Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Your Mendeley pairing has expired. Please reconnect
ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Tri-, Tetra-, and Hexanuclear Copper(II) Phosphonates Containing N-Donor Chelating Ligands: Synthesis, Structure, Magnetic Properties, and Nuclease Activity

View Author Information
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur-208016, India
Departament de Química Inorgànica i, Institut de Nanociència i Nanotecnologia, Universitat de Barcelona, Diagonal 647, 08028 Barcelona, Spain
§ CNRS, UPR 8641, Centre de Recherche Paul Pascal (CRPP), Equipe “Matériaux Moléculaires Magnétiques”, 115 avenue du Dr. Albert Schweitzer, Pessac, F-33600, France
Université de Bordeaux, UPR 8641, Pessac, F-33600, France
*To whom correspondence should be addressed. E-mail: [email protected]
Cite this: Inorg. Chem. 2009, 48, 13, 6192–6204
Publication Date (Web):June 5, 2009
Copyright © 2009 American Chemical Society

    Article Views





    Other access options
    Supporting Info (2)»


    Abstract Image

    Reaction of Cu(ClO4)2·6H2O with cyclopentyl phosphonic acid and 2,2′-bipyridine (bpy) in presence of triethylamine afforded a trinuclear compound [Cu3(C5H9PO3)2(bpy)3(MeOH)(H2O)](ClO4)2 (2). The latter dimerizes to a hexanuclear derivative [Cu6(C5H9PO3)4(bpy)6(MeOH)4](ClO4)4 (1) under prolonged reaction conditions. Reaction of CuCl2 with cyclopentyl phosphonic acid and 2,2′-bipyridylamine (bpya) affords a tetranuclear derivative [Cu4(C5H9PO3)2(μ-Cl)2(bpya)4](Cl)2, (MeOH)2 (3). Reaction of the latter with NaClO4 also affords a trinuclear compound [Cu3(C5H9PO3)2(μ-Cl)(bpya)3(H2O)](ClO4) (4). Double and single-bridged hexanuclear species, [{Cu3(C5H9PO3)2(bpy)3(bpp)}(MeOH)2(H2O)(CH2Cl2)(ClO4)2]2 (5), [{Cu3(i-PrPO3)2(bpy)3(4.4′-bpy)(H2O)}(H2O)2(ClO4)2]2 (6), [{Cu3(C5H9PO3)2(bpya)3(4.4′-bpy)(H2O)}(MeOH)(H2O)(ClO4)2]2 (7), and [Cu6(t-BuPO3)4(phen)6(4,4′-bpy)(MeOH)4](CH2Cl2)(H2O)(ClO4)4 (8) (phen = 1,10-phenanthroline) were obtained by the reaction of an in situ generated trinuclear complex with appropriate bridging ligands 4,4′-bipyridine (4,4′-bpy) or 1,3-bis(4-pyridyl)propane (bpp). ESI-MS studies of these complexes reveal that 24 retain their structures in solution. Molecular structures of 28 were determined by X-ray crystallography. All the compounds reveal a capping coordination mode by tridentate phosphonate [RPO3]2− ligands. Detailed magnetic studies on 2 and 48 reveal intramolecular antiferromagnetic interactions between Cu(II) S = 1/2 spins. 2 and 4 are excellent artificial nucleases and can convert supercoiled plasmid DNA (pBR322) into its nicked form without the aid of an external oxidant.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.


    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    Jump To

    Further details are given in Tables S1−S2 and Figures S1−S13. This material is available free of charge via the Internet at

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 56 publications.

