Supporting Information

Lamellar mono-amidosil hybrids doped with Rhodamine (B) methyl ester perchlorate dye

S. C. Nunes,1a,b , V. T. Freitas,c R. A. S. Ferreira,c L. D. Carlos,c P. Almeida,a V. de Zea Bermudezb,d* a Chemistry Department and CICS- Health Sciences Research Centre, University of Beira Interior, 6200-001 Covilhã, Portugal bChemistry Department, University of Trás-os-Montes and Alto Douro, 5000-801 Vila Real, Portugal cPhysics Department and CICECO, University of Aveiro, 3810-193 Aveiro, Portugal d CQ-VR, University of Trás-os-Montes e Alto Douro, 5001-801 Vila Real, Portugal.

1 Corresponding author V. de Zea Bermudez: *Tel: +351-259-350253; Fax: +351-259-350480, E-mail address: [email protected] S. C: Nunes *Tel: +351-275-242021 Fax: +351-275-319730, E-mail address: [email protected] 1 Table S1 – Details of the synthesis of the m-A(14)nRh(B)CH3ClO4 mono-amidosils.

First Step – Synthesis of the m-ADPTES(14) precursor PC 1.00 mL (3.30 mmol) APTES 774 L (3.30 mmol) Amberlyst A-21 0.841 gr (3.90 mmol) Py 50 L (0.660 mmol) THF 20 mL

Second step – Synthesis of the m-A(14)nRh(B)CH3ClO4 hybrids

CH3CH2OH 700 L (13.20 mmol)

H2O 118 L (6.60 mmol) n = 20 n = 5

Rh(B)CH3ClO4 0.0459 g 0.3676 g (MM = 557.05 gmol-1) (0.0825 mmol) (0.66 mmol)

2 13 Table S2 – C CP/MAS NMR data ( in ppm) of the m-A(14)nRh(B)CH3ClO4 mono- amidosils.

n Attribution [30,34,36-38]

 20 5 12 174 vw 173.0 C=O (C ) - - 165.0, w C=O (dye) - - 158-153, w - - 135-127,w Car (dye) - - 115-110, w - - 99-94, w 3 43.1 H2CNH (C ) and NCH2CH3 (dye) 3 42 42.5 - H2CNH (C ) 6 36 sh 36.4 (C=O)CH2( C ) 9 34 w w CH2CH2CH2 (C ) 8 32 32.8 32.7 CH2CH2CH2 (C trans) 8 - - 30.7 CH2CH2CH2 (C gauche) 7 26 26.0 26.8 CH2CH2CH2 (C ) 2 10 24 24.2 24.3 CH2CH2CH2 (C / C ) 11 14 14 14.3 CH3 (C ) 1 11 Sh 11.5, w SiCH2 (C )

Notes: R=CH3(CH2)14C(=O)NH-(CH2)3-

3 Table S3 UV–Vis spectral data for Rh(B)CH3ClO4 in ethanolic solution (concentration 2×10-5 M)

Uv-Vis e

3 -1 -1 λmáx (nm) (dm mol cm ) 556 87329

4 Table S4. Absolute emission quantum yields () of the m-A(14)nRh(B)CH3ClO4 mono-amidosils obtained for different excitation wavelengths.

exc (nm) n 280 310 330 355 375 400 450 560  <0.01 - <0.01 - <0.01 - <0.01 - 20 0.03 0.04 0.02 0.03 0.02 0.02 0.01 0.04 5 <0.01 - <0.01 - <0.01 - <0.01 -

5 33

n y t i 5

s * * * * * * n

e t n I

d e z i l a m r o N

20

200 160 120 60 40 20 0  (ppm)

13 Fig. S1 C CP/MAS NMR spectra of the m-A(14)nRh(B)CH3ClO4 mono-amidosils.

6

2 7 0 n m A 3 0 0 n m 3 2 0 n m 3 4 0 n m 3 4 0 n m ) . u . a (

y t i s n e t n I

5 0 0 5 5 0 6 0 0 6 5 0 7 0 0 7 5 0 8 0 0 W a v e l e n g t h ( n m )

2 6 0 n m B 2 8 5 n m 3 1 0 n m 3 5 0 n m 4 1 0 n m 5 2 0 n m 5 6 5 n m ) . u . a (

y t i s n e t n I

5 0 0 5 5 0 6 0 0 6 5 0 7 0 0 7 5 0 8 0 0 W a v e l e n g t h ( n m )

Fig. S2 Emission spectra of the m-A(14)nCH3ClO4 mono-amidosil with n = 20 (A) and n = 5 (B) excited between 260 and 565 nm.

7 6 5 5 ) . u . a (

e c n a b r o 0 s 2 b 5 A

475 500 525 550 575 600 Wavenumber (nm-1)

Fig. S3. Absorption spectrum of Rh(B)CH3ClO4 in ethanolic solution (concentration 2×10-5 M)

In the UV-Vis absorption spectra of the Rh(B)CH3ClO4 ethanolic solution the pronounced peak at 556 nm is due to the monomer absorption band and the shoulder at 520 nm is attributed to the occurrence of the dimer.

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