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-85326 Bydgoszcz, Poland Faculty of Chemistry, University of Łódź, Tamka 12, PL-91403 Łódź, Poland. Faculty of Natural Sciences, Matej Bel University, Tajovského 40, 974 01 Banská Bystrica, Slovakia. Laboratoire CEISAM, UMR CNRS 6230, Universite de Nantes, 2 Rue de la Houssinière, BP92208, 44322 Cedex 3 Nantes, France. Faculty of Chemistry, Wrocław University of Technology, Wyb. Wyspiańskiego 27, PL-50370 Wrocław, Poland # Institut Universitaire de France, 1, Rue Descartes, 75005 Paris, France. e-mail: borys.osmialowski@utp.edu.pl, phone +48 52 3749027 S1
Table of contents S1 Experimental section... 4 S2 NMR Spectra... 5 S3 Cartesian coordinates determined by DFT/TD-DFT... 11 S3.1 Ground-state structures... 11 S3.2 Excited-state structures... 16 S4 Absorption, fluorescence and excitation spectra... 20 S2
S3
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, 220-440 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
S2 NMR Spectra NMR spectra of 1 1 H NMR 13 C NMR S5
NMR spectra of 2 1 H NMR 13 C NMR S6
NMR spectra of 3 1 H NMR 11 B NMR 13 C NMR S7
19 F NMR S8
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
19 F NMR S10
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 = -781.696767 C 1.10920-5242 -0.30504 C 1515 3379-6070 C 1.53867 1.45239 0.19724 C 2.89755 1.20372 4265 C 3.40217-9928 1605 C 2.46715-1.12069-7321 C -2655 0035-8881 O -1.19882 1.95964-1813 N 4.74433-0.36024 6926 C 5.68229 0.72379 8705 N -1.70294-5037 5584 C -3.10170-3123 4573 N -3.63546-1.42364 0.32786 C -4.96533-1.52673 0.33574 C -5.82254-6677 6655 C -5.24835 0.76806-2685 C -3.86763 0.90734-4157 C 5.23334-1.69257-2611 H -5.36044-2.51243 0.57040 H -6.89708-0592 8696 H -5.87409 1.62812-4490 H 1.16498 2.45716 0.36719 H 3.57383 2.02276 5376 H 2.80440-2.12746-8546 H 3943-1.66805-0.56515 H 5.61571 1.48424-0.50162 H 5.50679 1.21381 1.25194 H 6.69481 0.32178 9104 H 6.31722-1.70565-0.11711 H 4.81298-2.43152 6608 H 4.98544-2.00107-1.25011 H -1.33059-1.15965 9809 S11
H -3.38483 1.84797-5917 S12
Compound 2 Energy = -1104.639468 N 3.32703-1.60071 0.51706 C 2.97728-0.38429 8460 C 3.89995 0.56432-0.36655 C 5.24368 0841-0.34516 C 5.62552-4769 0.11351 C 4.62058-1.91516 0.53011 N 1.57977-2115 0.11456 C 0.75253 3853-4929 S 1.24176 2.42534-3963 C -7820 6192-3148 C -1.64890 1.35981 3463 C -2.98873 2744 6764 C -3.43785-3510 0930 C -2.46216-1.13110-8669 C -1.12230-0.78663-9493 N -4.76170-0.57147 3968 C -5.19245-1.85849-7090 C -5.74441 0.39883 8310 H 3.57566 1.53287-0.71395 H 5.98775 0.91956-8971 H 6.66525-1.35144 0.14558 H 4.86170-2.91207 9075 H 1.13918-9096 0.39996 H -1.33053 2.33429 0.78980 H -3.69563 1.75101 5422 H -2.75431-2.09560-8273 H -1785-1.49529-0.92306 H -6.26986-1.95060-0.33922 H -4.96421-1.96966-1.53869 H -4.71116-2.68083 7113 H -6.73643-4675 2063 H -5.56911 9711 1.52346 H -5.73151 1.30133-0.14068 S13
