SUPPORTING INFORMATION FOR Coumarin derivative directly coordinated to lanthanides acts as an excellent antenna for UV-vis and NIR emission

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1 SUPPORTING INFORMATION FOR Coumarin derivative directly coordinated to lanthanides acts as an excellent antenna for UV-vis and NIR emission 1. General methods Synthesis of the ligand and NMR spectrum Synthesis and characterization of the lanthanide complexes Single crystal data and figures Ligand spectra: experimental vs calculated. 7 Table S2 Absorption and emission data on the ligand... 7 Calculation methods Fluorescence measurements Instrumentation - Absorption and excitation spectra of the complexes of Sm, Eu, Tb and Dy - Solid state emission spectra of all the emitting complexes, including the transition assignments and the corresponding wavelengths. - Decay profiles 7.- Photostability estimation General methods All reagents and solvents were purchased from commercial suppliers and used without further purification. Solvents for fluorescence measurements were HPLC grade. 1 H NMR spectra were measured on 400Mhz, 9.4T, Varian VNMRS spectrometer. IR spectra (ATR mode) were recorded in a Perkin Elmer FTIR/FIR Spectrum 400 spectrophotometer. High resolution mass spectra were recorded in a UltrafleXtreme MALDI-TOF/TOF Bruker Daltonics. Uv-vis spectra for solutions were recorded in an Agilent 8453 diode array spectrophotometer; solid sample spectra were recorded in DR Ocean Optics DT 1000 spectrophotometer. Elemental analyses were performed by Unidad de servicios de apoyo a la investigación y la industria of Facultad de Química, UNAM. Room Temperature (20 C) Magnetic susceptibilities were measured in a Mark 1 Sherwood Scientific Magnetic Balance. 2. Synthesis of the ligand 4g (0.023 mol) of 4 hydroxy coumarin were acetylated using 2.28mL (0.023 mol) of acetic anhydride, using pyridine as the solvent and four drops of piperidine as catalyst. The reaction mixture was kept stirring at 40 C for 48 hours. The product was crystalized from H 2O/EtOH. Mp = C. Elemental Analysis: Calc. for C 11H 8O 4: (%) C: 64.71, H: 3.95; Found: C: 64.96, H: MS (m/z): 204 [M-H] +. IR 1715cm -1, 1615 cm -1 (ν C=O) 1393 cm- 1 ( sim CH 3), 1490 cm- 1 ( asim CH 3). 1

2 UV-Vis UV-Vis (EtOH) [M -1 cm -1 ]: λ nm (21 645), λ nm (14 589), λ nm (10 050). 1 H NMR (400 MHz, CDCl 3) δ 8.01 (ddd, J = 7.9, 1.7, 0.8 Hz) 1H), δ 7.84 (td, J = 7.84, 1.4 Hz, 1H), δ (m, 2H), δ 3.18 (s, 1H), δ 2.67 (s, 3H). Figure S1 1 H NMR spectrum of the Cum ligand 3.- Synthesis of the Ln complexes 0.75 mmol (0.1531g) of the Cum ligand were dissolved in 40 ml of ethanol together with 0.75 mmol of NaMeO ( g). To this, a 10mL ethanolic solution containing 0.25 mmol of the corresponding lanthanide nitrate hydrate was added dropwise. This mixture was kept at 60 C and vigorously stirred for five hours after which it was concentrated by evaporation to a final volume of ca. 5 ml; and the products were precipitated by the addition of 15 ml of distilled water. The washed, filtered and dried products were recrystallized from methanol or ethanol, from which crystals were collected for X-ray diffraction. Pr Yield = 56.7 % MALDI- TOF (m/z): 569 [M-HL+Na]+, 773 [M+Na] ] +. Elemental analysis calc. Pr(C 11H 7O 4) 3(H 2O) 2(EtOH) 2 (%): C: 51.39, H: 4.28, Experimental: C: 51.49, H IR- ATR (cm -1 ): 1580 (νc=o, COCH3), 1607 (νo-c=o), 1386 (δs CH3), 1465 (δas CH3). µ eff (20 C) = 3.31 MB. Nd Yield = 66.3%. MALDI- TOF (m/z): 550 [M-L] +, 572 [M-HL+Na] +, 776 [M+Na] +. Elemental analysis calc. for Nd(C 11H 7O 4) 3(H 2O) 2(EtOH) 2 C: 50.39, H: 4.23, Experimental: C: 50.58, H IR- ATR (cm - 1 ): 1580 (νc=o, COCH 3), 1608 (νo-c=o), 1387 (δ s CH 3), 1465 (δ as CH 3). µ eff (20 C) =3.59 MB. Sm Yield = 71.4% MALDI- TOF (m/z): 580 [M-HL+Na] +, 784 [M+Na] +. Elemental analysis calc. for Sm(C 11H 7O 4) 3(H 2O)(MeOH) 2 (%): C: 49.93, H: Found: C: 49.69, H: IR- ATR (cm -1 ): 1580 (νc=o, COCH 3), 1609 (νo-c=o), 1389 (δ s CH 3), 1466 (δ as CH 3). UV-Vis (10-5 M, ethanol, λ [nm]/ ɛ [M - 1 cm -1 ]): 301 (36 091), 316 (31 538), (10-5 M, THF, ɛ [nm], M -1 cm -1 ): 306 (33 988), 320 (37 664), 322 (31 705). eff (20 C) = 1.47 MB Eu Yield = 79.6 %. MALDI- TOF (m/z): 565 [M-L] +, 786 [M+Na] +. Elemental analysis calc. for Eu(C 11H 7O 4) 3(H 2O)(MeOH) 2 (%): C: 49.83, H: 3.70, Experimental: C: 49.97, H:

