Supporting Information

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1 Supporting Information Polymorphism in Sn(IV)-Tetrapyridyl Porphyrins with Halogenated Axial Ligand: Structural, Photophysical, and Morphological Study. Jyoti Rani, a Anju Raveendran, b Sushila, a Arvind Chaudhary, c Manas K. Panda* b,d and Ranjan Patra *a a Department of Chemistry and Centre for Advanced Studies, Panjab University, Chandigarh , INDIA. ranjanpatra06@gmail.com b Photosciences & Photonics Section, Chemical Science & Technology Division, CSIR-National Institute for Interdisciplinary Science and Technology, Thiruvananthapuram , mannup25@gmail.com, manas.panda@niist.res.in c Science and Engineering Research Board, New Delhi , INDIA d Academy of Scientific and Innovative Research (AcSIR), New Delhi , India. Synthesis and Experimental Section Materials. Reagents and solvents were purchased from commercial sources and purified by standard procedures before use. Sn(TpyP)(OH)2 were prepared by literature method reported previously. 1 Preparation of [Sn(T 4 PyP)(L)2][L = 3,5-dichlorobenzoic acid]; trans- Dihydroxo[5,10,15,20-tetrakis(4-pyridyl)porphyrinato]tin(IV) (15.4 mg, 0.02mmol) and 3,5- dichlorobenzoic acid (9.55mg, 0.05mmol) was placed in a sealed reactor with 5 ml of CHCl3 and 0.5 ml of DMF. The mixture was heated for 1 hour at 70 ⁰C, and after cooling to room temperature, solvent was removed by rotary evaporator which provided product as pink solid (8.5 mg, yield 75%). FT-IR (KBr, cm 1 ): 3080, 1655, 1406, 1289, 1031, 797, 722, 660, 571, 413. UV vis in a CHCl3 (1 x 10-6 M): λmax/nm 420, (5.48), 552 (4.01), 589 (3.10). The pink solid (10 mg) is then dissolved in 10 ml CHCl3, filtered and divided into two parts. one tube is layered with 5 ml of diethyl ether and kept for slow diffusion/evaporation, X-ray quality crystal of 1α was obtained after one week. Other part was layered with 5 ml of hexane from which crystal of 1β was obtained after 10 days. 1

2 Preparation of 2, [Sn(T 4 PyP)(L)2][L = 3,5-dibromobenzoic acid ]; trans- Dihydroxo[5,10,15,20-tetrakis(4-pyridyl)porphyrinato]tin(IV) (7.7 mg, 0.01 mmol) and 3,5- dibromobenzoic acid (6.95 mg, mmol) was placed in a sealed reactor with 5 ml of CHCl3 and 0.5 ml of DMF. The mixture was heated for 1 hour at 70⁰C, and after cooling to room temperature, remove the solvent through rotary evaporator gives the pink solid (10.64 mg, yield 84%). X-ray quality small thin plate red crystals of the porphyrin complex were obtained by slow evaporation of CHCl3 solution of the complex. FT-IR (KBr, cm -1 ): 3081, 1968, 1657, 1406, 1277, 1032, 989, 868, 737, 705, 659, 568, 482. UV Vis in a CHCl3 (1 x 10-6 M): λmax/nm 420 (5.45), 553 (4.05), 589 (3.22). Instrumentation and Methods Solution and solid-state absorption spectra were recorded on Shimadzu UV-2401C spectrophotometer. For thin film absorption and emission spectra, the crystals of the polymorphs were carefully grinded on the surface of quartz plate to make a thin film and then placed in the sample space for spectral data collection. Fluorescence spectra were recorded on a HORIBA SPEX Fluorolog spectrofluorimeter FL-1039 and spectra were recorded accordingly. The crystals were glued (with non-fluorescent grease) on the groove of solid sample holder and covered with quartz plate and then placed on the optical path of the fluorimeter and spectra were recorded. Fluorescence lifetime measurements were carried out on a Modular Time correlated single photon counting (TCSPC) spectrometer equipped with Delta Flex detector: PPD850. Thermogravimetric analyses (TGA) were performed on a TA instrument SDT Q600 V20.9 Build 20, in a temperature range of C with heating rate of 10 C per minute under nitrogen flow. Differential Scanning Calorimetry (DSC) experiments were carried out on a TA Instruments DSC Q2000 model with a Peltier cooling system with heating and cooling rate of 10 C min 1 under nitrogen atmosphere. InfraRed spectra were recorded in a SHIMADZU IR Prestige-21 spectrometer using KBr as matrix. Optical images were captured using Leica DM 2500P microscope in transmission mode. Scanning Electron Microscopy (SEM) images were obtained from JEOL-JSM5610 instrument using 8-15 kv of energy. Samples were prepared by drop-casting (from corresponding solvent mixture from which they were crystallized on silicon wafer substrate and dried at ambient temperature inside a desiccator. Samples were coated with gold prior to the SEM study. Transmission Electron Microscopy (TEM) measurements were performed in a FEI Tecnai T30 with EDAX microscope using accelerating voltage of 300 kv. The samples of 1 were 2

