铕--芳香羧酸--丁二酸三元配合物的合成及荧光性能研究
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[20,21] −1 −1
Δνas−s (152 cm−1 )[22] ,
©
ÔÀ
259
Δνas−s
² ¸Ø Õ ¨ Í Å Õ ¨ Í Ñ Äß
2.3 ,
1
Fig.1 IR spectra of the complexes and ligands (a) Eu(BA)(BDA)·2H2 O; (b) Eu(PMBA)(BDA)·H2 O; (c) Eu2 (MCBA)3 (BDA)0.5 Cl2 ·H2 O; (d) Eu2 (PCBA)3 (BDA)Cl·H2 O; (e) Eu(PHBA)(BDA)·H2 O; (f) Eu2 (MBA)2 (BDA)Cl2 ·2H2 O; (g) BAH; (h) PMBAH; (i) MCBAH; (j) PCBAH; (k) PHBAH; (l) MBAH; (m) BDAH
µ Â Ú ×°ÜÚÏ© É ¬ ¤. ¤ § ¥ 3+ Ñ ·, Eu ° ¿ , Í Ì Ú , Õ¨Í ¨Ú Ï À Ì Ä ¥ ¤ ¯ Ì Ó ,± Ú Ï ©, ¢ ¡ À¯ Àըͧ°ÜÚÏ©° . 1 ÖÔ
258
Á ¨Ã ; Í (BAH), ¢ Ñ Á Ë, Í (PMBAH), Î Í (MCBAH), ¢ Î Í (PCBAH), ¢ Ñ Í (PHBAH) Ì¢ Ä Ñ Í (MBAH) ² Â; Õ ¨ Í (BDAH) ¡ Û² ¬Â. Þ Ð 1.2 Ú Ï © Ï Æ Ñ È, Eu(PMBA)(BDA)·H2 O Å . ¯ 20 mmol Eu2 O3 , Ù Í , ß ·, EuCl3 ¬ . ¨Ã Á 0.4 mol/L EuCl3 Ë. ¯ 2 mmol ¢ Ñ Í, 10 mL ¨ à Á . ¯ É 2 mmol EuCl3 ¨ à Á Ë ß ¢ Ñ Í Ë °, £ ª ¬, Á ¨ à Á Ë Ó Æ pH 5∼6. ¯ 0.5 h , ´ Ë ° ßÉ 2 mmol Õ ¨ Í ¨Ã Á Ë, Á ¨Ã Á ËÓÆ pH 6∼7, Ý ¯ 4 h, , ÒÞ ¬ , , ¨ à Á ¤ Ä, ¦ Ó Ì Ä , ¼ ·¨ Ú Ï ©, ¨ »Ì . À ¬ ¨ ÜÚ ° Ü Ú Ï © « ¦ ß, Ï À Eu3+ Ú Í §Ú 1:1 ¨ Ü Ú Ï ©, ¡ ÆÚ°ÜÚÏ© Ï Æ È. ÖÔ 1.3 (450–4000 cm−1 ) PERKIN– Ú Ï ¾Ø, Æ ELMER Spectrum One Ú Þ; ¾ Ú (220–380 nm) ¨ Ë Æ , Ð Lab Tech UV–2100 ¾ Ú º¥ ß Ü ¾Ø;
( 410082)
, . EDTA ; ; . . , , , , , O614 1005-3093(2009)03-0257-07
¶ – Õ ·¯ – ÒÓ¯ ¨ß Ñß Û ¦ ¢ ¼ Å ÄÐÈ Áµ ¾º¸
∗
Synthesis and fluorescent properties of the ternary complexes of europium with aromatic carboxylic acid and butanedioic acid
Û¯
(νC=O =1705–1680 cm
−1
(νC−O =1275 cm−1
Ì
Ô)
C—O
1
Table 1 Elemental analysis data of the complexes (mass fraction, %)
Complex Eu(BA)(BDA)·2H2 O Eu(PMBA)(BDA)·H2 O Eu2 (MCBA)3 (BDA)0.5 Cl2 ·H2 O Eu2 (PCBA)3 (BDA)Cl·H2 O Eu(PHBA)(BDA)·H2 O Eu2 (MBA)2 (BDA)Cl2 ·2H2 O Eu/% 36.81(35.74) 37.97(36.08) 32.96(33.05) 33.36(31.72) 34.56(35.91) 37.51(36.65) C/% 29.83(31.07) 33.02(34.22) 31.76(30.04) 30.99(31.34) 32.40(31.22) 29.01(28.97) O/% 28.84(30.10) 25.66(26.59) 15.43(15.66) 19.23(20.04) 31.04(30.25) 22.43(23.15)
(νO−H =3200–2700 cm
−1
ª
¾ÜÉ Í
.
