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Supplementary Information

Highly efficient visible light sensitized red emission from europium tris[1-
(4-biphenoyl)-3-(2-fluoroyl)propanedione](1,10phenanthroline) complex
grafted on silica nanoparticles

V. Divya, S. Biju, R. Luxmi Varma and M. L. P. Reddy*

Chemical Sciences and Technology Division, National Institute for Interdisciplinary
Science & Technology (NIIST), CSIR, Thiruvananthapuram-695019, India
E mail: [email protected]
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Physical Characterization of SiBFPD-Na and Eu3+ luminescent hexagonal
mesoporous silica particles Eu(SiBFPD)3(phen)/MCM-41 (3)
For the modified ligand SiBFPD-Na a broad peak at = 5.12 ppm in the 1H NMR (Fig.
S6) and = 159 ppm in the solid state 13C NMR spectra (Fig. S7) indicates the formation
of amide CONH linkage. The propyl chain in the ligand gives peaks at 0.57-3.62 ppm
in the 1H NMR and 8.77, 18.63 and 36.79 ppm in the solid state 13C NMR spectra. The
purity of the product was confirmed by the absence of signal at = 6.98 ppm
characteristic of the free H in between the two carbonyl groups of HBFPD in the 1H
29 29
NMR spectrum. The Si CPMAS NMR spectrum of 3 is shown in Fig. S8. The Si
CPMAS NMR spectrum of 3 displays two broad overlapping resonances at = 103.59
and 115.01 ppm, which correspond to Q3 and Q4 species of the silica framework [Qn =
Si(OSi)n(OH)4n]. A weak shoulder is also observed at = 95.13 ppm for the Q2 species.
The Q3 sites are associated with single SiOH groups that include both free and
hydrogen-bonded silanols, and the Q2 sites correspond to geminal silane diols. Two
additional signals appear at = 56.9 and 68.16 ppm, which can be assigned to T2 and
T3 organosilica species [Tm = RSi(OSi)m(OEt)3m], respectively, indicates that the organic
groups are covalently bonded to the silica matrix. 1-3
The carbonyl stretching frequency of complex 3 has been shifted to lower wave
number (1590 cm-1 of the free ligand, SiBFPD-Na to 1568 cm1), indicating the
involvement of carbonyl oxygen in the complex formation with Eu3+ ion. Further, a red
shift observed in the characteristic peak of phen (1561 cm1) in complex 3 (1519 cm1),
shows the involvement of nitrogen in the complex formation with Eu3+ ion.4 The FT-IR
spectra of the grafted ligand SiBFPD-Na and complex 3 are shown in Fig. S4. The
presence of the amide group in SiBFPD-Na was confirmed by the appearance of new
bands at 3335 ( NH), 1629 cm1 ( NHCO) and 1443 cm-1 ( NH). Three peaks at 2961,
2923 and 2851 cm-1 are related to C-H stretching of sp3 carbon. An intense band at 1076
cm-1 can be observed and is assigned to an asymmetric stretching of siloxane groups.5
The FT-IR spectrum of complex 3 consists of a broad band located at around 1083 cm-1
(as, SiO), 847 cm-1 ( , SiO), and 548 cm-1 (, SiOSi), which attributes to the
success of hydrolysis and copolycondensation reactions ( represents stretching, in
plane bending, ring deformation, s symmetric, and as asymmetric vibrations).2 The
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band at 960 cm1 can be assigned to stretching vibrations of SiOH surface groups. The
peak at 1629 cm1 originating from the CONH group of SiBFPD-Na, can also be
observed in 3 which is consistent with the fact that the carbonyl group of the precursor
remain invariably after hydrolysis and condensation reactions, confirming that the two
carbonyl groups of -diketones are coordinated to the Eu3+ ions, not the carbonyl group
of the TESPIC.2,3
The FT-Raman spectra of the SiBFPD-Na ligand and complex 3 are shown in Fig. S5.
The peak at 1404 cm-1 in the ligand and at 1421 cm-1 in 3 are due to the symmetric
stretching vibrations of the C=O group (sC=O). The peak at 1606 cm1 originating from
the CONH group of SiBFPD-Na, remains as the same in the complex 3 proves that
carbonyl group of the TESPIC is not involved in the coordination with metal ions.2 The
peaks at around 1384 cm1 in both the ligand and in 3 are due to the in-plane bending of
CH2 group (CH2). In the vibrational spectrum of 3, band arising from the ancillary
ligand phen was observed at 1520 cm-1,4 indicating the presence of phen in 3. The
detailed vibrational spectral data are given in Table S1.
From the dynamic light scattering (DLS) measurements it is evident that the
mesoporous hybrid material has an average particle size of 364 nm (Fig. S9). Scanning
electron microscopy (SEM) picture of the mesoporous hybrid material is given in Fig.
S10. The SEM picture of mesoporous hybrid material is typical for the covalently bonded
hybrids with mesoporous host and show the morphology of aggregated spherical particles
of diameter of around 100-300 nm. Meanwhile, the different tendency of the
polycondensation reaction of SiOSi in the three dimensions caused the different
sizes in length and in width.6a The morphology and size of the grafted nanoparticles were
examined by TEM analysis (Fig. S11). The picture indicate that the monodispersity of the
nanosized MCM-41 units was conserved in the mesoporous hybrid material.2,6b
The X-ray diffraction (XRD) patterns are popular and efficient method to characterize
highly ordered mesoporous materials with hexagonal symmetry. The XRD pattern for
MCM-41 is characteristic of three well-defined Bragg peaks in the low angle range
corresponded to the d (100), (110), and (200) planes of the solid that are fully indexed to
a hexagonal unit cell (Fig. S12). In addition to the d (100) peak, a broad diffraction peak
was noted in the low 2 region at 3.27 in 3, which is a characteristic peak of the
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formation of periodic hexagonal mesostructures.5a,7a-b The broadening of peaks also
reveals that the structure ordering decreases with the anchoring of 2. This result also
provides indirect evidence that complex 2 is indeed incorporated into the mesoporous
silica framework. The presence of d (100) peak suggested that the framework stability
was still maintained for the grafted complex.7c
Nitrogen adsorption-desorption isotherms obtained for the complex 3 shows that the
reduction of the surface area from 731 m2 g1 for the MCM-41 to 11 m2 g1, suggesting
that micro-environment of MCM-41 has drastically changed due to the introduction of
luminescent centers on the pore surface. Likewise, the pore volume for MCM-41 for 0.73
cm3 g1 decreased to 0.02 cm3 g1 which might be due to the fact that the presence of
bulky organic ligand on the pore surface interact with surfactant reduce the pore volume.
This loss in surface area may be explained by the fact that N2 molecules are repelled from
the silica surface by the grafted organosilanes so that they cannot adsorb any more.2,8
The thermal behavior of the complex 3 was examined by means of thermogravimetric
analysis (TGA) under nitrogen atmosphere and the results are depicted in the Fig. S3.
Complex 3 showed two distinct stages of decomposition. The first weight loss around
100 C as related to absorbed water and the other one between 100-600 C was assigned
to the decomposition of organic matter and water from sylanol group condensation.5a In
addition, compared with the weight loss at 600C (~ 68 %) of pure complex 2, the
decomposition of 3 was lower (~ 38 %), indicating that the thermal stability of the pure
complex was enhanced as it was covalently bonded to the mesoporous matrix.