3 prepared by drop casting from chloroform: diethyl ether solution on a carbon coated copper grid. Single crystal X-ray diffraction: Single-crystal X-ray diffraction data for 1α and 1β were collected using Bruker SMART APEX CCD diffractometer equipped with low-temperature apparatus (CRYO Industries) and intensity data were collected using graphite-monochromated Mo Kα radiation (λ= Å) using APEX II program. 2 Data reduction was carried out with SAINT software and were analyzed for agreement using XPREP. 2 Absorption correction was carried out with the SADABS program. 3 The structure was determined by the method included in SHELXT program of the APEX software suite and refined using SHELXL The atoms other than hydrogens were refined anisotropically. Details of crystallographic parameters are given in Table 1. Single-crystal X-ray diffraction data for 2 were collected using Rigaku Saturn 724+ CCD diffractometer [Mo-Kα radiation (λ = Å)]. Crystallographic parameters are given in Table 1 in main text. The CCDC numbers for the structure are (for 1 ), (for 1 ), (for 2). Powder X-ray diffraction (PXRD) Powder X-ray Diffraction (PXRD) was measured by a XEUSS SAXS/WAXS system by Xenocs, operated at 50 kv and 0.60 ma. The X-ray radiation was collimated with FOX2D mirror and two pairs of scatter less slits from Xenocs. The data were collected in the transmission mode geometry using Cu Kα radiation (wavelength λ = 1.54 Å). Crystals of 1α, 1 and 2 were grinded carefully to obtain powder crystalline sample and subjected to X-ray diffraction. In order to see the crystallinity of the drop-casted samples, we have repeatedly drop-casted to acquire sufficient amount of sample. The diagrams were recorded using an image plate system (Mar 345 detector) and processed using Fit2D software. Computational Details. Computational Details: DFT calculations have been carried out by employing a B3LYP hybrid functional using, Gaussian 09, revision B.04, package. 8 Becke s three-parameter hybrid exchange functional, 9 the nonlocal correlation provided by the Lee, Yang, and Parr expression, 10 and Vosko, Wilk, and Nussair 1980 correlation functional (III) for local correction was used for these calculations. For heavy atom Sn, LANL2DZ basis set was used and 3-21G basis set for C, N, O, Cl and H -atoms. The coordinates are taken directly from the single-crystal X-ray data of 1α and 1β. Since in the X-ray structure, hydrogen atoms were 3

4 generally located on the calculated position, we have carried out energy optimization with hydrogens atoms. Single point energy calculation was performed using the coordinates without hydrogen atom. The total energy was calculated by simply adding the energy obtained from coordinates without hydrogen atom and the energy of the hydrogen atom added to it and then compared the energy between two polymorphs. Figure S1. Optical microscope pictures of polymorphs1α and 1β. Figure S2. TGA/DTGA thermogram of 1α and 1. 4

5 Figure S3. DTA thermogram of the polymorphs 1α and 1. Figure S4. DSC plots of 1 and 1β. 5

6 Figure S5. Packing features of 1α along different axis Figure S6. Packing features and intermolecular interaction of 1β. 6