Compound 3 Energy = -1005.765497 O 0.97460-1.22960-2851 B 2.36561-1.52468 0.12815 N 3.17111-0.16955-4807 C 2.50606 0687 5635 N 1.14858 5599 0.17327 C 5541-3897 -1085 F 2.89600-2.45861-0.72753 C 4.51024-1362 -1912 C 3.24455 2.20667 1992 C -0491 1963-1925 C 4.61139 2.16641-0.14031 C 5.26746 0.93063-7043 C -1.77029-1.14690-0.15157 C -3.15101-1.10064-0.15959 C -3.83575 0.13316-3277 C -3.05465 1.30904 0.10105 C -1.67606 1.24458 0.10560 H -1.26623-2.10267-4618 H -3.70544-2.02507-6170 N -5.19970 0.18879-3909 H -3.53484 2.27453 0.19968 H -9211 2.15315 0643 C -5.87501 1.46540 9695 C -5.97436-3023 -0.17426 H -6.95163 1.30227 6980 H -5.62518 1.95253 4728 H -5.61072 2.14800-0.71973 H -5.77156-1.72752 4761 H -7.03460-0.78115-0.15694 H -5.75661-1.54050-1.12024 H 2.69660 3.13625 0.11021 H 5.18067 3.08964-0.17185 H 6.33953 6736-0558 H 4.93015-1.20859-0.30926 F 2.46166-1.90994 1.44808 S14
Compound 4 Energy = -1328.684508 S 4713-1.63882-9810 B 2.70353-1.46666 9104 N 3.21298 1245 2825 C 2.35229 6180 8216 N 0053 0.92646 1153 C 0.33002-0.13957-0.12585 F 3.63386-2.34738-0130 C 4.54099 0641-0.14261 C 2.87276 2.36762-0688 C -1.13413-6119 -8481 C 4.22433 2.56830-0.18070 C 5.08386 1.46314-5881 C -1.95508-1.19666-0.16363 C -3.33282-9919 -0.12605 C -3.96918 0.15986-0620 C -3.13930 1.30686 7606 C -1.76576 1.18900 3895 H -1.50403-2.18094-3537 H -3.92136-2.00652-0.17764 N -5.32886 6622 3066 H -3.57844 2.29296 0.16314 H -1.14757 2.07809 9628 C -5.95194 1.56754 0.18316 C -6.15139-0.92572-5609 H -7.03383 1.44285 0480 H -5.64290 2.05325 1.11657 H -5.70008 2.23296-5134 H -5.97353-1.46568-0.99362 H -5.95637-1.61055 0.77823 H -7.20092-3645 -2292 H 2.16785 3.18734 5289 H 4.61932 3.57580-5810 H 6.15139 1.57939-0.39575 H 5.13570-9745 -0.17638 F 2.48754-1.60103 1.64000 S15
S3.2 Excited-state structures Compound 1 Energy = -781.689420 C 9660-0.90297-1389 C 0.58564 3386-4698 C 1.55295 1.49270 6739 C 2.89322 1.24452 9063 C 3.39547-0.10054-1719 C 2.44382-1.15564-0.18609 C -0599 1103-0075 O -1.19988 2.00115 0359 N 4.73672-0.35643 2858 C 5.68799 0.72765 0.18771 N -1.71000-6490 3947 C -3.08139-4491 3064 N -3.63852-1.46130 2982 C -4.96502-1.54138 1989 C -5.81647-5617 1841 C -5.22755 0.79526-0.18703 C -3.85017 0.92258-0.18496 C 5.22752-1.71453-0.10343 H -5.37717-2.53558 0.38400 H -6.89194-0.58920 2290 H -5.84533 1.67351-0.34977 H 1.17318 2.50415 0.15077 H 3.58474 2.07256 0.19114 H 2.78612-2.17629-0.30948 H 2966-1.73812-0.39791 H 5.62736 1.43188-5168 H 5.49918 1.28019 1.11593 H 6.69420 0.31532 2520 H 6.31191-1.71294-1647 H 4.81134-2.35706 8237 H 4.95210-2.13932-7728 H -1.34555-1.19525 0558 H -3.34783 1.86663-0.33518 S16
Compound 2 Energy = -1104.629744 N 3.51487-1.48503 0.72528 C 2.95889-3271 0.10601 C 3.69016 3696-0.72406 C 5.04335 0.19422-8173 C 5.63874-8972 -3280 C 4.82005-1.69554 0.54868 N 1.59333-0.33216 0.30399 C 0.73768 0.75312 0.15169 S 1.26207 2.39524 4348 C -5477 2175 3363 C -1.67343 1.43262 0.11772 C -3.00499 1.12156 8229 C -3.44491-3105 -5805 C -2.44018-1.24288-0083 C -1.10899-0.92668-0.16288 N -4.76279-0.54668-7850 C -5.19154-1.92480-6047 C -5.76757 9453 6750 H 3.19943 1.26625-1.21512 H 5.63428 4808-1.51616 H 6.69593-1.10528-0.33336 H 5.23062-2.56018 6626 H 1.23912-1.12519 3216 H -1.35619 2.46310 2173 H -3.73170 1.92152 0.15326 H -2.72926-2.27520-0.35551 H -0.38603-1.71896-0.32088 H -6.27836-1.96439-3282 H -4.85075-2.31716-1.22548 H -4.79706-2.56396 0.53737 H -6.75514 3834 6513 H -5.63133 3500 1070 H -5.70950 1.21311-0.75850 S17