References
1 S. M. Bruno, A. C. Coelho, R. A. S. Ferreira, L. D. Carlos, M. Pillinger, A. A.
Valente, P. Ribeiro-Claro and I. S. Goncalves, Eur. J. Inorg. Chem., 2008, 3786.
2 D. B. Ambili Raj, S. Biju and M. L. P. Reddy, J. Mater. Chem., 2009, 19, 7976.

3 (a) X.-F. Qiao and B. Yan, Inorg. Chem., 2009, 48, 4714; (b) X. Qiao and B. Yan,
J. Phys. Chem. B, 2008, 112, 14742.
4 L.-J. Bian, H. Xi, X.-F. Quan, J. Yin, Z.-K. Zhu and Q.-H. Lu, Mater. Res. Bull.,
2002, 37, 2293.
Supplementary material (ESI) for Journal of Materials Chemistry
This journal is The Royal Society of Chemistry 2010
5 (a) E. De Oliveira, C. R. Neri, O. A. Serra and A. G. S. Prado, Chem. Mater.,
2007, 19, 5437; (b) P. T. Tanav and T. J. Pinnavaia, Chem. Mater., 1996, 8, 2068.

6 (a) J. L. Liu and B.Yan, J. Phys. Chem. B, 2008, 112, 10898; (b) S. Cousini,
M.Gressier, C. Reber, J. Dexpert-Ghys and M.-J. Menu, Langmuir, 2008, 24,
6208.

7 (a) Y. Li, B. Yan and H. Yang, J. Phys. Chem. C., 2008, 112, 3959; (b) M.
Ogawa, K. Ikeue and M. Anpo, Chem. Mater., 2001, 13, 2900; (c) Y.-S. Lin, Y.
Hung, J.-K. Su, R. Lee, C. Chang, M.-L. Lin and C. Y. Mou, J. Phys. Chem. B.,
2004, 108, 15608.

8 (a) B. Yan and B. Zhou, J. Photochem. Photobiol. A., 2008, 195, 314; (b) S.
Cousini, M.Gressier, C. Reber, J. Dexpert-Ghys and M.-J. Menu, Langmuir,
2008, 24, 6208.
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Fig. S1. 1H NMR spectrum of the ligand HBFPD.

Fig. S2 13C NMR spectrum of the ligand HBFPD.

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Fig. S3 Thermogravimetric curves for the complexes 1-4.

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Fig. S4 FT-IR spectra of the ligand SiBFPD-Na and complex 3.

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Fig. S5 FT-Raman spectra of the ligand SiBFPD-Na and complex 3.

Fig. S6 1H NMR spectrum of the ligand SiBFPD-Na.

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Fig. S7 Solid state 13C NMR spectrum of the ligand SiBFPD-Na.

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T3

T2
Q3

Q4

Q2

Fig. S8 Solid state 29Si CPMAS NMR spectrum of complex 3.

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Fig. S9 DLS particle size distribution curve for 3.

Fig. S10 SEM micrograph of the complex 3.

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Fig. S11 TEM micrograph of the complex 3.

Fig. S12 Powder XRD patterns of MCM-41 and complex 3.

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Fig. S13. Diffuse reflectance spectra of complexes 1-3 and the standard phosphor
perylene.
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Table S1 Wavenumbers observed in FT-IR and FT-Raman Spectra of the samples

and the respective vibrational assignments for the silylated ligand SiBFPD-Na and
complex 3

SiBFPD-Na 3
IR Raman IR Raman description
3335 3410 (N-H)
1629 1606 1629 1606 (NHC=O)
1443 1448 (N-H)
1590 1404 1568 1421 S(C=O)
2923 2925 (CSP3-H)
2961 2961 (CSP3-H)
2851 2851 (CSP3-H)
1284 1283 v (C-C)
1384 1384 1384 (CH2)
1519 (C=N)
1486 1486 (C=C)
1076 1195 1083 1195 as (Si-O)
748 847 748 (Si-O-Si)
548 (Si-O-Si)
961 969 960 969 (Si-OH)