7 Figure S7. Packing feature showing stacking interactions of the molecules of 1β. Figure S8. DTA thermogram and PXRD plot (recorded at 298 K) of 2,. Figure S9. IR spectra (KBr pellet) of two polymorphs 1α and 1β. 7

8 Figure S10. Hirshfeld fingerprint plot of 1α Figure S11. Hirshfeld fingerprint plot of 1 8

9 Figure S12. SEM morphology of the slightly bigger crystals of polymorphs 1 (a,b) and 1 (c,d) grown from drop-casted samples. Concentration of the solution used for drop casting is 1 x 10-3 M. 9

10 Figure S13. Comparative PXRD plots of the drop-casted (1 from CHCl3:Et2O, 1:1 v/v solution, 1 x 10-3 M) sample and grinded powder from crystal of 1. Figure S14. TEM images and Selected Area Electron Diffraction (SAED) pattern of the drop-casted sample (from chloroform/diethyl ether 1:1 v/v mixture, for 1 ). Concentration of the solution used for drop casting is 1 x 10-3 M. 10

11 Figure S15. (a) Expanded view of the emission spectra of grinded films of 1,1 and 2, (b). excitation spectra of the films (grinded film on quartz plate). Figure S16. Fluorescence life time plots. For polymorph 1, 1 x 10-4 M solution in CHCl3: diethyl ether (1:1 ) were used, and for 1, CHCl3: hexane (1:1 ) mixture were used. 418 nm excitation source was employed for collecting the data. Table S1 Photophysical Parameters of two polymorphs 1 and 1 Compound Absorption /nm Emission nm 1 in CHCl3 420, 553, ,

12 1 film 435, 557, , 650, film 435, 557, , 655, film , 653, crystal - 596, 653, crystal - 599, 655, 708 Table S2. Fluorescence life time values in different solvent mixture (conc. 1 x 10-4 M) Compound 1 in CHCl3 : Diethylether (1:1) For 1 Life time ( ) / ns 1.13 em = 650 nm, 2 = 1.17) 1.18 ( em = 695 nm, 2 = 1.17) ( ex = 418 nm) 1 in CHCl3 : Hexane (1:1) For em = 650 nm, 2 = 1.03) 1.34 ( em = 705 nm, 2 = 1.14) ( ex = 418 nm) Table S3. Coordinates of output geometry of 1α Sn Cl Cl C O O C N C

13 C N C C C C C N C C C C C C C N C C C C C C C C C C C C N C

14 C N C C C C N C C C C N C C C C C C C C C Cl Cl C O O C C C C

15 C C Table S4. Coordinates of output geometry of 1β Sn Cl Cl O N N C C N C C C C C C C N C C C C C C C C C C C

16 O C C C C C C C N N C C N C C C C C C C N C C C C C C C C C C C Cl

17 Cl O C C C O C C C C References: 1. Patra, R.; Titi, H. M.; Goldberg, I. Cryst. Growth Des. 2013, 13, APEX DUO, version 2.1 4, and SAINT, version 7.34A, Bruker AXS Inc., Madison, WI, Sheldrick, G. M. SADABS, University of Göttingen, Göttin-gen, Germany, Sheldrick, G. M. SHELXL2014. University of Go ttingen, Go ttingen, Germany, Sheldrick, G. M, SHELXTL XT Crystal Structure Solution, version 2014/4, Bruker AXS, Sheldrick, G. M. Acta Crystallogr. A 2015, 71, Sheldrick, G. M. Acta Crystallogr. A 2008, 64, Gaussian 09, Revision A.1, Frisch, M. J.; Trucks, G. W.; Schle-gel, H. B.; Scuseria, G. E.; Robb, M. A. ; Cheeseman, J. R.; Scal-mani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Na-katsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A.F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M. ; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakaji-ma, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgom-ery, J. A.; Peralta, J.E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K.N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S.S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jara-millo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C. ; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V.G.; Voth, G. A.; Salvador, P.; Dannenberg, J.J.; Dapprich, S.; Daniels, A. D. ; Farkas, O.; For-esman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc., Wallingford CT, (2009). 9. Becke, A. D. J. Chem. Phys. 1993, 98, Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37,