Synthesis and Photophysical Properties of Novel Donor- Acceptor N-(Pyridin-2-Yl) Substituted Benzo(thio)amides and Their Difluoroboranyl Derivatives

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1 Supporting information for Synthesis and Photophysical Properties of Novel Donor- Acceptor N-(Pyridin-2-Yl) Substituted Benzo(thio)amides and Their Difluoroboranyl Derivatives Beata Jędrzejewska, Anna Zakrzewska, Grzegorz Mlostoń, Šimon Budzák,, Karina Mroczyńska, Anna M. Grabarz, Małgorzata A. Kaczorowska, Denis Jacquemin,# and Borys Ośmiałowski * Faculty of Chemical Technology and Engineering, UTP University of Science and Technology, Seminaryjna 3, PL Bydgoszcz, Poland Faculty of Chemistry, University of Łódź, Tamka 12, PL Łódź, Poland. Faculty of Natural Sciences, Matej Bel University, Tajovského 40, Banská Bystrica, Slovakia. Laboratoire CEISAM, UMR CNRS 6230, Universite de Nantes, 2 Rue de la Houssinière, BP92208, Cedex 3 Nantes, France. Faculty of Chemistry, Wrocław University of Technology, Wyb. Wyspiańskiego 27, PL Wrocław, Poland # Institut Universitaire de France, 1, Rue Descartes, Paris, France. borys.osmialowski@utp.edu.pl, phone S1

2 Table of contents S1 Experimental section... 4 S2 NMR Spectra... 5 S3 Cartesian coordinates determined by DFT/TD-DFT S3.1 Ground-state structures S3.2 Excited-state structures S4 Absorption, fluorescence and excitation spectra S2

3 S3

4 S1 Experimental section General remarks. Compounds used in synthesis of 1-4 (2-aminopyridine, ethyl 4- N,N-dimethylaminobenzoate, NEtiPr 2, BF 3 etherate, anisole and teraphosphorus decasulfide) were commercially available. The solvents used in purification were analytically pure. Silica gel (high purity, mesh, Aldrich) was used for column chromatography (compounds 3 and 4, eluent DCM) and neutral alumina for compound 2. The detection during column chromatography was realized by the use of UV/Vis detector (Büchi Sepacore flash chromatography system). The complexation (with BF 3 etherate) was performed under slow flow of the nitrogen over the magnetically stirred solution of (thio)amide in dry dichloromethane with NEtiPr 2 as a base. Melting points were determined in a capillary using a Büchi apparatus, and they are uncorrected. The IR spectra were recorded on a NEXUS FT-IR spectrophotometer in KBr; absorptions in cm 1. The 1 H- and 13 C{ 1 H}-NMR spectra were measured on a Bruker Avance III instrument (400 and 100 MHz, respectively). Chemical shifts (δ) are given in ppm and coupling constants J in Hz. Absorption spectra were recorded using Dynamica Halo RB-10 spectrophotometer with thermostated cell holder (20 C) in 10mm cuvettes and fluorescence spectra were recorded with F-7000 spectrofluorimeter from (Hitachi). All NMR spectra ( 1 H, 11 B, 13 C, 19 F) and 15 N chemical shift data (based on 1 H, 15 N HMBC experiments) were recorded at r.t. using CDCl 3 as a solvent and the following references TMS (for 1 H and 13 C), BF 3 etherate (for 11 B), CFCl 3 (for 19 F) and MeNO 2 (for 15 N). Mass spectrometry analysis was performed on a Q-Exactive mass spectrometer (Thermo Scientific). Samples of studied compounds were dissolved in methanol/formic acid solutions (98:2, v/v) to give a final concentration of 10 mm and next were introduced to the mass spectrometer by use of electrospray source. Data acquisition and analysis were conducted using the Xcalibur (Thermo Scientific) software. Collective mass spectra for 1 (a), 2 (b), 3 (c) and 4 (d) More detailed studies of 1-4 with other MS techniques are under progress. S4

5 S2 NMR Spectra NMR spectra of 1 1 H NMR 13 C NMR S5

6 NMR spectra of 2 1 H NMR 13 C NMR S6

7 NMR spectra of 3 1 H NMR 11 B NMR 13 C NMR S7

8 19 F NMR S8

9 NMR spectra of 4 1 H NMR 11 B NMR 13 C NMR Note: one carbon atom is splitted into triplet due to the presence of BF 2 group. S9

10 19 F NMR S10

11 S3 Cartesian coordinates determined by DFT/TD-DFT The structures were optimized at M06-2X/6-31G(d) level of theory using IEF-PCM continuum solvation model to simulate the chloroform solvent. Energies are given in au, coordinates in Å. Numbers visible on the structure figures correspond to the length of specific bonds [Å] S3.1 Ground-state structures Compound 1 Energy = C C C C C C C O N C N C N C C C C C H H H H H H H H H H H H H H S11

12 H S12

13 Compound 2 Energy = N C C C C C N C S C C C C C C N C C H H H H H H H H H H H H H H H S13

14 Compound 3 Energy = O B N C N C F C C C C C C C C C C H H N H H C C H H H H H H H H H H F S14

15 Compound 4 Energy = S B N C N C F C C C C C C C C C C H H N H H C C H H H H H H H H H H F S15

16 S3.2 Excited-state structures Compound 1 Energy = C C C C C C C O N C N C N C C C C C H H H H H H H H H H H H H H H S16

17 Compound 2 Energy = N C C C C C N C S C C C C C C N C C H H H H H H H H H H H H H H H S17

18 Compound 3 Energy = O B N C N C F C C C C C C C C C C H H N H H C C H H H H H H H H H H F S18

19 Compound 4 Energy = S B N C N C F C C C C C C C C C C H H N H H C C H H H H H H H H H H F S19

20 S4 Absorption, fluorescence and excitation spectra normalized absorbance Compound 1 MCH THF MeCN normalized fluorescence Compound 1 MeCN; Ex=325 nm THF; Ex=325 nm MCH; Ex=310 nm λ [nm] λ [nm] normalized absorbance Compound 2 MCH THF MeCN normalized fluorescence Compound 2 MCH; Ex=354 nm THF; Ex=364 nm DMF; Ex=369 nm λ [nm] λ [nm] normalized absorbance Compound 3 MCH THF MeCN normalized fluorescence Compound 3 MeCN; Ex=404 nm THF; Ex=404 nm MCH; Ex=366 nm λ [nm] λ [nm] normalized absorbance Compound 4 MCH THF MeCN normalized fluorescence Compound 4 MeCN; Ex=450 nm THF; Ex=450 nm MCH; Ex=420 nm λ [nm] Figure S1 Normalized, steady-state absorption (left panel) and fluorescence (right panel) spectra of the studied compounds in MCH, THF and MeCN. λ [nm] S20

21 Compound 1 Em = 400 nm Abs Compound 3 Em = 500 nm Abs absorbance absorbance λ [nm] λ [nm] Compound 4 Em = 550 nm Abs absorbance absorbance Compound 2 Em = 465 nm Abs λ (nm) λ [nm] Figure S2 Normalized electronic absorption and fluorescence excitation spectra for compounds 1-4 in CHCl 3. 2 in CHCl 3 Exp 1 2 fluorescence ν [cm -1 ] S21

22 fluorescence 3 in CHCl 3 Exp ν [cm -1 ] 4 in CHCl 3 Exp 1 2 fluorescence ν [cm -1 ] Figure S3 Decomposed fluorescence spectra for compounds 2-4 in CHCl 3. S22