Compound 3 Energy = -1005.765497 O 0.97460-1.22960-2851 B 2.36561-1.52468 0.12815 N 3.17111-0.16955-4807 C 2.50606 0687 5635 N 1.14858 5599 0.17327 C 5541-3897 -1085 F 2.89600-2.45861-0.72753 C 4.51024-1362 -1912 C 3.24455 2.20667 1992 C -0491 1963-1925 C 4.61139 2.16641-0.14031 C 5.26746 0.93063-7043 C -1.77029-1.14690-0.15157 C -3.15101-1.10064-0.15959 C -3.83575 0.13316-3277 C -3.05465 1.30904 0.10105 C -1.67606 1.24458 0.10560 H -1.26623-2.10267-4618 H -3.70544-2.02507-6170 N -5.19970 0.18879-3909 H -3.53484 2.27453 0.19968 H -9211 2.15315 0643 C -5.87501 1.46540 9695 C -5.97436-3023 -0.17426 H -6.95163 1.30227 6980 H -5.62518 1.95253 4728 H -5.61072 2.14800-0.71973 H -5.77156-1.72752 4761 H -7.03460-0.78115-0.15694 H -5.75661-1.54050-1.12024 H 2.69660 3.13625 0.11021 H 5.18067 3.08964-0.17185 H 6.33953 6736-0558 H 4.93015-1.20859-0.30926 F 2.46166-1.90994 1.44808 S18
Compound 4 Energy = -1328.678441 S 6666-1.73081-6349 B 2.68310-1.43479 0.38416 N 3.19812-0422 0928 C 2.31986 7559-3607 N 0.99526 0.95722-4805 C 0.32124-0.18888-4245 F 3.63453-2.36720 3311 C 4.52930 0.19700-0.10965 C 2.87963 2.38573-0.10403 C -1.11546-8714 -0.16950 C 4.23236 2.57486-1270 C 5.08784 1.44589-3880 C -1.97627-1.21025-0.35244 C -3.33868-9412 -7104 C -3.95527 0.16787 0364 C -3.09937 1.29911 0.18586 C -1.73970 1.17186 0.10375 H -1.53778-2.18103-0.55442 H -3.95029-1.97545-1883 N -5.30079 8562 8190 H -3.52534 2.27359 0.39025 H -1.10021 2.03421 4401 C -5.91151 1.57628 0.36257 C -6.15720-7507 -0.11342 H -6.99199 1.45622 0092 H -5.56725 1.96800 1.32594 H -5.66548 2.30285-1984 H -6.00829-1.30558-1.10966 H -5.94821-1.64487 3746 H -7.19649-0.56787-1879 H 2.17862 3.21256-0.10011 H 4.64274 3.57673-8177 H 6.16154 1.54749-0.33468 H 5.12964-0.70468-8189 F 2.38636-1.45814 1.73135 S19
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 250 300 350 400 340 360 380 400 420 440 460 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 300 350 400 450 500 λ [nm] 400 450 500 550 600 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 250 300 350 400 450 500 400 450 500 550 600 650 700 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 300 350 400 450 500 550 λ [nm] 450 500 550 600 650 700 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
Compound 1 Em = 400 nm Abs Compound 3 Em = 500 nm Abs absorbance absorbance 260 280 300 320 340 360 380 λ [nm] 280 320 360 400 440 480 λ [nm] Compound 4 Em = 550 nm Abs absorbance absorbance Compound 2 Em = 465 nm Abs 280 320 360 400 440 480 λ (nm) 280 320 360 400 440 480 520 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 18000 20000 22000 24000 26000 ν [cm -1 ] S21
fluorescence 3 in CHCl 3 Exp 1 2 18000 20000 22000 24000 ν [cm -1 ] 4 in CHCl 3 Exp 1 2 fluorescence 18000 20000 22000 ν [cm -1 ] Figure S3 Decomposed fluorescence spectra for compounds 2-4 in CHCl 3. S22