1
), O—H
−1
Ú
Û¯ ¼
.
(σO−H =940–900 cm
), C=O )
Æ «
Ú Ï © » ¯ ² ¶ , § ¾ Ú Ï © °, Í § 1530 cm−1 Ì 1391 cm−1 , ¢ Ñ Í § 1521 cm−1 Ì 1401 cm−1 , Î Í § 1530 cm−1 Ì 1410 cm−1 , ¢Î ͧ −1 −1 1521 cm Ì 1403 cm , ¢ Ñ Í§ 1521 cm−1 Ì 1401 cm−1 , ¢ ÄÑ Í§ 1539 cm−1 Ì 1390 cm−1 À Ñ ¯¢ ¼ Û¯ νas (oco) Ì¢ ¼ Û¯
23
¯
§
¡ ¥ ³µ
(X =BA, PMBA, MCBA, PCBA, PHBA, MBA;
l=1∼2; m=1∼3; n=0.5∼1; p=0∼2; q =1∼2),
¾ Ú Ñ °. 2.2 Ú × ÚÏ©Ö¡Ú Ú Õ ¨ Õ 1g–1l Ú Õ 1a–1f ¢ º : Ñ ² Æ § ¯ : O—H ¼ ¼ Û¯ Û¯
2009Ö6
23 3
±
µ
Â
¯
Vol.23 No.3 June 2 0 0 9
CHINESE JOURNAL OF MATERIALS RESEARCH
°Á̳¾ ϲÏÞ¡£ ÜÒ «ÏÒ¡Ç¡ÏÞË ÆÏ¡¡£Ï ÜÏ¢¡£Ù ÒÆ¡ ÏÜ¡£ ÅÆÒÎ ÜÏ ÍÆÜ ÙÁתÏÜ «ªÜ Ø º Æ Á Á Ü « §Ù Õ ÒÇ ÆÁ Á Ü «Ø£ ªÞÜ « Õ Å ¦ Ü «Û£ ªÞÜ « § ÉÉ º Ù ÓÓº ¶Ã Ï Ü « ×ªÏ Ø¤Ý ±Ý
* 04GK3035
Ñ¿ ¹ Ò 05JJ30020 Î Ñ¿¹ÚÐ¹Ú¶Ò ½¹³ . »; 2009 × 2 ¡ 13 µ». 2008 × 9 ¡ 27 ¥ : Àݸ, «
ÆÏ Ì Ä ÚÏ©, ß 18– –6 , ¡ ËÀÚ¡Ã ¡ , ª¦ÀÚÏ© ¦ß Ö ; Niyama [7] Eu3+ °¿ , Ý (DBM) Ì Ú , Ç ² Ë Â ½ © « ¨Ú Ï ÀDz°ÜÚÏ©, ¬À ¦ ß, ± Ë ß , ¹ ÀÚ ´ ° ¿ Ó Ó , °ÜÚÏ© « ¦ß ¹ Ø ¨ Ü Ú Ï ©; Ü· [8−11] Eu3+ Ð Tb3+ ° ¿ , Ç ´ÁÐ Í ÌÚ , ª ¨ ÄÕ ¨Í ¨Ú Ï ÀÌ Ä° Ò « Ó Ï©. ÃÚ, Ç ´Á [12−14] ° Ñ Ä Ê [15,16] 2,2 ¢– à [17,18] ¨
(Eu2 O3 ),
[19]
1.1
Æ © Ä Í
Æ
Âß
99.99%;
§ ²
± HIACHI F–4500 Ï ¾Ø, ³ Ì 1200 nm/min, Ñ 700 V, ¹ 5 nm, ¾Ø Æ ; Ú Ï © ° × Ü É É Ð EDTA Æ ¾Ø, Ú Ï © V(HNO3 ):V(HClO4 )=1:1 Íß µ , Ë Ë ÑǨ Ë Ó pH=5∼6, ¨ Û, Ü É C O É Á LECO TC–436 CS–444 Ü É ¬Ï ¾ Ø; ¦ Ø Ó Á NETZSCH STA449C Ï ¬Ï ¾Ø, ¼ © ¼ , N2 £ , ¾ £ Ì 10 £/min. 2 Ü 2.1 Þ Ð ÚÏ©² , Ò Ø Ã Á Ó Û, Ø ¨ Ë N,N– ¨ Ñ ¨ Û, ¡ Ü É ¬ ¯ à ¥ 1, º Ù ¡ ³ÚÏ© ¯ Ñ Eul Xm (BDA)n Clp · q H2 O
Û ª ÝÊ Ä
Note: the calculated values is in the parentheses
3
Ø :Î – ° Î – ֩αÝÛ ª
1453
3+
×
cm−1 ),
Ú Eu  ڡ . ÒÚÏ©§ 3100–3700 cm ² ̽ (à ۯ ), ©§ 490–510 cm ² À ¼Ã ÚǪ (Ñ Ñ ¯ ), ÚÏ©° à ҼÚÚ¡ , ± Ì ´ ÀÚÏ© ¯ .
