The most characteristic of solid state reaction at low temperature is that reaction is in progress at room temperature or near room temperature. Compare with liquid state reaction

solid state reaction is high selection and high yield. Because solid state reaction don’t need solvent

and this is environtly friendly

so it is a green synthesis method. A lot of people are interested in it recently.We have synthesized four solid complexes of rare earth with phenylacetic acid (L) by method of solid state reaction at low temperature. Elemental analysis

rare earth coordination titration

Molar conductivity studies suggest that the composition of the complexes is RE(L)

3

·nH

2

O(n=0.5～1.5;RE=La

Nd

Eu

Tb;L= C

6

H

5

CH

2

COO

-

).TGA curve of La

3+

complex began to lose weight at 65.41～86.03℃ and weight loss was 1.835%

which was good accordance with the theoretical data 1.628% when complex had 0.5 water molecular. The temperature of losing water was lower

so water is induced to be crystal water. At 345.78～376.52 ℃ there is a great lose weight which was caused by the decomposition of La

3+

complex.The IR spectra of sodium salt of the ligand show bands at 1571cm

-1

(s) and 1386cm

-1

(s)

assigned to carboxyl group’s antisymmerty stretch vibration ν

as

(COO

-

) and symmetry stretch vibration ν

s

(COO

-

). In addition

the band at 3 026

1 491

706cm

-1

are individaully assigned to phenyl’sν

C—H

ν

C—C

δ

C—H

vibration. The IR spectra of complexes shows bands at nearby 1546～1553cm

-1

(s) assigned to ν

as

(COO

-

) with a shift of 18～25cm

-1

to the lower frequency region

which compared with sodium salt of ligand; The band at nearby 1393～1403 cm

-1

(s) is assigned to ν

s

(COO

-

) with a shift of 7～17cm

-1

to the higher frequency region

which still compared with sodium salt of ligand.These results indicate that the carboxyl group is bonded to the metal ions through two oxygen atoms as a symmetrical chelating bidentate group.The

1

H NMR of the ligand in DMSO shows the proton of phenyl resonance is multiplet peaks at (7.22~7.33)×10

-6

and integral intensity shows it has five protons; The proton of methylene group resonance peak is at 3.56×10

-6

and integral intensity shows it has two protons. The proton resonance of the —COOH is at 12.33×10

-6

. The

1

H NMR spectra of the complexes are similar. The proton of phenyl and methylene group resonance peaks are all clearly

and all shift to high field at different degree. The result indicated the carboxyl group’s oxygen of ligand coordinated with metal ions

which produced the shielded effect

it led to the proton resonance peaks shifting to high field. The absence of the —COOH proton resonance indicates that the carboxyl group is bonded to the metal ions through COO

-

group.Fluorescence spectra of Eu

3+

complex show main emission peaks at 592.2 nm and 614.0 nm

which correspond to magnetic dipole transition

5

D

0

→

7

F

1

and

5

D

0

→

7

F

2

electric dipole transition of Eu

3+

ion

respectively. The intensity ratio of the latter to the former is 2.1. It indicates that there is no inversion symmetry at the site of Eu

3+

ion

[10]

. Fluorescence of complexes of Eu

3+

with phenylacetic acid is part of M→M and L→M mixed luminescence.Fluorescence spectra of Tb

3+

complex show main emission peaks at 546.0 nm

which correspond to

5

D

4

→

7

F

5

transition

respectively. The emission intensity is 459.5 a.u. Fluorescence of complexes of Tb

3+

with phenylacetic acid is part of L→M luminescence

and emission intensity is stronger than Eu

3+

complex. The ligand has sensitized Tb

3+

ion in fluorescence intensity.