    1. Elena Melnic, Eduard B. Coropceanu, Alessandra Forni, Elena Cariati, Olga V. Kulikova, Anatolii V. Siminel, Victor Ch. Kravtsov, and Marina S. Fonari . Discrete Complexes and One-Dimensional Coordination Polymers with [Cu(II)(2,2′-bpy)]2+ and [Cu(II)(phen)]2+ Corner Fragments: Insight into Supramolecular Structure and Optical Properties. Crystal Growth & Design 2016, 16 (11) , 6275-6285.
    2. Joydeb Goura and Vadapalli Chandrasekhar . Molecular Metal Phosphonates. Chemical Reviews 2015, 115 (14) , 6854-6965.
    3. Joydeb Goura, Prasenjit Bag, Valeriu Mereacre, Annie K. Powell, and Vadapalli Chandrasekhar . Molecular Iron(III) Phosphonates: Synthesis, Structure, Magnetism, and Mössbauer Studies. Inorganic Chemistry 2014, 53 (15) , 8147-8154.
    4. Vadapalli Chandrasekhar, Joydeb Goura, and Andrew Duthie . Molecular Indium(III) Phosphonates Possessing Ring and Cage Structures. Synthesis and Structural Characterization of [In2(t-BuPO3H)4(phen)2Cl2] and [In3(C5H9PO3)2(C5H9PO3H)4(phen)3]·NO3·3.5H2O. Inorganic Chemistry 2013, 52 (9) , 4819-4824.
    5. V. Georgantas, M. Menelaou, V. Psycharis, C. P. Raptopoulou, A. Terzis, V. Tangoulis, C. Mateescu, and A. Salifoglou . Aromatic Chelator-Specific Lattice Architecture and Dimensionality in Binary and Ternary Cu(II)-Organophosphonate Materials. Inorganic Chemistry 2013, 52 (9) , 4963-4976.
    6. Vadapalli Chandrasekhar, Joydeb Goura, and E. Carolina Sañudo . Carboxylate-Free Manganese(II) Phosphonate Assemblies: Synthesis, Structure, and Magnetism. Inorganic Chemistry 2012, 51 (15) , 8479-8487.
    7. Vadapalli Chandrasekhar, Loganathan Nagarajan, Sakiat Hossain, Kandasamy Gopal, Surajit Ghosh, and Sandeep Verma . Multicomponent Assembly of Anionic and Neutral Decanuclear Copper(II) Phosphonate Cages. Inorganic Chemistry 2012, 51 (10) , 5605-5616.
    8. Vadapalli Chandrasekhar, Tapas Senapati, Atanu Dey, and E. Carolina Sañudo . Rational Assembly of Soluble Copper(II) Phosphonates: Synthesis, Structure and Magnetism of Molecular Tetranuclear Copper(II) Phosphonates. Inorganic Chemistry 2011, 50 (4) , 1420-1428.
    9. Xiao-Qiang Liang, Dong-Ping Li, Xin-Hui Zhou, Yan Sui, Yi-Zhi Li, Jing-Lin Zuo and Xiao-Zeng You. Metal−Organic Coordination Polymers Generated from Chiral Camphoric Acid and Flexible Ligands with Different Spacer Lengths: Syntheses, Structures, and Properties. Crystal Growth & Design 2009, 9 (11) , 4872-4883.
    10. Jing-Yun Wu, Zhi-Jia Hu, Hui-Ling Sung. A water-stable molecular cadmium phosphonate bearing 2-(2-pyridyl)benzimidazole as a highly sensitive luminescence sensor for the selective detection of bisphenol AF and bisphenol B. CrystEngComm 2021, 23 (15) , 2842-2853.
    11. Hui-Ling Sung, Wen-Pin Weng, Shen-Fu Lin, Hung-Chun Yang, Jing-Yun Wu. Temperature-influenced M2L and M2L2 molecular metal phosphonates and diversity of ligand conformation. Inorganica Chimica Acta 2021, 514 , 119998.
    12. Lu Feng, Wen-Tao Huang, Hai-Long Xu, Hong Zhou, Zhi-Quan Pan. Structural and fluorescent diversities of Cd(II)/Zn(II) phosphonates with varying auxiliary ligands. Journal of Solid State Chemistry 2019, 270 , 104-111.
    13. Wentao Huang, Hong Zhou. Coordination polymers of transition metal diphosphonates: Synthesis, crystal structure and magnetic behaviour. Polyhedron 2018, 154 , 420-429.
    14. Lu Feng, Hong Zhou, Hailong Xu, Wentao Huang, Tianyu Zeng. Fe(III) and Cu(II) coordination polymers assembled from di/tris-phosphonic acid and auxiliary ligands:Structure, SOD-like activity and magnetic behavior. Journal of Solid State Chemistry 2018, 266 , 83-92.
