Hydrazone derivatives appended to diphenylphosphine oxide as anion sensors

We’re sorry, something doesn't seem to be working properly.

Please try refreshing the page. If that doesn't work, please contact support so we can address the problem.


Phosphine substituted hydrazones with or without nitro substituents were synthesized and characterized by multinuclear NMR, FT-IR, UV-Vis spectroscopy and single crystal X-ray diffraction. The anion recognition properties of phosphine oxides {Ph2P(O)C6H4CHNNHPh} (2) and {Ph2P(O)C6H4 CHNNHC6H3(2,4-NO2)2} (4) with anions (F, Cl , Br , I , CH3COO and H2 \(_{2}\textit {PO}_{4}^{\mathrm {-}}\)) were investigated. The selectivity towards these anions is attributed to the hydrogen bonding capability of the NH bond. Competitive titrations have shown that the binding ability of fluoride with 4 is not influenced by the presence of other anions.

Synthesis of hydrozone derivatives appended to phosphineoxide and anion sensing properties are described.

This is a preview of subscription content, log in to check access.

Scheme 1
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10
Figure 11
Scheme 2


  1. 1.

    (a) Kirk K L 1991 In Biochemistry of the Halogens and Inorganic Halides (New York: Plenum Press); (b) Sessler J L, Gale P A and Cho W S 2006 In Anion Receptor Chemistry (Cambridge: The Royal Society of Chemistry, Cambridge, UK) pp. 171–226

  2. 2.

    (a) Kim K, Tsay O G, Atwood D A and Churchill D G 2011 Destruction and Detection of Chemical Warfare Agents Chem. Rev. 111 5345; (b) Yang Y, Zhao Q, Feng w and Li F 2013 Luminescent Chemodosimeters for Bioimaging Chem. Rev. 113 192; (c) Gale P A, Busschaert N, Haynes C J E, Karagiannidis L E and Kirby I L 2014 Anion receptor chemistry: Highlights from 2011 and 2012 Chem. Soc. Rev. 43 205; (d) Santos-Figueroa L E, Moragues M, Climent E E, Agostini A, Martinez-Manez R and Sancenon F 2013 Chromogenic and fluorogenic chemosensors and reagents for anions. A comprehensive review of the years 2010–2011 Chem. Soc. Rev. 42 3489; (e) Gupta V K, Goyal R N and Sharma R A 2008 Anion recognition using newly synthesized hydrogen bonding disubstituted phenylhydrazone-based receptors: Poly(vinyl chloride)-based sensor for acetate Talanta 76 859

  3. 3.

    Dale T J and Rebek J 2006 Fluorescent Sensors for Organophosphorus Nerve Agent Mimics J. Am. Chem. Soc. 128 4500

    CAS  Article  Google Scholar 

  4. 4.

    (a) Beer P D and Cadman J 2000 Electrochemical and optical sensing of anions by transition metal based receptors Coord. Chem. Rev. 205 131; (b) Xiong J, Cui L, Liu W, Beves J E, Li Y Y and Zuo J L 2013 Large and selective electrochemical response to fluoride by a tetrathiafulvalene-based sensor Tetrahedron Lett. 54 1998

  5. 5.

    (a) Lin Z H, Ou S J, Duan C Y, Zhang B G and Bai Z P 2006 Naked-eye detection of fluoride ion in water: A remarkably selective easy-to-prepare test paper Chem. Commun. 624; (b) Khanmohammadi H and Rezaeian K 2014 Naked-eye detection of inorganic fluoride in aqueous media using a new azo-azomethine colorimetric receptor enhanced by electron withdrawing groups RSC Adv. 4 1032; (c) Khanmohammadi H and Rezaeian K 2014 A catalyst-free approach to a novel imidazo [4,5-f][1,10] phenanthroline ligand and its corresponding ruthenium(II) complex: Insights into their applications in colorimetric anion sensing New J. Chem. 38 5536; (d) Gupta V K, Mergu N, Kumawat L K and Singh A K 2015 A reversible fluorescence “off–on–off” sensor for sequential detection of aluminum and acetate/fluoride ions Talanta 144 80; (e) Gupta V K, Singh A K and Kumawat L K 2014 Thiazole Schiff base turn-on fluorescent chemosensor for Al 3+ ion Sens. Actuators B 195 98

  6. 6.

    (a) Su X and Aprahamian I 2014 Hydrazone-based switches, metallo-assemblies and sensors Chem. Soc. Rev. 43 1963; (b) Foy J T, Ray D and Aprahamian I 2015 Regulating signal enhancement with coordination-coupled deprotonation of a hydrazone switch Chem. Sci. 6 209

  7. 7.

    Amendola V, Esteban-Gómez D, Fabbrizzi L and Licchelli M 2006 What Anions Do to N-H-Containing Receptors Acc. Chem. Res. 39 343

    CAS  Article  Google Scholar 

  8. 8.

    Shao J, Lin H, Yu M, Cai Z and Lin H 2008 Study on acetate ion recognition and sensing in aqueous media using a novel and simple colorimetric sensor and its analytical application Talanta 75 551

    CAS  Article  Google Scholar 

  9. 9.

