Accepted Manuscript Self-assembly of Terbium(III)-based Metal-organic Complexes With Two-photon Absorbing Active Dandan Li, Nanqi Shao, Xianshun Sun, Guocui Zhang, Shengli Li, Hongping Zhou, Jieying Wu, Yupeng Tian PII: DOI: Reference:

S1386-1425(14)00818-X http://dx.doi.org/10.1016/j.saa.2014.05.038 SAA 12200

To appear in:

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Received Date: Revised Date: Accepted Date:

16 January 2014 3 April 2014 9 May 2014

Please cite this article as: D. Li, N. Shao, X. Sun, G. Zhang, S. Li, H. Zhou, J. Wu, Y. Tian, Self-assembly of Terbium(III)-based Metal-organic Complexes With Two-photon Absorbing Active, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy (2014), doi: http://dx.doi.org/10.1016/j.saa.2014.05.038

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Self-assembly of Terbium(III)-based Metal-organic Complexes With Two-photon Absorbing Active

Dandan Li, Nanqi Shao, Xianshun Sun, Guocui Zhang, Shengli Li, Hongping Zhou, Jieying Wu*, Yupeng Tian*

Department of Chemistry, Key Laboratory of Functional Inorganic Materials Chemistry of Anhui Province, Anhui University, Hefei 230039, P. R. China; (phone: +86-551-5108151; fax: +86-551-5107342; e-mail: [email protected];)

Abstract: Hybrid complexes based on D- -A type dyes p-aminostyryl-pyridinum and Terbium(III) complex anion (1, 2) have been synthesized by ionic exchange reaction. Meanwhile two different alkyl-substituted amino groups were used as electron donors in organic dyes cations. The synthesized complexes were characterized by element analysis. In addition, the structural features of them were systematic studied by single crystal X-ray diffraction analysis. Their linear properties have been systematically investigated by absorption spectra and fluorescence, the results show that the energy transfer takes place from the trans-4-[4‟ -(N, N-diethylamino)styryl]-N-methyl pyridinium (2 ) cation to Tb(III). In addition, complex 2 exhibit a large two-photon absorption coefficient : 0.044 cm/GW at 710 nm. Keywords: Terbium(III) complex; Organic dyes cations; X-ray diffraction analysis; Linear properties; Energy transfer; Two-photon absorption;

1. Introduction The design and synthesis of metal-organic complexes have attracted much attention due to their intrinsic physicochemical properties which promote applications in the areas

of

luminescent

materials,

heterogeneous

catalysis,

magnetism,

and

electrochemistry, as well as their intriguing variety of architectures and topologies [1-10]. In this area, one important branch is the construction of lanthanide-based metal-organic

complexes

because

of

their

potential

applications

in

fluoroimmunoassays [11], spectroscopic structural probes in biological systems [12], laser systems [13], optical amplification [13], organic light-emitting diodes [14], single-molecule magnets [15, 16], and pressure/damage sensors [17] owing to their unique luminescence properties, such as the characteristic narrow-line emission and long luminescence lifetimes [18-26]. Along with the development of two-photon absorption (TPA) materials [27, 28] and ultrafast lasers, two-photon scanning microscopy have been used extensively. Two-photon absorption materials extends the excitation wavelength to the long-wavelength region, which is in favor of less-harmful labeling and deep-penetrating bioimaging applications [29-32]. Therefore, with a combination of the advantages of both lanthanide and two-photon scanning microscopy, two-photon absorption lanthanide complexes attracts great attention [33-36], in which the TPA active is aroused via TPA of chromophores and subsequent energy transfer to the lanthanide ions. However, examples for the lanthanide complexes with excellent TPA properties are still very limited. To achieve effective two-photon sensitized probes, the „antennae‟‟ with efficient two-photon absorption (TPA) for light-harvesting are needed to overcome the poor extinction coefficients of the Ln(III) ions caused by the symmetry-forbidden nature of the inner-shell f–f transition [37]. Initially, the „antenna‟‟ effects were utilized sensitize the luminescence of Eu(III) and Tb(III), which were directly linked to proteins, nucleic acids, and biologically relevant chromophores [38, 39]. Accordingly, in the present work, we report two novel Tb(III) complex (as shown in Scheme 1) that meets the urgent need described above. In these complexes, the important point is using trans-4-[p-(N,Ndialkylamino)styryl]-N-methylpyridinium as a one- and two-photon sensitizer for Tb(III) ion. The photophysical properties demonstrate that the

energy

transfer

takes

place

from

the

trans-4-[4‟ -(N,

N-diethylamino)styryl]-N-methyl pyridinium (2 ) cation to Tb(III) and complex 2

exhibit a large two-photon absorption coefficient : 0.044 cm/GW at 710 nm.