    15. Song-Song Bao, Li-Min Zheng. Magnetic materials based on 3d metal phosphonates. Coordination Chemistry Reviews 2016, 319 , 63-85.
    16. Shikha Narang, Udai P. Singh, P. Venugopalan. Solvent-mediated supramolecular templated assembly of a metal organophosphonate via a crystal–amorphous–crystal transformation. CrystEngComm 2016, 18 (1) , 54-61.
    17. Joydeb Goura, Itziar Oyarzabal, Enrique Colacio, Vadapalli Chandrasekhar. Synthesis, Structure, and Magnetic Properties of Phosphinate‐Bridged Hexanuclear Fe III Complexes Containing Two Butterfly‐Shaped Fe 3 O Cores. European Journal of Inorganic Chemistry 2015, 2015 (34) , 5601-5610.
    18. Deividi Alexandre Cavarzan, Carlos Basilio Pinheiro, Marcio Peres de Araujo. Neutral and cationic ruthenium carbonyl complexes [Ru(CO)(2,2′-dipyridylamine)(PR3)Cl2] and [Ru(CO)(N–N)(PPh3)2(H)]Cl: synthesis, structural characterization and transfer-hydrogenation. Transition Metal Chemistry 2015, 40 (1) , 117-123.
    19. Palanisamy Rajakannu, Rana Howlader, Alok Ch. Kalita, Raymond J. Butcher, Ramaswamy Murugavel. Role of 4,4′-bipyridine versus longer spacers 4,4′-azobipyridine, 1,2-bis(4-pyridyl)ethylene, and 1,2-bis(pyridin-3-ylmethylene)hydrazine in the formation of thermally labile metallophosphate coordination polymers. Inorganic Chemistry Frontiers 2015, 2 (1) , 55-66.
    20. Jin-ying Liu, Cheng-bing Ma, Hui Chen, Chang-neng Chen. Synthesis, crystal structures and magnetic properties of a family of manganese phosphonate clusters with diverse structures. CrystEngComm 2015, 17 (45) , 8736-8745.
    21. Ximing Huang, Chunhua Fan, Jing Lu, Cai‐Ming Liu, Zhengliang Lu, Yong Nie. Structure and Magnetic Properties of a Trinuclear Nickel(II) Complex Constructed by bpca – Anions. Zeitschrift für anorganische und allgemeine Chemie 2014, 640 (12-13) , 2439-2443.
    22. Zhengliang Lu, Jing Lu, Ximing Huang, Cai-Ming Liu, Chunhua Fan, Yong Nie, Guoxin Sun. Structure and magnetic properties of a chiral dinuclear copper(II) complex assembled from a bpca− anion. Journal of Molecular Structure 2014, 1064 , 76-80.
    23. Vadapalli Chandrasekhar, Joydeb Goura, Kandasamy Gopal, Junjie Liu, Paul Goddard. Synthesis, structure and magnetism of the mixed-valent phosphonate cage, [MnIIMnIII12(μ4-O)6(μ-OH)6(O3P–t-Bu)10(OH2)2(DMF)4]·[2MeOH·4DMF]. Polyhedron 2014, 72 , 35-42.
    24. P. Haribabu, Yogesh P. Patil, K. Hussain Reddy, M. Nethaji. Synthesis, crystal structure, DNA interaction and cleavage activities of mononuclear and trinuclear copper(II) complexes. Transition Metal Chemistry 2014, 39 (2) , 167-175.
    25. Jing Lu, Jun-Ling Li, Qian Sun, Lin Jiang, Bi-Wei Wang, Wen Gu, Xin Liu, Jin-Lei Tian, Shi-Ping Yan. Synthesis, crystal structure, DNA cleavage properties, and protein binding activities of an unsymmetrical dinuclear copper(II) complex. Journal of Coordination Chemistry 2014, 67 (2) , 300-314.
    26. Saurabh Kumar Singh, Gopalan Rajaraman. Can Anisotropic Exchange Be Reliably Calculated Using Density Functional Methods? A Case Study on Trinuclear Mn III ‐M III ‐Mn III (M=Fe, Ru, and Os) Cyanometalate Single‐Molecule Magnets. Chemistry – A European Journal 2014, 20 (1) , 113-123.
    27. Jian-Di Lin, Rodolphe Clérac, Mathieu Rouzières, Munuswamy Venkatesan, Theresa O. Chimamkpam, Wolfgang Schmitt. Exploring the coordination chemistry of bifunctional organoarsonate ligands: syntheses and characterisation of coordination polymers that contain 4-(1,2,4-triazol-4-yl)phenylarsonic acid. CrystEngComm 2014, 16 (34) , 7894-7905.