    Choi K and Hamilton A D 2001 Synthesis of exceptionally stable iron and ruthenium η 1-tetrahedro-tetraphosphorus complexes: Evidence for a strong temperature dependence of M −P4 π back donation Angew. Chem., Int. Ed. 40 3912

    CAS  Article  Google Scholar 

  10. 10.

    (a) Jose D A, Kumar D K, Ganguly B and Das A 2004 Efficient and simple colorimetric fluoride ion sensor based on receptors having urea and thiourea binding sites Org. Lett. 6 3445; (b) Okudan A, Erdemir S and Kocyigit O 2013 Naked-eye’ detection of fluoride and acetate anions by using simple and efficient urea and thiourea based colorimetric sensors J. Mol. Struct. 1048 392

  11. 11.

    Bose P, Ahamed B N and Ghosh P 2011 Functionalized guanidinium chloride based colourimetric sensors for fluoride and acetate: Single crystal X-ray structural evidence of −NH deprotonation and complexation Org. Biomol. Chem. 9 1972

    CAS  Article  Google Scholar 

  12. 12.

    (a) Lakshmi V and Ravikanth M 2014 Boron-dipyrromethene based multi-anionic sensor and a specific cationic sensor for Fe 3+ J. Mater. Chem. C 2 5576; (b) Swami S, Agarwala A, Malik B and Shrivastavaa R 2016 A new class of efficient 4-[(nitro substituted-phenyl)- hydrazonomethyl]-1-phenyl-1H-pyrazole-3-carboxylate derived colorimetric chemosensor for selective sensing of fluoride and other biologically important anions J. Chem. Sci. 128 1451

  13. 13.

    (a) Zhou L, Zhang X and Wu S 2004 Fluoride-selective Colorimetric Sensors Based on Hydrazone Functionality Chem. Lett. 33 850; (b) Amendola V, Bonizzoni M, Esteban-Gómez D, Fabbrizzi L, Licchelli M, Sancenón F and Taglietti A 2006 Some guidelines for the design of anion receptors Coord. Chem. Rev. 250 1451; (c) Dalapati S, Jana S and Guchhait N 2014 Anion recognition by simple chromogenic and chromo-fluorogenic salicylidene Schiff base or reduced-Schiff base receptors Spectrochim. Acta A 129 499

  14. 14.

    Shang X F and Xu X F 2009 The anion recognition properties of hydrazone derivatives containing anthracene Biosystems 96 165

    CAS  Article  Google Scholar 

  15. 15.

    Liu G and Shao J 2012 Selective Ratiometric Fluorescence Detection of Acetate Based on a Novel Schiff Base Derivative J. Fluoresc. 22 397

    Article  Google Scholar 

  16. 16.

    (a) Xu Z, Singh N J, Lim J, Pan J, Kim H N, Park S, Kim K S and Yoon J 2009 Unique Sandwich Stacking of Pyrene-Adenine-Pyrene for Selective and Ratiometric Fluorescent Sensing of ATP at Physiological pH J. Am. Chem. Soc. 131 15528; (b) Lee M, Moon J H, Swamy K M K, Jeong Y, Kim G, Choi J, Lee J Y and Yoon J 2014 A new bis-pyrene derivative as a selective colorimetric and fluorescent chemosensor for cyanide and fluoride and anion-activated CO 2 sensing Sens. Actuators B 199 369

  17. 17.

    Zhang B, Li Y and Sun W 2011 Anion-Sensitive 2,4-Dinitrophenylhydrazone-Containing Terpyridine Derivative and Its Platinum Chloride Complex Eur. J. Inorg. Chem. 4964

  18. 18.

    Chawla H M, Shrivastava R and Sahu S N 2008 A new class of functionalized calix[4]arenes as neutral receptors for colorimetric detection of fluoride ions New J. Chem. 32 1999

    CAS  Article  Google Scholar 

  19. 19.

    (a) Klare H, Hanft S, Neudörfl J M, Schlörer N E, Griesbeck A and Goldfuss B 2014 Anion Recognition with Hydrogen-Bonding Cyclodiphosphazanes Chem. Eur. J. 20 11847; (b) Cranwell P B, Hiscock J R, Haynes C J E, Light M E, Wells N J and Gale P A 2013 Anion recognition and transport properties of sulfamide-, phosphoric triamide- and thiophosphoric triamide-based receptors Chem. Commun. 49 874

  20. 20.

    (a) Siddiqui M M, Mobin S M, Senkovska I, Kaskel S and Balakrishna M S 2014 Multifunctional Hybrid Zeolitic Phosphane Cluster Frameworks (ZPCFs) with Luminescence, Sorption and Redox Properties Chem. Commun. 50 12273; (b) Naik S, Mague J T and Balakrishna M S 2014 Novel Trisphosphine Ligand Containing 1,3,5-Triazine Core, [2,4,6-C 3 N 3{C 6 H 4PPh 2-p} 3]: Synthesis and Transition Metal Chemistry Inorg. Chem. 53 3864; (c) Kumaravel M, Mague J T and Balakrishna M S 2014 Chalcogenide Derivatives of 1,2,5-Triphenyl-1H-phosphole: Structure and Photophysical Properties Tetrahedron Lett. 55 2957

  21. 21.

