Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A. This journal is © The Royal Society of Chemistry 2018 Electronic Supplementary Information A Highly Emissive Fluorescent Zn-MOF: Molecular Decoding Strategies for Solvents and Trace Detection of Dunnite in Water Prasenjit Das and Sanjay K Mandal* Department of Chemical Sciences, Indian Institute of Science Education and Research Mohali, Sector 81, Manauli PO, S.A.S. Nagar, Mohali, Punjab 140306, India Corresponding Author *E-mail: [email protected] S-1 Contents Item Description Page No Section-S1 General information – Materials and physical S-3 - S-6 measurements Section-S2 Synthesis of H4MTAIA and Zn-MOF (1) (Schemes 1 S-7 - S-8 and 2) Section-S3 Characterization of H4MTAIA (Fig. S1-S4) S-9 - S-11 (NMR, FTIR, HRMS and UV-Vis) Section-S4 Characterization of 1 (Fig. S5-S13) S-12 - S-18 ( FTIR, XRD, TGA, UV-Vis, Fluorescence) Section-S5 Gas/vapor sorption of 1 (Fig. S14-S18) S-19 - S-21 Section-S6 Fluorescence experiments and calculations S-22 - S-23 Section-S7 Solvent dependent fluorescence spectra of activated 1 S-24 - S-27 (Fig. S19-S24) Section-S8 Selective detection of Dunnite by activated 1 S-28 - S-34 (Scheme 3, Fig. S25-S36) Section-S9 Stern-Volmer plots (Fig. S37-S48) S-35 - S-40 Section-S10 Ammonium nitrate (AN) detection in water (Fig. S49- S-41 S50) Section-S11 Dunnite sensing in EtOH and DMF (Fig. S51-S54) S-42 - S-43 Section-S12 Calculation of detection limit (Fig. S55-S59) S-44 - S-47 Section-S13 Lifetime measurement and spectral overlap S-48 - S-49 (Fig. S60–S62) Section-S14 DFT calculation (Fig. S63-S66) S-50 - S-52 Section-S15 CNA test of activated 1 (Fig. S67-S74) S-53 - S-56 Section-S16 Recyclability and retention of crystallinity S-57 - S-59 (Fig. S75-S78) Table S1 DFT calculation of different solvents S-60 Table S2 Summary of Ksv and Kq S-61 Table S3 Literature survey of TNP detection S-62 Table S4 Lifetime calculation S-63 Table S5 DFT calculation of nitro-explosives S-64 S-2 Section S-1: General Information Experimental section Caution! Dunnite and TNT, TNP are highly explosive and should be carefully handled. The explosives were handled as dilute solutions and with safety measures to avoid explosion. Materials. All chemicals and solvents used for synthesis of MOF, and sensing experiment were obtained from commercial sources and were used as received, without further purification. Physical measurements FTIR spectra were measured on a Perkin-Elmer Spectrum I spectrometer with samples prepared as KBr pellets in the 4000-400 cm-1 range. Melting points were determined by a Büchi M-565 instrument with the heating rate of 10 oC per minute. High resolution mass spectrometry (HRMS) data were measured by Thermo Scientific LTQ XL LC-MS instrument for the 50-2000 amu range with ESI ion source. Atmospheric Pressure Chemical Ionization (APCI) has been used for solid state mass spectrometry. 1 13 The H and C NMR spectra of the ligands were obtained in sodium salt of D2O solution at 25 ◦C on a Bruker ARX-400 spectrometer. Elemental analysis (C, H, N) was carried out using a Leco TruSpec Micro analyzer. Thermogravimetric analysis was carried out from 25 to 600 ◦C (at a heating rate of 10 ◦C/min) under dinitrogen atmosphere on a Shimadzu DTG-60H instrument. UV-Vis-NIR and Solid state reflectance spectra were recorded using Cary 5000 by Agilent Technology. Single crystal X-ray data collection and refinements. Crystals of the compound were transferred from mother liquor to mineral oil for manipulation, selection and mounting. One appropriate block shaped crystal was selected by monitoring under an optical microscope and then put inside the nylon loop attached to a goniometer head. It was then S-3 placed under a cold stream of nitrogen gas for slow cooling to 100 K temperature. Bruker Kappa APEX II diffractometer equipped with a CCD detector (with the crystal-to-detector distance fixed at 60 mm) and sealed-tube monochromated MoK radiation was used to perform initial crystal evaluation and data collection. The diffractometer was interfaced to a PC with APEX2S1 program installed in it that controlled the crystal centering, unit cell determination, refinement of the cell parameters and data collection. The program SAINT1 was used for data integration, fitting of reflection profiles, and values of F2 and (F2) for each reflection were obtained. Data were also corrected for Lorentz and polarization effects. The subroutine XPREPS1 was used for the processing of data that included determination of space group, application of an absorption correction (SADABS),S1 merging of data and generation of files necessary for solution and