3 IR- ATR (cm -1 ): 1582 (νc=o, COCH 3), 1609 (νo-c=o), 1390 (δ s CH 3), 1466 (δ as CH 3). UV-Vis (10-5 M, etanol, λ [nm]/ ɛ [M -1 cm -1 ]): 301 (36 882), 314 (35 043), (10-5 M, THF, λ [nm]/ ɛ [M -1 cm -1 ]): 302 (42 721), 320 (46 698), 322 (40 525), eff(20 C) = 3.45 MB Tb Yield = 85.6 %. MALDI- TOF (m/z): 565 [M-L] +, 769 [M+H] +, 791 [M+Na] +. Elemental analysis calc. for Tb(C 11H 7O 4) 3(H 2O)(EtOH) 2 (%): C: 50.58, H: 4.02, found: C: 50.58, H: IR- ATR (cm -1 ): 1581 (νc=o, COCH 3), 1606 (νo-c=o), 1387 (δ s CH 3), 1465 (δ as CH 3). UV-Vis (10-5 M, etanol, λ [nm] / ɛ[m -1 cm -1 ]): 301 (43 148), 312 (41 672), (10-5 M, THF, λ [nm]/ ɛ [M -1 cm -1 ]): 304 (33 096), 319 (36 730), 322 (31 315). eff (20 C) = 9.38 MB Dy Yield = 61.4 % MALDI- TOF (m/z): 592 [M-HL+Na] +, 796 [M+Na] +. Elemental analysis calc. for: Dy(C 11H 7O 4) 3 (EtOH) 2 (%): C: 51.43, H: found: C: 51.32, H: IR- ATR (cm -1 ): 1580 (νc=o, COCH 3), 1608 (νo-c=o), 1388 (δ s CH 3), 1466 (δ as CH 3). UV-Vis (10-5 M, etanol, λ [nm]/ ɛ [M -1 cm -1 ]): 300 (43 736), 323 (35 741), (10-5 M, THF, λ [nm]/ ɛ [M -1 cm -1 ]): 304 (38 620), 319 (41 539), 322 (35 382). eff (20 C) = MB Ho Yield = %. MALDI- TOF (m/z): 593 [M-HL+Na] +, 797 [M+Na] +. Elemental analysis calc. for Ho(C 11H 7O 4) 3(EtOH) 2(H 2O) 2 (%): C: 49.24, H: found: C: 49.04, H: IR- ATR (cm -1 ): 1583 (νc=o, COCH 3), 1612 (νo-c=o), 1392 (δ s CH 3), 1467 (δ as CH 3). µ eff (20 C) = MB. Er Yield = 56.5 %. MALDI- TOF (m/z): 596 [M-HL+Na] +, 800 [M+Na] +. Elemental analysis calc. for Er(C 11H 7O 4) 3(EtOH) 2(H 2O) 2 (%): C: 50.11, H: found: C: 49.87, H: IR- ATR (cm -1 ): 1579 (νc=o, COCH 3), 1609 (νo-c=o), 1389 (δ s CH 3), 1466 (δ as CH 3). µ eff (20 C) = 9.75 MB. Tm Yield = 60.7 %. MALDI- TOF (m/z): 597 [M-HL+Na] +, 801 [M+Na] +. Elemental analysis calc. for Tm(C 11H 7O 4) 3(EtOH) 2(H 2O) (%): C: 50.01, H: found: C: 49.93, H: IR- ATR (cm -1 ): 1581 (νc=o, COCH 3), 1608 (νo-c=o), 1387 (δ s CH 3), 1466 (δ as CH 3). µ eff (20 C) = 7.41 MB. Yb Yield =55.2%. MALDI- TOF (m/z): 602 [M-HL+Na] +, 806 [M+Na] +. Elemental analysis calc. for Yb(C 11H 7O 4) 3(EtOH) 2(H 2O) (%): C: 49.78, H: found: C: 49.99, H: 3.9. IR- ATR (cm -1 ): 1580 (νc=o, COCH 3), 1611 (νo-c=o), 1392 (δ s CH 3), 1468 (δ as CH 3). µ eff (20 C) = 4.84 MB. 3

