fluorescence intensity 0_I n. 0_I 1 3365302 0_I 2 3359530 0_I 3 3353356 standard deviation  5974.127 10 59741.27

Calculations used to determine LOD and LOQ for pesticides and nitro aromatics:

for LOD and for LOQ

𝑦𝐼0 𝐼 = ln (_{𝐼0― 3𝜎}𝐼0 ) 𝑦𝐼0 𝐼 = ln (_{𝐼0― 10𝜎}𝐼0 ) LOD or LOQ = 𝑦 ― 𝑏_𝐾 𝑠𝑣

0.0E+0 1.0E-4 0 0.5 1 1.5 2 2.5

TCA

Concentration of TCA in M Ln (I 0 /I)

Figure S47. Plotting of ln(I0/l) of 4 in acetonitrile upon addition of solution of TCA (stock solution is

1 mM) in acetonitrile with em is 450 nm (ex is 375 nm).

Table S2. Calculation of LOD and LOQ for TCA with 4. for LOD 𝑦𝐼0 𝐼 for LOQ 𝑦𝐼0 𝐼

Ksv b LOD mol/L LOQ mol/L LOD,

ppb LOQ, ppb 0.005131 0.017206 54263 0.0018 6.13832E-08

(61 nM) 2.83917E-07(0.28 M)

16.5 76

0.0E+0 5.0E-6 1.0E-5 1.5E-5 2.0E-5

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

SIM

Concentration of SIM in M

Ln

(I

0

/I)

Figure S48. Plotting of ln(I0/l) of 4 in acetonitrile upon addition of solution of SIM (stock solution is

1 mM) in acetonitrile with em is 450 nm (ex is 375 nm).

Table S3. Calculation of LOD and LOQ for SIM with 4. for LOD 𝑦𝐼0 𝐼 for LOQ 𝑦𝐼0 𝐼

Ksv b LOD mol/L LOQ mol/L LOD, ppb LOQ, ppb

0.007263 0.024419 35977 0.0096 4.77894E-07

(478 nM) 3.64698E-06(3.65 M)

0.0E+0 1.0E-4 -0.5 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5

TNP

Concentration of TNP in M

Ln

(I

0

/I)

Figure S49. Plotting of ln(I0/l) of 4 in acetonitrile upon addition of solution of TNP (stock solution is

1 mM) in acetonitrile with em is 450 nm (ex is 375 nm).

Table S4. Calculation of LOD and LOQ for TNP with 4 for 𝑦𝐼0 𝐼 LOD for 𝑦𝐼0 𝐼 LOQ

b Ksv LOD mol/L LOQ mol/L LOD, ppb LOQ, ppb

0.007175 0.024121 0.0036 66798 5.35253E-08

(54 nM) 3.07209E-07(0.31 M)

15.5 89.5

0.0E+0 2.0E-5 4.0E-5 6.0E-5 8.0E-5

0 0.5 1 1.5 2 2.5

TNB

Concentration of TNB in M

Ln

(I

0

/I)

Figure S50. Plotting of ln(I0/l) of 4 in acetonitrile upon addition of solution of TNB (stock solution is

1 mM) in acetonitrile with em is 450 nm (ex is 375 nm).

0.00E+00 2.00E-04 0 0.2 0.4 0.6 0.8 1 1.2

2,6-DNT

Concentration of 2,6-DNT in M

Ln

(I

0

/I)

Figure S51. Plotting of ln(I0/l) of 4 in acetonitrile upon addition of solution of 2,6-DNT (stock solution

is 1 mM) in acetonitrile with em is 450 nm (ex is 375 nm).