2. Experiments 2.1. General All chemicals used were of analytical grade and the solvents were purified by conventional methods before use. The 1H NMR spectra were performed on Bruker 400 MHz spectrometer with TMS as the internal standard. Elemental analysis was performed on PerkineElmer 240 instrument. Mass spectra were determined with MALDI-TOF-MS.

IR

spectra

were

recorded

on

NEXUS

870

(Nicolet)

spectrophotometer in the 400-4000 cm-1 region using a powder sample on a KBr plate. Single crystals of the complexes 1 and 2 used in X-ray determination were obtained by slow evaporation of methanol covered with acetonitrile at room temperature. X-ray diffraction data of them were collected on a Bruker Smart 1000 CCD area detector diffractometer. Both of the radiation sources were MoK (9 = 0.713 Å). Empirical absorption correction was applied to the data. The structures were solved by direct methods and refined by full-matrix least-squares methods on F2. All the nonhydrogen atoms were located from the trial structure and then refined anisotropically with SHELXTL using the full matrix least-squares procedure. The hydrogen atom positions were geometrically idealized and generated in idealized positions and fixed displacement parameters. Cambridge Crystallographic Data Centre (CCDC) as supplementary publication numbers CCDC-974956 (for 1), 974957 (for 2). Electronic absorption spectra were obtained on a UV-265 spectrophotometer. Fluorescence measurements were performed using a Hitachi F-7000 fluorescence spectrophotometer. Two-photon absorbing active were measured using femtosecond laser pulse and Ti: sapphire system (680–1080 nm, 80 MHz, 140 fs, Chameleon II) as the light source. All measurements were carried out at room temperature. 2.2 Synthesis

Scheme 1 Synthesis route of 1 and 2

2.2.2 Preparation of 4-(N,N-Diethylamino)benzaldehyde (A2) 4-(N, N-diethylamino)benzaldehyde was synthesized according to the literature method [43]. At room temperature, the compound is pale yellow solid. Yield 90%. Mp: 42 C. IR (KBr, cm-1) 2974 (m), 1665 (s), 1598 (s), 1566 (m), 1528 (s), 1470 (m), 1409 (s), 1357 (s), 1330 (m), 1179 (s), 1002 (w), 839 (m), 591 (w); 1H NMR (400 MHz, d6-Acetone) / 9.6 (s, 1H,) 7.69 (d, J = 8.3 Hz, 2H,) 6.79 (d, J = 8.3 Hz, 2H,) 3.51 (q, J = 7.0 Hz, 4H), 1.20 (t, J = 7.0 Hz, 6H); 13C NMR (100 MHz, d6-Acetone)/ 189.7, 153.1, 132.6, 125.8, 111.5, 45.1, 12.7. 2.2.1 Preparation of 1,4-Dimethylpyridinium iodide (B) 1,4-Dimethylpyridinium iodide was synthesized according to the literature method [40, 41]. White powder product was collected. Yield 90%. Mp: 155 ºC [42]. IR (KBr, cm-1) selected bands: 3451 (m), 3023 (m), 1644 (s), 1517(m), 1517 (m), 1477 (m), 1289 (s), 1182 (s), 1043 (m), 809 (s), 697 (s), 485 (s); 1H NMR (400 MHz, d6-DMSO) / 8.84 (d, J = 6.0 Hz, 2H), 7.97 (d, J = 6.0 Hz, 2H), 4.29 (s, 3H), 2.60 (s, 3H);