ABSTRACT Six new ternary complexes of europium were synthesized with the first ligands of benzoic acid, p-methylbenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, p-hydroxylbenzoic acid, methoxybenzoic acid and the second ligand of butanedioic acid. Their molecular composition and structures were characterized by means of elemental analysis, EDTA titrimetric method, FT–IR and UV spectroscopies. The thermal stability properties of the title complexes were studied by thermal analysis instrument. The luminescent properties of the title complexes and their corresponding binary complexes were investigated by means of fluorescence instrument. The fluorescence spectra data show that the new ternary complexes have much higher luminescence intensity than their corresponding binary complexes. KEY WORDS organic polymer materilas, europium, complex, synthesis, butanedioic acid, fluorescence
Δνas−s (152 cm−1 )[22] ,
©
ÔÀ
259
Δνas−s
² ¸Ø Õ ¨ Í Å Õ ¨ Í Ñ Äß
2.3 ,
1
Fig.1 IR spectra of the complexes and ligands (a) Eu(BA)(BDA)·2H2 O; (b) Eu(PMBA)(BDA)·H2 O; (c) Eu2 (MCBA)3 (BDA)0.5 Cl2 ·H2 O; (d) Eu2 (PCBA)3 (BDA)Cl·H2 O; (e) Eu(PHBA)(BDA)·H2 O; (f) Eu2 (MBA)2 (BDA)Cl2 ·2H2 O; (g) BAH; (h) PMBAH; (i) MCBAH; (j) PCBAH; (k) PHBAH; (l) MBAH; (m) BDAH
µ Â Ú ×°ÜÚÏ© É ¬ ¤. ¤ § ¥ 3+ Ñ ·, Eu ° ¿ , Í Ì Ú , Õ¨Í ¨Ú Ï À Ì Ä ¥ ¤ ¯ Ì Ó ,± Ú Ï ©, ¢ ¡ À¯ Àըͧ°ÜÚÏ©° . 1 ÖÔ
258
Á ¨Ã ; Í (BAH), ¢ Ñ Á Ë, Í (PMBAH), Î Í (MCBAH), ¢ Î Í (PCBAH), ¢ Ñ Í (PHBAH) Ì¢ Ä Ñ Í (MBAH) ² Â; Õ ¨ Í (BDAH) ¡ Û² ¬Â. Þ Ð 1.2 Ú Ï © Ï Æ Ñ È, Eu(PMBA)(BDA)·H2 O Å . ¯ 20 mmol Eu2 O3 , Ù Í , ß ·, EuCl3 ¬ . ¨Ã Á 0.4 mol/L EuCl3 Ë. ¯ 2 mmol ¢ Ñ Í, 10 mL ¨ à Á . ¯ É 2 mmol EuCl3 ¨ à Á Ë ß ¢ Ñ Í Ë °, £ ª ¬, Á ¨ à Á Ë Ó Æ pH 5∼6. ¯ 0.5 h , ´ Ë ° ßÉ 2 mmol Õ ¨ Í ¨Ã Á Ë, Á ¨Ã Á ËÓÆ pH 6∼7, Ý ¯ 4 h, , ÒÞ ¬ , , ¨ à Á ¤ Ä, ¦ Ó Ì Ä , ¼ ·¨ Ú Ï ©, ¨ »Ì . À ¬ ¨ ÜÚ ° Ü Ú Ï © « ¦ ß, Ï À Eu3+ Ú Í §Ú 1:1 ¨ Ü Ú Ï ©, ¡ ÆÚ°ÜÚÏ© Ï Æ È. ÖÔ 1.3 (450–4000 cm−1 ) PERKIN– Ú Ï ¾Ø, Æ ELMER Spectrum One Ú Þ; ¾ Ú (220–380 nm) ¨ Ë Æ , Ð Lab Tech UV–2100 ¾ Ú º¥ ß Ü ¾Ø;
