Anion Recognition of Indole-3-Aldehyde-o-Nitrophenylsemicarbazone†

doi:10.7503/cjcu20150835

Abstract

Abstract:

A novel anion recognition receptor with inner hydrogen band, indole-3-aldehyde-o-nitrophenylse-micarbazone, was designed and synthesized via indole-3-aldehyde and o-nitrophenylsemicarbazide. The receptor was characterized by ¹H NMR, ESI-MS and elemental analysis. The anion recognition properties of this receptor with AcO^-, F^-, H₂P $O 4 -$ , Cl^-, Br^-, I^-, HS $O 4 -$ were investigated with fluorescence and ¹H NMR spectrometry, respectively. The association constants and association ratio of the receptor with AcO^-, F^-, H₂P $O 4 -$ , Cl^-, Br^-, I^-, HS $O 4 -$ are 6.98, 1∶2; 6.85, 1∶2; 5.40, 1∶2; 13.51, 1∶2; 6.34, 1∶1; 5.40, 1∶1; 2.88, 1∶1, respectively. Because the receptor with inner hydrogen band has special structure and is well matching with Cl^- having appropriate bulk and basicity, the results of the fluorescence titration and ¹H NMR titration indicate the receptor has very strong bind capability and very high selectivity for Cl^-.

Key words: Indole-3-aldehyde-o-nitrophenylsemicarbazone, Fluorescence, Anion recognition, Cl- anion

CLC Number:

O626.23

TrendMD:

LIN Hai, LI Yawei, LIN Huakuan. Anion Recognition of Indole-3-Aldehyde-o-Nitrophenylsemicarbazone^†[J]. Chem. J. Chinese Universities, 2016, 37(3): 480.

Figures/Tables 10

Scheme 1 Synthesis of receptor indole-3-aldehyde-o-nitrophenylsemicarbazone

Fig.1 1H NMR spectrum of receptor

Fig.2 Fluorescence spectrum changes of receptor 1(4.0×10-5 mol/L) in DMSO with increasing concentration of AcO-(A), F-(B), H2PO4-(C), Cl-(D), Br-(E), I-(F) and HSO4-(G) λex=404 nm. Concentration step/(μmol·L-1): (A)—(C) 22.2; (D) 1.1; (E) 6.0; (F) 18.8; (G) 80.

Fig.3 Fluorescence spectra of 4.0×10-5 mol/L receptor 1(a) in DMSO with addition of 2×10-4 mol/L AcO-(b), F-(c), H2PO4-(d), HSO4-(e), 5.2×10-6 mol/L Cl-(f), 1.36×10-5 mol/L Br-(g) and 1.6×10-4 mol/L I-(h), respectively

Fig.4 1H NMR titration of 0.01 mol/L receptor (DMSO-d6)with [Bu4N]AcOc(AcO-)/(mol·L-1) from a to g: 0, 0.001, 0.003, 0.008, 0.023, 0.073, 0.193.

Fig.5 1H NMR titration of 0.01 mol/L receptor (DMSO-d6)with [Bu4N]Clc(Cl-)/(mol·L-1) from a to j: 0, 0.0001, 0.0003, 0.0005, 0.0007, 0.0010, 0.0025, 0.0060, 0.0260, 0.1060.

Table 1 Association constants and ratios for various anions toward receptor

Anion	lgK_ass	Association ratio^*	Anion	lgK_ass	Association ratio^*
AcO^-	6.98	1∶2	Br^-	6.34	1∶1
F^-	6.85	1∶2	I^-	5.40	1∶1
H₂P $O 4 -$	5.40	1∶2	HS $O 4 -$	2.88	1∶1
Cl^-	13.51	1∶2

Table 1 Association constants and ratios for various anions toward receptor

Anion	lgK_ass	Association ratio^*	Anion	lgK_ass	Association ratio^*
AcO^-	6.98	1∶2	Br^-	6.34	1∶1
F^-	6.85	1∶2	I^-	5.40	1∶1
H₂P $O 4 -$	5.40	1∶2	HS $O 4 -$	2.88	1∶1
Cl^-	13.51	1∶2

Fig.6 Proposed receptor-Br- binding mode in solution(Association ratio 1∶1)

Fig.7 Proposed receptor-Cl- binding mode in solution(Association ratio 1∶2)

Fig.8 Proposed receptor-AcO- binding mode in solution(Association ratio 1∶1)

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