Table S6. Calculation of LOD and LOQ for 2,6-DNT with 4 for 𝑦𝐼0 𝐼 LOD for 𝑦𝐼0 𝐼 LOQ

b Ksv LOD mol/L LOQ mol/L LOD,

ppb LOQ, ppb 0.004646 0.015573 0.0099 45743 3.18002E-07 (320 nM) 5.56863E-07 (0.56 M) 73.6 128.9 Table S7. Comparison table of LOD for reported sensors for detection of TNP

Sensor

type

K

SV a

_M

-1

_cv

b

_{LOD M (ppb or}

ppm)

c

LOQ µM

Reference

Zn-MOF

3.11×10

4

_-

_{0.45 (102 ppb)}

_-

1

ACR-1

1.50×10

4

_-

_{10.49 (2.4 ppm)}

_-

2

Zn-MOF

6.19×10

4

_{0.56 (128 ppb)}

3

Zr-MOF

2.49×10

4

_-

_{7.12 (1.63 ppm)}

_-

4

SBA-15

2.50×10

5

_-

_{1.74 (400 ppb)}

_-

5

Zn-MOF

1.36×10

4

_-

_{0.49 (110 ppb)}

_-

6

Cd-MOF

2.68×10

4

_{0.27 (62 ppb)}

_-

7

Cd-MOF

2.43×10

4

_{0.15 (35 ppb)}

_-

8

Cd-MOF

4.86×10

4

_{6.3 (1.4 ppm)}

_-

9

Zn-MOF

4.60×10

4

_{0.013 (2.9 ppb)}

_-

10

Eu-MOF

1.50×10

4

_-

_{4.98 (1.14 ppm)}

_-

11

Cd-CP (4)

13.9×10

4

₆₆₈₀₀

_{0.054 (12.4 ±0.1}

_{0.31 (90)}

_{This work}

a_{Determined at low analyte concentration.} b_{Determined according to eq(2).} c_{In ppm/ppb by volume.}

8. Powder X-Ray diffraction of complexes

Figure S54. Powder diffraction of {[Cd(2-BA)2(ClO4)2]·n(DCM)}n (4).

9. Thermal stability of the complexes

Thermal analyses (TGA) for 1, 2, 4, 5 were performed under N2 flow at the heating rate of 10 oC min-1

from 20 to 600o_{C in a Mettler Toledo SDTA 851a (Fig. S56-S59). Complex 1 shows mass loss of ~11.5%}

starting from rt upon heating to 120o_{C which can be assigned to the removal of the uncoordinated}

MeOH and DCM guest molecules. Further heating over 330o_{C leads to the decomposition of organic}

linkers and coordinated p-Tos anions with mass loss of ~51%. Similar trend was observed for complex

2, upon heating from rt to 100o_{C coordination polymer loses uncoordinated MeOH molecules,}

continuous heating over 330o_{C results in decomposition of 1D polymer followed by destruction of}

organic ligands. 2D polymer network of compound 4 also shows instability under heating from rt to 80o_{C obviously followed by losing DCM molecules trapped in the network structure of 4. Further}

heating over ~340o_{C leads to decomposition of organic part of the compound and collapsing of the 2D}

structure. Interesting behaviour demonstrates complex 5, upon heating in the range from 20 to 600o_C

complex shows a multistep decomposition. First step begins from 20o_{C to 80}o_{C with mass loss of ~14%}

corresponding to the evaporation of uncoordinated dioxane molecules. Further heating to 150o_C

results in removal of coordinated to Cd(II) dioxane molecule with integrated mass loss of ~14%. The third step begins after heating over 250o_{C leading to mass loss of ~36%, it presumably corresponds to}

the decomposition of organic linkers. Additional mass loss of ~6% might be assigned to the decomposition of SiF62- anions.

Figure S57. TGA of complex 2.

10. FT-IR spectra

4000 3500 3000 2500 2000 1500 1000 500 wavenumber/cm-1

Figure S60. FT-IR of complex {[Zn(2-BA)(MeOH)2(p-Tos)2]}n (1).

4000 3500 3000 2500 2000 1500 1000 wavenumber/ cm-1

4000 3500 3000 2500 2000 1500 1000 wavenumber/ cm-1

Figure S62. FT-IR of complex {BA@[Zn(2-BA)(MeOH)2(H2O)2](CF3SO3)2}n (3).

4000 3500 3000 2500 2000 1500 1000 wavenumber/ cm-1

4000 3500 3000 2500 2000 1500 1000 wavenumber/cm-1

Figure S64. FT-IR of complex {[Cd(2-BA)(MeOH)2(Dioxane)(2-SiF6)]·mDioxane}n (5).