13

C

NMR (100 MHz, d6-DMSO/) 158.2,4793 2.2.3 Preparation of trans-4-[4‟ -(N, N-dialkylamino)styryl]-N-methyl pyridinium iodides was synthesized according to a literature method [43]. Yield 84%. Mp: 261 C. Found: C, 52.55; H, 5.32; N, 7.48%, C16H19N2I requires C, 52.46; H, 5.19; N, 7.65%; M+, 239.2. IR (KBr, cm-1) selected bands: 2917 (w), 1644 (m), 1577 (s), 1527 (w), 1507 (w), 1432 (w), 1371 (m), 1164 (s), 982 (m), 824 (m). 1H NMR (400 MHz, d6-DMSO) / 8.69 (d, J = 6.3 Hz, 2H,) 8.05 (d, J = 6.3 Hz, 2H,) 7.91 (d, J = 16. Hz, 1H), 7.60 (d, J = 8.5 Hz, 2H), 7.17 (d, J = 16.1 Hz, 1H), 6.79 (d, J = 8.5 Hz, 2H), 4.18 (s, 3H), 3.02 (s, 6H);

13

C NMR (100 MHz, d6-DMSO) / 152.

5, 147.9, 145.8, 142.5,

131.5, 125.5, 123.2, 118.2, 112.5, 47.2, 44.9. was synthesized according to a literature method [43]. Yield 89%. Mp: 225 C. .Found: C, 54.75; H, 5.72; N, 7.18%, C18H23N2I requires C, 54.82; H, 5.84; N,

7.11%; M+, 267.3. IR (KBr, cm-1): 2967 (w), 1644 (m), 1585 (s), 1521 (s), 1471 (w), 1434 (w), 1344 (m), 1180 (s), 1152 (m), 1078 (w), 974 (m), 825 (m). 1H NMR (400 MHz, d6-DMSO)/d (8.67 ,J=H 6.3 z,2H,)d 8.03( ,J=H 6.4 z,2H,)d 7.90( ,J=016. Hz, 1H), 7.57 (d, J = 8.5 Hz, 2H), 7.13 (d, J = 16.1 Hz, 1H), 6.75 (d, J = 8.5 Hz, 2H), 4.17 (s, 3H), 3.53 – 3.37 (m, 4H), 1.13 (t, J = 6.9 Hz, 6H); d6-DMSO)/154.

13

C NMR (100 MHz,

8, 150.1, 144.2, 142.5, 130.5, 128.5, 121.9, 117.4, 111.3, 46.8, 43.8,

12.5. 2.2.4 Preparation of Tb(III) complexes To an aqueous ethanol solution of stoichiometric molar ratios of pyridinium iodides and -diketone ligands (HTTA) neutralized with aqueous NaOH solution was added dropwise stochiometric aqueous Tb(NO3)3 under vigorous stirring. The resulting mixture was refluxed half an hour in a water bath. Isolated precipitate was filtered out and purified by recrystallization from suitable solvent. Complex 1: Yield 95%. Mp: 197 C. IR (KBr, cm-1): 3080 (w), 2920 (w), 1604 (m), 1577 (m), 1534 (m), 1508 (m), 1478 (w), 1356 (w), 1305 (m), 1229 (w), 1246 (w), 1182 (m), 1163 (w), 1138 (m), 1060 (w), 1038 (w), 933 (w), 785 (m), 749 (w), 724 (m), 681 (w), 641 (m), 580 (m). 1

H NMR (400 MHz, d6-Acetone) / 10.30 (d, J = 6.43 Hz, 2H), 8.89 (d, J = 6.46 Hz,

2H), 8.13 (d, J = 16.03 Hz, 1H), 7.69 (d, J = 8.93 Hz, 2H), 7.43 (d, J = 16.03 Hz, 1H), 7.25 (d, J = 4.89 Hz, 4H), 6.84 (d, J = 8.91 Hz, 2H), 6.75 (d, J = 4.88 Hz, 4H), 6.67-6.61 (m, 4H), 5.69 (s, 4H), 4.03 (s, 3H), 3.11 (s, 6H).