4 4. Table S1. Single crystal data Sm Eu Tb Dy Formula C35H31O15Sm C35H31O15Eu C37H35O15Tb C37H35O15Dy fw Crystal size (mm 3 ) Space group P-1 P-1 P21/c P21/c a (Å) (10) (8) (3) (4) b (Å) (6) (6) (6) (10) c (Å) (13) (13) (3) (4) α ( ) (6) (7) β ( ) (7) (7) (2) (3) γ ( ) (7) (6) V (Å 3 ) (2) (2) (16) (2) Z, Z 2, 1 2, 1 4, 1 4, 1 Diffractometer Xcalibur Xcalibur Stadivari Stadivari Radiation Mo-Kα Cu-Kα Ag-Kα Ag-Kα T (K) Abs. coef. (mm -1 ) Transmission fact Refl. collected Senθ/λ (Å -1 ) Rint (%) Completeness (%) Data/parameters 6720 / / / / 495 Restraints R1, wr2 [I > 2σ(I)] 3.27, , , , 6.87 R1, wr2 [all data] 4.39, , , , 7.39 GOF on F Single crystals of Sm, Eu, Tb and Dy complexes were stable in air and diffraction data were collected on an Agilent Xcalibur (Sm and Eu, work done in Mexico DF; Atlas detector) or a Stoe Stadivari diffractometer (Tb and Dy, work done in Puebla; 100K Pilatus detector). With the Xcalibur diffractometer [1], intensities were measured at 130 K using Cu or Mo radiation, while a Ag microfocus source was used on the Stadivari [2] at room-temperature. Data collections were straightforward in all cases, except in the case of Dy, since only small single crystals were available for this sample. Structures were refined [3] using SHELXL 2017/1 to a resolution d = 0.8 Å, on the basis of absorption-corrected data, and no disordered parts were detected. Hydroxyl H atoms for water molecules and alcohol molecules were found in difference maps, however their positions were refined with soft geometric restraints for O H bond lengths and H O H angles (water molecules). Other H atoms were placed in idealized positions and refined as riding on their carrier atoms. Full data have been deposited in the CCDC with numbers

5 Figure S2: Perspective view of the asymmetric unit for [Sm(Cum)3(MeOH)(H2O)].MeOH with displacement ellipsoids for non-h atoms at the 50% probability level. Figure S3: Perspective view of the asymmetric unit for [Eu(Cum)3(MeOH)(H2O)].MeOH with displacement ellipsoids for non-h atoms at the 50% probability level. 5

6 Figure S4: Perspective view of the asymmetric unit for [Tb(Cum)3(EtOH)(H2O)].EtOH with displacement ellipsoids for non-h atoms at the 30% probability level. Figure S5: Perspective view of the asymmetric unit for [Dy(Cum)3(EtOH)(H2O)].EtOH with displacement ellipsoids for non-h atoms at the 30% probability level. 6