    (a) Naik S, Kumaravel M, Mague J T and Balakrishna M S 2014 Bis(diphosphonite) with dangling olefin functionalities: Synthesis, Transition metal chemistry and catalytic studies Dalton Trans. 43 1082; (b) Ananthnag G S, Mague J T and Balakrishna M S 2015 Cyclodiphosphazane Based Pincer Ligand, {2-I-1,3-C 6 H 3(OP(μ-N tBu) 2PN(H) tBu) 2}: Ni II, Pd II, Pt II and Cu I Complexes and Catalytic Studies Dalton Trans. 44 3785; (c) Kumar P, Siddiqui M M, Reddi Y, Mague J T, Sunoj R B and Balakrishna M S 2013 New bisphosphomide ligands, 1,3-phenylenebis((diphenylphosphino)methanone) [1,3-Ph 2PC(O)} 2 C 6 H 4] and (2-bromo-1,3-phenylene)bis ((diphenylphosphino)methanone) [1,3-Ph 2PC(O)} 2 C 6 H 4 Br]: Synthesis, coordination behavior, DFT calculations and catalytic studies Dalton Trans. 42 11385

  22. 22.

    (a) Ares R, Vázquez-García, D, Lopez-Torres M, Fernández A, Gómez-Blanco N, Vila J M and Fernández J J 2008 Synthesis, characterization and crystal structures of cyclometallated palladium (II) compounds containing difunctional ligands with [P,P], [As, As], [N,N], [P,As], [P,N] and [P,O] donor atoms J. Organomet. Chem. 693 3655; (b) Adams C J, Bruce M L, Duckworth P A, Humphrey P A, Kühl O, Tiekink E R T, Cullen W R, Braunstein P, Coco Cea S, Skelton B W and White A H 1994 Cluster chemistry: XC. Some complexes obtained from reactions between M 3(CO) 12 (M = Ru or Os) or Ru 3(μ-dppm)(CO) 10 and 2-substituted triphenylphosphines and related keto-phosphine ligands J. Organomet. Chem. 467 251

  23. 23.

    Sheldrick G M 2008 A short history of SHELX Acta Crystallogr. A64 112

    Article  Google Scholar 

  24. 24.

    Kim Y H, Choi M G, Im H G, Ahn S, Shim I W and Chang S K 2012 Chromogenic signalling of water content in organic solvents by hydrazone-acetate complexes Dyes Pigm. 92 1199

    CAS  Article  Google Scholar 

  25. 25.

    (a) Moon J O, Kim Y H, Choi M G and Chang S K 2011 Bull. Korean Chem. Soc. 32 3517; (b) Saravanakumar D, Devaraj S, Iyyampillai S, Mohandoss K, Kandaswamy M 2008 Schiff’s base phenol-hydrazone derivatives as colorimetric chemosensors for fluoride ions Tetrahedron Lett. 49 127

  26. 26.

    (a) Amendola V and Fabbrizzi L 2009 Anion receptors that contain metals as structural units Chem. Commun. 513; (b) Vega I E D, Gale P A, Light M E and Loeb S J 2005 NH vs. CH hydrogen bond formation in metal-organic anion receptors containing pyrrolylpyridine ligands Chem. Commun. 4913; (c) Soriano M L, Lenthall J T, Anderson K M, Smith S J and Steed J W 2010 Enhanced Anion Binding from Unusual Coordination Modes of Bis(thiourea) Ligands in Platinum Group Metal Complexes Chem. Eur. J. 16 10818; (d) Mendoza C, Benet-Buchholz J, Pericas M A and Vilar R 2009 Di-platinum complexes containing thiolato-urea ligands: Structural and anion binding studies Dalton Trans. 2974

Download references


The work is supported by a grant 01(2799)/14/EMR-II from CSIR, New Delhi, India. J. T. M. thanks the Louisiana Board of Regents for the purchase of the APEX CCD diffractometer, NSF-MRI grant number 1228232 for the purchase of the D8 VENTURE diffractometer and the Chemistry Department of Tulane University for support of the X-ray laboratory. MK thanks the Council of Scientific Industrial Research (CSIR), New Delhi, for Senior Research Fellowship (SRF).

Author information



Corresponding author


Additional information

Supplementary Information (SI)

Crystallographic information of compounds 3 and 4, absorption spectra, NMR (1H, 31P and 13C) and IR spectra for compounds 14 are provided. The Supplementary Information is available at www.ias.ac.in/chemsci.

Electronic supplementary material

Below is the link to the electronic supplementary material.

(DOC 8.66 MB)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

KUMARAVEL, M., MAGUE, J.T. & BALAKRISHNA, M.S. Hydrazone derivatives appended to diphenylphosphine oxide as anion sensors. J Chem Sci 129, 471–481 (2017). https://doi.org/10.1007/s12039-017-1258-6

Download citation


  • Hydrazones
  • phosphine oxides
  • anion recognition
  • colorimetric sensing