( 410082)
, . EDTA ; ; . . , , , , , O614 1005-3093(2009)03-0257-07
¶ – Õ ·¯ – ÒÓ¯ ¨ß Ñß Û ¦ ¢ ¼ Å ÄÐÈ Áµ ¾º¸
∗
Synthesis and fluorescent properties of the ternary complexes of europium with aromatic carboxylic acid and butanedioic acid
Û¯
(νC=O =1705–1680 cm
−1
(νC−O =1275 cm−1
Ì
Ô)
C—O
1
Table 1 Elemental analysis data of the complexes (mass fraction, %)
Complex Eu(BA)(BDA)·2H2 O Eu(PMBA)(BDA)·H2 O Eu2 (MCBA)3 (BDA)0.5 Cl2 ·H2 O Eu2 (PCBA)3 (BDA)Cl·H2 O Eu(PHBA)(BDA)·H2 O Eu2 (MBA)2 (BDA)Cl2 ·2H2 O Eu/% 36.81(35.74) 37.97(36.08) 32.96(33.05) 33.36(31.72) 34.56(35.91) 37.51(36.65) C/% 29.83(31.07) 33.02(34.22) 31.76(30.04) 30.99(31.34) 32.40(31.22) 29.01(28.97) O/% 28.84(30.10) 25.66(26.59) 15.43(15.66) 19.23(20.04) 31.04(30.25) 22.43(23.15)
(νO−H =3200–2700 cm
−1
ª
¾ÜÉ Í
.
1
), O—H
−1
Ú
Û¯ ¼
.
(σO−H =940–900 cm
), C=O )
Æ «
Ú Ï © » ¯ ² ¶ , § ¾ Ú Ï © °, Í § 1530 cm−1 Ì 1391 cm−1 , ¢ Ñ Í § 1521 cm−1 Ì 1401 cm−1 , Î Í § 1530 cm−1 Ì 1410 cm−1 , ¢Î ͧ −1 −1 1521 cm Ì 1403 cm , ¢ Ñ Í§ 1521 cm−1 Ì 1401 cm−1 , ¢ ÄÑ Í§ 1539 cm−1 Ì 1390 cm−1 À Ñ ¯¢ ¼ Û¯ νas (oco) Ì¢ ¼ Û¯
23
¯
§
¡ ¥ ³µ
(X =BA, PMBA, MCBA, PCBA, PHBA, MBA;
l=1∼2; m=1∼3; n=0.5∼1; p=0∼2; q =1∼2),
¾ Ú Ñ °. 2.2 Ú × ÚÏ©Ö¡Ú Ú Õ ¨ Õ 1g–1l Ú Õ 1a–1f ¢ º : Ñ ² Æ § ¯ : O—H ¼ ¼ Û¯ Û¯
2009Ö6
23 3
±
µ
Â
¯
Vol.23 No.3 June 2 0 0 9
CHINESE JOURNAL OF MATERIALS RESEARCH
°Á̳¾ ϲÏÞ¡£ ÜÒ «ÏÒ¡Ç¡ÏÞË ÆÏ¡¡£Ï ÜÏ¢¡£Ù ÒÆ¡ ÏÜ¡£ ÅÆÒÎ ÜÏ ÍÆÜ ÙÁתÏÜ «ªÜ Ø º Æ Á Á Ü « §Ù Õ ÒÇ ÆÁ Á Ü «Ø£ ªÞÜ « Õ Å ¦ Ü «Û£ ªÞÜ « § ÉÉ º Ù ÓÓº ¶Ã Ï Ü « ×ªÏ Ø¤Ý ±Ý
* 04GK3035
Ñ¿ ¹ Ò 05JJ30020 Î Ñ¿¹ÚÐ¹Ú¶Ò ½¹³ . »; 2009 × 2 ¡ 13 µ». 2008 × 9 ¡ 27 ¥ : Àݸ, «
