Preparation and Photophysical Properties of Materials Obtained by Co-intercalation of 4-MAA and 2-NSA into Mg-Al-LDH

doi:10.3724/SP.J.1077.2012.00122

Abstract

Abstract:

A pair of chromophores with donor-acceptor properties, 4-methoxyphenylacetic acid (4-MAA) and 2-naphthalene sulfonic acid (2-NSA), were intercalated into the layered double hydroxide (LDH), [Mg_0.66Al_0.34(OH)₂](CO₃)_0.17·0.67H₂O by the method of ion-exchange procedures in ethylene glycol. The obtained co-intercalation compounds were characterized by X-ray diffraction, infrared and thermogravimetry techniques. The photochemical properties of the obtained compounds were studied by UV-Vis absorption and fluorescence spectroscopy. The guest molecular sizes and structures were investigated utilizing an ab initio (HF/6-31G) method by G03w. It was believed that the molecular axis of the interlayer 4-MAA molecule was tilted approximately 45°to the layers, and the molecular axis of the interlayer 2-NSA molecule was perpendicular to the plane of the host layer. Both of them were arranged in monolayer between the metal hydroxide layers. These results indicate that the confinement of the pair of chromophores, 4-MAA-2-NSA, within the interlayer region of hydrotalcites are in favor of guest-host interaction and guest-guest interaction, and that the pair of chromophores, 4-MAA-2-NSA can give rise to energy transfer processes because of the characteristics of their excited states.

Key words: hydrotalcites, co-intercalation, donor-acceptor, energy transfer

CLC Number:

O641

LI Lei, ZHU Kai, ZHANG Li, CHEN Da-Zhou. Preparation and Photophysical Properties of Materials Obtained by Co-intercalation of 4-MAA and 2-NSA into Mg-Al-LDH[J]. Journal of Inorganic Materials, 2012, 27(2): 122-128.

Figures/Tables 13

Fig. 1 XRD patterns of (a) Mg-Al-CO3-LDH, (b) Mg-Al-4- MAA-LDH and (c) Mg-Al-2-NSA-LDH

Fig. 2 FTIR spectra of (a) Mg-Al-CO3-LDH, (b) 2-NSA, (c) Mg-Al-2-NSA-LDH, (d) 4-MAA and (e) Mg-Al-4-MAA-LDH

Fig. 3 TG-DTA curves of Mg-Al-4-MAA-LDH (A) and Mg- Al-2-NSA-LDH(B)

Table 1 Chemical compositions of co-intercalation compounds

Sample (n_4-MAA/n_2-NSAin mixture of solution)	Composition
3:1	[Mg_0.66 Al_0.34 (OH) ₂] (4-MAA)_0.22 (2-NSA)_0.10·0.67H₂O
2:1	[Mg_0.66 Al_0.34 (OH) ₂] (4-MAA)_0.17(2-NSA)_0.15·0.66H₂O
1:1	[Mg_0.66 Al_0.34 (OH) ₂] (4-MAA)_0.11(2-NSA)_0.21·0.67H₂O
1:2	[Mg_0.66 Al_0.34 (OH) ₂] (4-MAA)_0.08(2-NSA)_0.24·0.64H₂O
1:3	[Mg_0.66 Al_0.34 (OH) ₂] (4-MAA)_0.05(2-NSA)_0.27·0.63H₂O

Fig. 4 DTA curves of co-intercalation compounds with different n4-MAA/n2-NSA in mixture of solution

Fig. 5 UV-Vis spectra of (a)2-NSA, (b)4-MAA, (c) Mg-Al-2- NSA-LDH and (d) Mg-Al-4-MAA-LDH

Fig. 6 UV spectra of co-intercalation compounds with different n4-MAA/n2-NSA in mixture of solution

Fig. 7 Emission spectra of (λexc=274 nm) (a) Mg-Al-4-MAA- LDH, (b) 4-MAA, (c) Mg-Al-2-NSA-LDH and (d) 2-NSA

Fig. 8 Emission spectra of co-intercalation compounds with different n4-MAA/n2-NSA in mixture of solution(λexc=274 nm)

Fig. 9 Absorption and emission spectra of 4-MAA and 2-NSA

Fig. 10 Molecular structure of (a) 4-MAA and (b) 2-NSA anion

Table 2 Calculated charges for O of 4-MAA and 2-NSA anions

Anion	Calculated charges
Anion	O¹	O²	O³
4-MAA	-0.7533	-0.7503	-0.6669
2-NSA	-0.6939	-0.7812	-0.6903

Fig. 11 Schematic illustration of (a) Mg-Al-4-MAA-LDH, (b) Mg-Al-2-NSA-LDH and (c) co-intercalation compounds

References 13

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