13

C NMR (100 MHz,

d6-Acetone) / 193.3, 182.5, 152.1, 147.2, 145.1, 142.0, 136.3, 132.7, 131.1, 129.4, 128.9, 125.1, 122.8, 117.5, 112.1, 46.5, 44.3. Anal. Calc. for C48H35TbF12N2O8S4: C 44.94, H 2.75, N 2.18 %; Found C 45.15, H 2.48, N 2.01 %. Complex 2: Yield 90%. Mp: 176 C. IR (KBr, cm-1): 3080 (w), 2974 (w), 2852 (w), 1606 (m), 1575 (m), 1536 (m), 1510 (m), 1473 (w), 1410 (m), 1355 (w), 1305 (m), 1244 (w), 1177 (m), 1138 (m), 1062 (w), 1038 (w), 932 (w), 859 (w), 784 (m), 750 (w), 720 (m), 685 (w), 641 (m), 580 (m). 1H NMR (400 MHz, d6-Acetone) ppm 10.00 (d, J = 6.48 Hz, 2H), 8.72 (d, J = 6.47 Hz, 2H), 8.08 (d, J = 15.97 Hz, 1H), 7.66 (d, J = 8.94 Hz, 2H), 7.34 (d, J = 15.98 Hz, 1H), 7.24 (d, J = 4.96 Hz, 4H), 6.81 (d, J = 8.94 Hz, 2H), 6.75 (s, J = 4.95 Hz, 4H), 6.68-6.62 (m, 4H), 5.46 (s, 4H), 4.04 (s, 3H), 3.59-3.42 (m, 4H), 1.21 (t,

J = 7.05 Hz, 6H).

13

C NMR (100 MHz, d6-Acetone) / 193.6, 182.7, 154.2, 149.3,

143.7, 142.1, 136.5, 132.9, 130.1, 129.7, 128.9, 127.6, 121.5, 117.1, 110.8, 105.6, 84.4, 46.5, 43.2, 12.3. Anal. Calc. for C50H39TbF12N2O8S4: C 45.81, H 3.00, N 2.14 %; Found C 45.92, H 3.06, N 2.07 %.

3. Results and discussion 3.1 Crystal Structure of Complexes 1 and 2 The crystallographic data are listed in Table 1. Complexes 1 and 2 crystallize in Monoclinic system with P21/n space group. The coordination environment of Tb(III) in 1 and 2 with atom labeling scheme are shown in Figure 1(b) and Figure 2(b), while a complete molecule of 1 and 2 are shown in Figure 1(a) and Figure 2(a). As shown in Fig.1 and Fig.2, the structure of complex 1 and 2 is similar except that the pyridinium cation moiety.

Fig.1. Crystal structure of 1 (In order to clear, hydrogen atoms are deleted).

Fig.2. Crystal structure of 2 (In order to clear, hydrogen atoms are deleted).

As shown in Fig. 1, the asymmetric unit contains a mononuclear Tb(III) ion coordinated to four bidentate TTA- ligand anions, in a typical eight-coordination fashion. The anionic TTA- appear as typical O,O-chelates via the ketone functional groups, forming eight-membered rings with an average bite angle of 72.22°, which indicate t -diketonate hat 2 TTA- has a strong coordinating ability. The symmetry can be approximately described as a distorted square antiprism, with the two “square” planes being defined by O1~O2~O5~O6 and by O3~O4~O7~O8. The dihedral angle between two planes is 1.02°. The Tb− O bond lengths range from 2.314(9) to 2.403(8) Å, and there is significant deviation from the average Tb− O bond length of 2.359 Å, slightly smaller than the sum of ionic radii of Tb3+ 1.04 Å (eight-coordinated) and O21.42 Å). Eight bonds with different lengths give rise to a slightly distorted square antiprism environment around the Tb(III) site. This kind of coordination configuration

around Tb(III) leads to the very low structural symmetry of 1. In these structures, the cationic pyridinium can offer net positive charge for the molecular, and the large conjugate system which is composed of phenylamine, vinyl and cationic pyridinium ensures the large ionic radius. In addition, we can learn from the crystal data (shown in Table 2), the C-C bond lengths of 1 (C5-C7: 1.44(2) Å, C8-C9: 1.49(2) Å) which link the benzene ring and pyridine ring are located between the normal C = C double bond (1.32 Å) and C–C single bond (1.53 Å ), which show that there is a-helectron ighly delocalized system in 1, it is the necessary condition for it bearing strong TPA response.