11. BET measurement for 4.

0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 Adsorption Desorption Q ua nt ity A bs or be d (m m ol /g ) Relative Pressure (P/P₀)

0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 1/ [Q (p °/ p - 1) ] Relative Pressure (p/p°) Fitted Excluded Fitting

Figure S66. BET surface area plot for 4 with output below for the fitting:

Table S8. Fitting result of isotherm for 4, N2 gas for BET surface determination was used.

BET Surface Area 30.2960 ± 0.7203 m²/g Slope 3.223349 ± 0.066188 g/mmol Y-Intercept 0.002696 ± 0.038506 g/mmol Correlation coefficient 0.9968526

Maximum pore volume 0.105483 cm3_/g

Median pore width 15.6925 nm

Micropore volume 0.042 cm3_/g 0 50 100 150 200 250 300 0.00 0.02 0.04 0.06 0.08 0.10 0.12 P o re V o lu m e ( cm 3 /g ) Pore width (nm)

12. Crystallographic data

Table S9. Crystallographic data for complexes 1-5.

Identification code 1- 1843186 2-1843187 3-1843188 4- 1843184 5-1843191

Empirical formula C40H38N2O8S2Zn C30H24F6N2O6Zn C52H44F6N4O10S2Zn C48H32CdCl2N4O8 C30H32CdF6N2O4Si

Formula weight 804.21 687.88 1128.40 976.07 739.06

Temperature/K 200 250 200 200 250

Crystal system triclinic monoclinic triclinic monoclinic monoclinic

Space group P-1 C2/c P-1 C2/c P21/c a/Å 7.4634(5) 10.5996(10) 10.1618(6) 13.7850(14) 15.5646(11) b/Å 11.3831(8) 11.6402(10) 10.4605(6) 25.4887(13) 16.3882(9) c/Å 12.4240(9) 22.1602(17) 13.6324(8) 16.1626(15) 15.3720(13) α/° 70.731(5) 90 71.447(5) 90 90 β/° 78.927(5) 92.636(7) 88.517(5) 101.201(8) 118.141(5) γ/° 78.523(5) 90 69.964(5) 90 90 Volume/Å3 _{967.29(12) 2731.3(4) 1285.00(14) 5570.7(8) 3457.5(4)} Z 1 4 1 4 4 ρcalcg/cm3 1.381 1.673 1.458 1.164 1.420 μ/mm-1 _{0.797 0.990 0.643 0.535 0.733} F(000) 418.0 1400.0 580.0 1976.0 1496.0 Crystal size/mm3 _{0.32 × 0.173 × 0.1 0.16 × 0.123 × 0.07 0.25 × 0.173 × 0.04 0.31 × 0.17 × 0.1 0.54 × 0.297 × 0.1}

Radiation MoKα (λ = 0.71073) MoKα (λ = 0.71073) MoKα (λ = 0.71073) MoKα (λ = 0.71073) MoKα (λ = 0.71073)

Reflections collected 12508 15488 16354 35269 43536

Independent reflections 3442 [Rint = 0.0633, Rsigma = 0.0475] 2441 [Rint = 0.0966, Rsigma = 0.0554] 4516 [Rint_0.0393] = 0.0491, Rsigma = 4976 [Rint = 0.1132, Rsigma = 0.0709] 6178 [Rint = 0.1114, Rsigma = 0.0747]

Data/restraints/parameters 3442/111/301 2441/74/234 4516/0/345 4976/24/294 6178/36/411

Goodness-of-fit on F2 _{0.964 1.160 1.066 1.090 0.837}

Final R indexes [I>=2σ (I)] R1 = 0.0451, wR2 = 0.1209 R1 = 0.0598, wR2 = 0.1136 R1 = 0.0466, wR2 = 0.1193 R1 = 0.0520, wR2 = 0.1234 R1 = 0.0406, wR2 = 0.0872

Final R indexes [all data] R1 = 0.0606, wR2 = 0.1294 R1 = 0.0876, wR2 = 0.1228 R1 = 0.0589, wR2 = 0.1250 R1 = 0.0938, wR2 = 0.1314 R1 = 0.0868, wR2 = 0.0996

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