7 5.- Ligand absorption spectra: experimental and calculated. Figure S6 absorption spectra for the ligand. Left: black line = experimental spectrum in EtOH, red line = calculated spectrum. Calculations Time-dependent density functional theory TD-DFT calculations were performed on the Cum ligand. Firstly, a ground state geometry optimization was performed in gas-phase on a single molecule set then in solution (ethanol) with the B3LYP exchange correlation functional and the 6-311G(d,p) [4] basis set through the polarisable continuum model (PCM) [5] of solvation. The singlet and triplet states values obtained from these calculations agree with the experimental results and in addition it was obtained that the lowest energy triplet state T 1 is at nm ( cm -1 ). Table S2 Absorption and emission data on the ligand Absorption max (nm) Emission ( exc) ( L mol -1 cm -1 ) Solid (360) EtOH 210 (21,645) 383 (325) solution 300 (14,584) 322 (10,050) THF solution 301 (10,400) 327 (8,680) 338 (7550) 367 (895) 380 (325) 410 (365) Calculated max (nm) assignment 303 S0 S2 318 S0 S1 326 T4 S0 331 T3 S0 367 T2 S0 407 T1 S0 7

8 6. Fluorescence measurements Photoluminescence: Steady state, lifetime and quantum yield measurements The emission and excitation spectra; luminescence decay curves and quantum yield measurements were performed in an Edinburgh Instruments FSP920 spectrofluorometer based on the method of single photon counting which combines steady state and phosphorescence lifetime measurements. In the latter case, the electronics operate in multichannel scaling mode. The spectrofluorometer is equipped with a 450 W xenon lamp as a CW light source and an R928P PMT for the UV-Vis spectral region and an InGaAs photodiode (Hamamatsu G ) with integrated lock-in for the spectral region between 900 nm and 1650 nm. To minimize the light dispersion, a double monochromator (two coupled 0.3 m) was employed to excite the samples. All the excitation and emission spectra were corrected for the wavelength dependent responses of the Xe-lamp and the detector, respectively. The emission spectra were recorded in the wavelength range between 420 nm and 1650 nm. For the measurements of luminescence decay, the excitation photons were provided by a 60W µf920h pulsed Xe flashlamp with a pulse width of 1.5 µs and a repetition rate of 100 Hz. For absolute quantum yield determination, a 150 mm in diameter BenFlect coated integrating sphere was employed. The spectral sensitivity of the spectrofluorometer and sphere was corrected using ad hoc data for the spectral light throughput. These data were obtained in our lab with a calibrated lamp by the manufacturer when the sphere was used for the first time. Excitation wavelength was chosen according to specific luminescence response of each complex to avoid the presence of harmonics in the emission spectra. All measurements were carried out at room temperature. Figure S7. Absorption and excitation spectra for Ln(Cum) 3 complexes in EtOH 8

9 Figure S8a. Emission spectra of solid samples of Ln(Cum) 3 complexes 9

10 Figure S8b. Emission spectra of solid samples of Ln(Cum) 3 complexes 10

11 Decay profiles Figure S9. Decay profiles for the tris coumarin complexes in solid state and in ethanol and THF solution. 11

12 7.-Photostability in solution Samples of the emitting complexes as 0.02mM ethanolic solutions were placed in a Cary Eclipse fluorescence spectrophotometer equipped with a Xe pulse lamp, pulsed at 80 Hz. Pulse width at half peak height ~ 2 μs, peak power equivalent to 75 kw. The shutter was kept open, with the maximum excitation slit of 20 nm to obtain continuous irradiation at of 340nm. Emission intensity was measured at the wavelength of the hypersensitive band for each compound. Figure S10. Photostability estimation. Relative intensity vs time plots. [1] Agilent CrysAlis PRO, Agilent Technologies Inc., 2013, Santa Clara, CA, USA. [2] Stoe & Cie. X-AREA. Stoe & Cie, 2015, Darmstadt, Germany. [3] Sheldrick, G. M. Crystal Structure Refinement with SHELXL. Acta Cryst. C71, 2015, 3-8. [4] Tirado-Rives, J.; Jorgensen, W.L. Performance of B3LYP Density Functional Methods for a Large Set of Organic Molecules. J. Chem. Theory Comput., 2008, 4, [5] Tomasi, J.; Mennucci, B.; Cammi, R. Quantum Mechanical Continuum Solvation Models. Chem. Rev., 2005, 105,