Table 1 Crystal data collections and structure refinements of 1, 2

Table 2 Selected bond lengths (Å) and angles (º) for complex 1 and 2

3.2 Linear spectroscopy The UV-vis absorption spectra of [N(n-Bu)4]+ [Tb(TTA)4]-, 1 and 2 in acetonitrile at the concentration of 1

10-5 mol L-1 are shown in Figure 3. The absorption band of

[N(n-Bu)4]+ [Tb(TTA)4]- is around 335 nm, while in the absorption spectrum of 1 and 2, two absorption bands around 335 nm and 480 nm are observed, in which, the ultraviolet absorption band is attributed to TTA- [44], and the blue one results from cationic pyridinium moiety [45].

Fig.3. The UV-vis absorption spectra of [N(n-Bu)4]+ [Tb(TTA)4]-, 1 and 2 in acetonitrile 1

10-5 mol L-1)

The emission spectra of [N(n-Bu)4]+ [Tb(TTA)4]-, 1 and 2 are shown in Figure 4 (

ex=335

nm). Characteristically bands from the Tb(III) cation are observed,

which we assign to the 5D4:

7

FJ transitions at ca. 490(J = 6), 545 (J = 5),

respectively. For the Tb(TTA)4-, we note the intensity of the 5D4:

7

F6 transition at

ca. 490 nm is enhanced compared to the case of the complexes 1 and 2. Since this transition has knownhypersensiti=v2) it [46], y(ßJ the decreased intensity of this peak in Tb(III) complexes 1 and 2 can be associated with an energy transfer in the Tb(III) complexes.

Fig.4. The emission spectra of [N(n-Bu)4]+ [Tb(TTA)4]-, 1 and 2 in acetonitrile 1

10-5 mol L-1,

ex=335

nm)

Importantly, for the Tb(III) complex 2 with the most intense band attributed to the 5D4:

7

F3 transition at ca. 613 nm. To further confirm this performance, the

emission spectrum of pyridinium 1 , 2 are shown in Figure 5 (

ex=335

nm), they

exhibit intense emission band between 600 and 605 nm. Considering above, we suggest that the energy transfer takes place from the trans-4-[4‟ -(N, N-diethylamino)styryl]-N-methyl pyridinium (2 ) cation to Tb(III). Whereas, no energy transfer occur can be observed for the introduction of trans-4-[4‟ -(N, N-dimethylamino)styryl]-N-methyl pyridinium (1 ).

Fig.5. The emission spectra of 1 and 2 in acetonitrile 1 ex=335

10-5 mol L-1,

nm)

3.3 Two-photon absorption (TPA) property As we known, the trans-4-[4‟ -(N, N-diethylamino)styryl]-N-methyl pyridinium possesses two-photon absorption properties in the wide wavelength range from 840 to 1000 nm. Furthermore, in our work, Tb(III) can be sensitized by the energy transfer from trans-4-[4‟ -(N, N-diethylamino)styryl]-N-methyl pyridinium (2 ) cation, it is an important characteristic for it (2) bearing TPA response. To study the TPA performance of 2, its absorption coefficient

were obtained by an

open-aperture Z-scan technique using a femtosecond laser pulse and a Ti:95 sapphire system (6801− nm, 80 MHz, 140 fs.)

The beam was spatially filtered to remove

higher-order modes and tightly focused using a 5 cm focal length lens. The incident average power of 100 mW was adjusted by a Glan prism. The thermal heating of the sample with high repetition rate laser pulse was removed by the use of a mechanical chopper running at 10 Hz. The sample (its thickness is 1 mm) was put in the light path, and all measurements were carried out at room temperature. As shown in Figure 6, the sample was recorded as Nujol mulls between quartz plates and determined under a laser wavelength of 710 nm (For other compounds: [N(n-Bu)4]+ [Tb(TTA)4]- and 2 , 2PA were not observed).

Fig.6. Z-scan data for 2 in the solid state, obtained under an open-aperture configuration. The black dots are the experimental data, and the solid curve is the theoretical fit (100 mW, 710 nm).