refinement. The crystal structures were solved and refined by using SHELXL 2014.S2 Several full-matrix least- squares/difference Fourier cycles were performed, locating the remainder of the non- hydrogen atoms and to have reasonable thermal parameters and converged refinement resulting in the lowest residual factors and optimum goodness of fit. The crystallographic figures were drawn using Mercury V 3.0, Diamond V 3.2, ViewerLite and TOPOS Pro softwares. (S1) APEX2, SADABS, and SAINT; Bruker AXS inc: Madison, WI, USA, 2008. (S2) G. M. Sheldrick, SHELXTL Version 2014/7. https://shelx.uniac. gwdg.de/SHELX/index.php. Crystal data for 1 (formula/MW: C26H29N7O13Zn2/MW 778.33) that were collected with the use of a Bruker Kappa APEX II diffractometer equipped with a CCD detector and sealed- tube monochromated MoKradiation ( = 0.071073 Å) are as follows at 100 K: monoclinic, space group P21/c (No. 14), a = 14.7622(12) Å, b = 14.6228(12) o o o 3 Å, c = 14.8907(13) Å, α = 90 , β = 103.074 (5) , γ = 90 , V = 3131.1(5) Å , Z = 4, Dc = 1.65 mg/cm3, = 1.609 mm-1, 23697 reflections collected. Refinement of 5586 reflections (414 parameters) with I > 2σ(I) converged at a final R1 = 0.0746, wR2 = 0.2208, GOF = 1.011. Crystallographic data for 1 has been deposited with the Cambridge Crystallographic Data Centre as supplementary material (CCDC 1860161). S-4 Power X-ray diffraction (PXRD) measurements were recorded on a Rigaku Ultima IV diffractometer equipped with a 3 KW sealed tube Cu KX-ray radiation (generator power settings: 40 kV and 40 mA) and a DTex Ultra detector using Bragg-Brentano geometry (2.5° primary and secondary solar slits, 0.5° divergence slit with 10 mm height limit slit) over an angle range 5° to 50° with a scanning speed of 1° per minute with 0.02° step with XRF reduction for the metals. Sorption studies. Data were recorded on a BELSORP MAX instrument for pressures in the range 0–1.2 bar by the volumetric method. Each solid sample was transferred to a pre-weighed analysis tube, which was capped with transeals and evacuated by heating at 120 °C (based on the thermal profile obtained from TGA) under dynamic vacuum until an outgas rate of less than 2 mTorr min−1 (0.27 Pa min−1) was achieved (12–24 h). The evacuated analysis tube containing the degassed samples was then carefully transferred to an electronic balance and weighed again to determine the mass of sample. The tube was then placed back on the analysis port of the gas adsorption instrument. The outgas rate was again confirmed to be less than 2 mTorr min−1 (0.27 Pa min−1). For all isotherms, warm and cold free-space (dead volume) correction measurements were performed using ultra-high-purity He gas (UHP grade 5.0, 99.999% purity). The change of the pressure was monitored and the degree of adsorption was determined by the decrease in pressure at the equilibrium state via computer controlled automatic operations that were set up at the start of each measurement. Oil-free vacuum pumps and oil-free pressure regulators were used for all measurements to prevent contamination of the samples during the evacuation process or of the feed gases during the isotherm measurements. Field emission scanning electron microscopy (FESEM) was utilized to record surface morphology on JEOL instrument; samples were well dispersed in MeOH, drop casted in a silicon wafer, dried and coated with gold using a working distance of 4.5 to 15 mm and voltage 10 to 15 kV. High resolution transmission electron microscopy (HRTEM) was performed on FEI Tecnai G2 F20 equipped with a field emission gun operated at 200 Kv with 1 mg sample well dispersed in ethanol (10 mL) using a sonicator for 20 minutes and then put on the copper grid, which was allowed to dry using a lamp for 30 minutes. S-5 Fluorescence microscopy experiment performed using Zeiss AXIO series, Scope.A1 with an optimos camera and excited the compound in DAPI (exc: 405 nm), FITC (exc: 510 nm) and rhodamine B (exc: 570 nm) region. Confocal microscopy experiment performed using OLYMPUS inspector series and excited the compound in DAPI (exc: 405 nm), FITC (exc: 510 nm) and rhodamine B (exc: 570 nm) region. Photoluminescence experiments were performed using Horiba Scientific Fluorolog Spectrofluorometer 3. Optical imaging were performed using benchtop 3UV trans-illuminator upon excitation from 254-365 nm. DFT calculations were carried out with Gaussian 09 suite of packages.S3 The structure was optimized by hybrid functional, Becke’s three parameter exchange and the Lee−Yang−Parr Correlation Functional (B3LYP) at a split valance basis set 6-31G (d,p). (S3) M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V.