ÆÏ Ì Ä ÚÏ©, ß 18– –6 , ¡ ËÀÚ¡Ã ¡ , ª¦ÀÚÏ© ¦ß Ö ; Niyama [7] Eu3+ °¿ , Ý (DBM) Ì Ú , Ç ² Ë Â ½ © « ¨Ú Ï ÀDz°ÜÚÏ©, ¬À ¦ ß, ± Ë ß , ¹ ÀÚ ´ ° ¿ Ó Ó , °ÜÚÏ© « ¦ß ¹ Ø ¨ Ü Ú Ï ©; Ü· [8−11] Eu3+ Ð Tb3+ ° ¿ , Ç ´ÁÐ Í ÌÚ , ª ¨ ÄÕ ¨Í ¨Ú Ï ÀÌ Ä° Ò « Ó Ï©. ÃÚ, Ç ´Á [12−14] ° Ñ Ä Ê [15,16] 2,2 ¢– à [17,18] ¨
(Eu2 O3 ),
[19]
1.1
Æ © Ä Í
Æ
Âß
99.99%;
§ ²
± HIACHI F–4500 Ï ¾Ø, ³ Ì 1200 nm/min, Ñ 700 V, ¹ 5 nm, ¾Ø Æ ; Ú Ï © ° × Ü É É Ð EDTA Æ ¾Ø, Ú Ï © V(HNO3 ):V(HClO4 )=1:1 Íß µ , Ë Ë ÑǨ Ë Ó pH=5∼6, ¨ Û, Ü É C O É Á LECO TC–436 CS–444 Ü É ¬Ï ¾ Ø; ¦ Ø Ó Á NETZSCH STA449C Ï ¬Ï ¾Ø, ¼ © ¼ , N2 £ , ¾ £ Ì 10 £/min. 2 Ü 2.1 Þ Ð ÚÏ©² , Ò Ø Ã Á Ó Û, Ø ¨ Ë N,N– ¨ Ñ ¨ Û, ¡ Ü É ¬ ¯ à ¥ 1, º Ù ¡ ³ÚÏ© ¯ Ñ Eul Xm (BDA)n Clp · q H2 O
Û ª ÝÊ Ä
Note: the calculated values is in the parentheses
3
Ø :Î – ° Î – ֩αÝÛ ª
1453
3+
×
cm−1 ),
Ú Eu  ڡ . ÒÚÏ©§ 3100–3700 cm ² ̽ (à ۯ ), ©§ 490–510 cm ² À ¼Ã ÚǪ (Ñ Ñ ¯ ), ÚÏ©° à ҼÚÚ¡ , ± Ì ´ ÀÚÏ© ¯ .
ABSTRACT Six new ternary complexes of europium were synthesized with the first ligands of benzoic acid, p-methylbenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, p-hydroxylbenzoic acid, methoxybenzoic acid and the second ligand of butanedioic acid. Their molecular composition and structures were characterized by means of elemental analysis, EDTA titrimetric method, FT–IR and UV spectroscopies. The thermal stability properties of the title complexes were studied by thermal analysis instrument. The luminescent properties of the title complexes and their corresponding binary complexes were investigated by means of fluorescence instrument. The fluorescence spectra data show that the new ternary complexes have much higher luminescence intensity than their corresponding binary complexes. KEY WORDS organic polymer materilas, europium, complex, synthesis, butanedioic acid, fluorescence