Figure 6 shows the typical Z-scan measurement of 2. The filled squares represent the experimental data, and the solid line is the theoretical curve modified from the following equations:

[ qo ( z )]m 3/ 2 0 ( m 1)

T ( z, s 1) m

qo ( z ) where x = z/z0, in which z0 & is the spot size at the focus,

0

2

I o Leff 1 x2

(1)

(2)

is the diffraction length of the beam, where &0

is the wavelength of the beam, and z is the sample

position. I0 is the input intensity at the focus z = 0 and equals the input energy divided by &

0

2

. Leff H

./

.

is the effective length, in which . is the linear absorption

coefficient and L is the sample length. The two-photon absorption coefficient

for complex 2 is calculated as 0.044

cm/GW, which indicated that the two-photon absorbing active of Tb(III) complex 2 can be sensitized by trans-4-[4‟ -(N, N-diethylamino)styryl]-N-methyl pyridinium (2 ) cation.

According to the results of optical measurements, it is tentatively suggested that the energy transfer occurred which may due to the fact that (i) the energy transfer can‟t take place from HTTA to Terbium(III) which result from the triplet level of -diketonate (HTTA) is below that of the resonance level 5D4 of Tb3+; (ii) in our work, when the complex 2 is excited, part of the energy absorbed by the trans-4-[4'-(N, N-diethylamino)styryl]-N-methyl pyridinium (2') cation is transferred onto Tb3+ excited states, and emission bands originating from the metal ion are detected after rapid internal conversion to the emitting level. Figure 7 describes the possible sensitization

processes

from

trans-4-[4'-(N,

N-diethylamino)styryl]-N-methyl

pyridinium (2') cation to Tb3+.

Fig.7. The sensitization processes of complex 2.

4. Conclusion Hybrid complexes based on D- -A type dyes p-aminostyryl-pyridinum and Terbium(III) complex anion (1, 2) have been synthesized, the structural features of them were systematic studied by single crystal X-ray diffraction analysis. One-photon absorption

and

emission

spectra

have

been

systematically

investigated.

Characteristically bands from the Tb(III) cation are observed, which we assign to the 5

D4:

7

FJ transitions at ca. 490(J = 6), 545 (J = 5), respectively. Whereas, for the

Tb(III) complex 2 with the most intense band attributed to the 5D4:

7

F3 transition at

ca. 613 nm which show that the energy transfer takes place from the trans-4-[4‟ -(N, N-diethylamino)styryl]-N-methyl pyridinium (2 ) cation to Tb(III). In addition, we have studied the TPA performance of 2, its absorption coefficient

were obtained by

an open-aperture Z-scan technique. The results show that complex 2 exhibit a large two-photon absorption coefficient : 0.044 cm/GW at 710 nm. As presented in this work,

the

Tb(III)

complex

2

can

be

sensitized

by

trans-4-[4‟ -(N,

N-diethylamino)styryl]-N-methyl pyridinium (2 ) cation. Once more it identifies the

promising direction for the synthesis of TPA lanthanide-based metal-organic complexes. Further optimizations of the “antennae” structure for needs of biological imaging are currently underway. Acknowledgements This work was supported by a grant for the National Natural Science Foundation of China (21271004, 21071001, 51372003, 21271003), the Natural Science Foundation of Anhui Province (1208085MB22, 1308085MB24), Ministry of Education Funded Projects Focus on returned overseas scholar, Department of Education of Anhui Province (KJ2012A025), Program for New Century Excellent Talents in University (China), Doctoral Program Foundation of Ministry of Education of China (20113401110004). Appendix A. Supplementary data Crystallographic data for the structural analysis have been deposited at the Cambridge Crystallographic Data Center, CCDC 1-974956, 2-974957. Copy of this information may be obtained free of charge via www: http:// www.ccdc.cam.ac.uk or from The Director, CCDC, 12 Union Road, Cambridge CB221EZ, UK (fax: +44 1223/ 336 033; email: [email protected]).

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Scheme 1

Fig.1.

1

Fig.2.

2

1

1

2

Fig.3.

1

2

(

Fig.4.

Fig.5.

1

1

2

2

(

2

(

Fig.6.

2

Fig. 7

2

3

Table(s)

Table 1 Crystal data collections and structure refinements of 1, 2 1

2

C48H35TbF12N2O8S4

C50H39TbF12N2O8S4

Formula weight

1282.94

1310.99

Crystal system,

Monoclinic

Monoclinic

P21/n

P21/n

a= 10.510(5)Å

a= 10.485(5)Å

b= 21.754(5)Å

b= 21.541(5)Å

c= 23.203(5)Å

c= 24.288(5)Å

= 100.804(5)°

= 98.857(5)°

Empirical formula

Space group Unit cell dimensions

5211(3) Å3

5420(3) Å3

4

4

1.635

1.607

1.613

1.553

Reflns. Collected

36300

38303

Reflns. Unique

9194

9554

Parameters

679

697

1.030

1.004

R1 = 0.1612, wR2 = 0.2350

R1 = 0.0706, wR2 = 0.1945

Volume Z Dc (mg m-3) (mm-1)

Goodness-of-fit on F2 R1, wR2 (all data)

Table 2 Selected bond lengths (Å) and angles (º) for complex 1 and 2 Complex 1 Tb(1)-O(6)

2.314(9)

Tb(1)-O(2)

2.341(8)

Tb(1)-O(4)

2.352(8)

Tb(1)-O(8)

2.365(7)

Tb(1)-O(7)

2.365(8)

Tb(1)-O(1)

2.366(8)

Tb(1)-O(5)

2.369(9)

Tb(1)-O(3)

2.403(8)

O(2)-C(27)

1.276(14)

O(3)-C(30)

1.236(13)

O(8)-C(17)

1.245(13)

O(4)-C(32)

1.246(13)

O(1)-C(25)

1.279(13)

O(5)-C(23)

1.249(14)

O(6)-C(21)

1.254(14)

O(7)-C(19)

1.246(13)

C(6)-C(7)

1.44(2)

C(8)-C(7)

1.31(2)

C(8)-C(9)

1.49(2)

O(8)-Tb(1)-O(7)

71.4(3)

O(2)-Tb(1)-O(1)

71.5(3)

O(6)-Tb(1)-O(5)

71.0(3)

O(4)-Tb(1)-O(3)

71.0(3)

2.401(5)

Tb(1)-O(2)

2.359(4)

Tb(1)-O(3)

2.369(5)

Complex 2 Tb(1)-O(1)

1

Tb(1)-O(4)

2.384(5)

Tb(1)-O(5)

2.372(5)

Tb(1)-O(6)

2.381(4)

Tb(1)-O(7)

2.335(5)

Tb(1)-O(8)

2.356(5)

C(44)-O(1)

1.249(8)

C(46)-O(2)

1.261(8)

C(38)-O(7)

1.243(10)

C(36)-O(8)

1.255(10)

C(30)-O(3)

1.243(8)

C(28)-O(4)

1.259(8)

C(22)-O(6)

1.220(9)

C(20)-O(5)

1.249(9)

C(6)-C(7)

1.455(12)

C(7)-C(8)

1.330(11)

C(8)-C(9)

1.437(12)

O(7)-Tb(1)-O(8)

72.77(18)

O(5)-Tb(1)-O(6)

71.72(16)

O(3)-Tb(1)-O(4)

71.09(16)

O(2)-Tb(1)-O(1)

72.05(16)

2

Self-assembly of Terbium(III)-based Metal-organic Complexes With Two-photon Absorbing Active

Hybrid complexes based on D- -A type dyes p-aminostyryl-pyridinum and Terbium(III) complex anion (1, 2) have been synthesized by ionic exchange reaction. Meanwhile two different alkyl-substituted amino groups were used as electron donors in organic dyes cations. Their linear properties have been systematically investigated by absorption spectra and fluorescence, the results show that the energy transfer takes place from the trans-4-

-(N, N-diethylamino)styryl]-N-methyl pyridinium (2 )

cation to Tb(III). In addition, complex 2 exhibit a large two-photon absorption coefficient : 0.044 cm/GW at 710 nm.

Hybrid Tb(III) complexes based on D- -A type dyes have been synthesized. The structural features of them were systematic studied. Linear absorption and emission spectra have been systematically investigated. The energy transfer takes place from the pyridinium (2 ) cation to Tb(III).