    28. Sakiat Hossain, Sourav Das, Amit Chakraborty, Francesc Lloret, Joan Cano, Emilio Pardo, Vadapalli Chandrasekhar. S-shaped decanuclear heterometallic [Ni 8 Ln 2 ] complexes [Ln( iii ) = Gd, Tb, Dy and Ho]: theoretical modeling of the magnetic properties of the gadolinium analogue. Dalton Trans. 2014, 43 (26) , 10164-10174.
    29. Dipankar Sahoo, Ramakirushnan Suriyanarayanan, Vadapalli Chandrasekhar. Di-, tri- and tetranuclear molecular vanadium phosphonates: a chloride encapsulated tetranuclear bowl. Dalton Trans. 2014, 43 (28) , 10898-10909.
    30. Vadapalli Chandrasekhar, Sourav Das, Atanu Dey, Sakiat Hossain, Francesc Lloret, Emilio Pardo. Synthesis, Structure, and Magnetic Properties of a Family of Heterometallic Pentanuclear [Co 4 Ln] (Ln = Gd III , Dy III , Tb III , and Ho III ) Assemblies. European Journal of Inorganic Chemistry 2013, 2013 (25) , 4506-4514.
    31. Saeed Dehghanpour, Ali Mahmoudi, Mohsen Mirsaeed-Ghazi, Najmeddin Bazvand, Sasan Shadpour, Ahlam Nemati. Cu2O microsphere, microspherical composite of Cu2O/Cu nanocrystals and various Cu microcrystals: In situ hydrothermal conversion of Cu-aminodiphosphonate complexes. Powder Technology 2013, 246 , 148-156.
    32. Ting-Ting Wang, Song-Song Bao, Jian Huang, Yi-Zhi Li, Li-Min Zheng. Chiral one-dimensional O–P–O bridged Mn III -Schiff base complexes. Dalton Trans. 2013, 42 (5) , 1842-1847.
    33. Vadapalli Chandrasekhar, Dipankar Sahoo, Ramesh K. Metre. Isomorphic Co(ii) and Zn(ii) phosphonates: co-crystal formation of [{M2(η1-DMPzH)4(Cl3CPO3)2}{M(η1-DMPzH)2Cl2}2](toluene)2 (M = Co(ii) and Zn(ii)). CrystEngComm 2013, 15 (37) , 7419.
    34. Vadapalli Chandrasekhar, Dipankar Sahoo, Ramakirushnan Suriya Narayanan, Raymond J. Butcher, Franscesc Lloret, Emilio Pardo. A hexaicosametallic copper(ii) phosphonate. Dalton Transactions 2013, 42 (23) , 8192.
    35. Vadapalli Chandrasekhar, Ramesh K. Metre, Ramakirushnan Suriya Narayanan. Lipophilic bismuth phosphates: a molecular tetradecanuclear cage and a 1D-coordination polymer. Synthesis, structure and conversion to BiPO4. Dalton Transactions 2013, 42 (24) , 8709.
    36. Hui Zhu, Jian Huang, Song-Song Bao, Min Ren, Li-Min Zheng. Racemic metal phosphonates based on 2-phenyl-2-(phosphonomethylamino)acetate. Dalton Transactions 2013, 42 (39) , 14075.
    37. Jian Huang, Ping‐Ying Liu, Hui Zhu, Song‐Song Bao, Li‐Min Zheng, Jing Ma. Supramolecular Isomerism of One‐Dimensional Copper(II) Phosphonate and Its Influence on the Magnetic Properties. ChemPlusChem 2012, 77 (12) , 1087-1095.
    38. Kogularamanan Suntharalingam, Douglas J. Hunt, Alexandra A. Duarte, Andrew J. P. White, David J. Mann, Ramon Vilar. A Tri‐copper(II) Complex Displaying DNA‐Cleaving Properties and Antiproliferative Activity against Cancer Cells. Chemistry – A European Journal 2012, 18 (47) , 15133-15141.
    39. Shi Zhou, Zhi-Guo Kong, Qing-Wei Wang, Chuan-Bi Li. Synthesis, structure and photocatalytic property of a novel 3D (3,8)-connected metal–organic framework based on a flexible triphosphonate and a pentanuclear Cu(II) unit. Inorganic Chemistry Communications 2012, 25 , 1-4.
    40. Wanyun Huang, Zilu Chen, Huahong Zou, Dongcheng Liu, Fupei Liang. Novel 1D Copper(II) Helical Chain Formed by Weak Coordination‐driven Self‐assembly: Synthesis, Structure, and Magnetic Property. Chinese Journal of Chemistry 2012, 30 (5) , 1052-1056.
    41. Franz A. Mautner, Roland C. Fischer, M. Salah El Fallah, Saskia Speed, Ramon Vicente. A new pentadecanuclear manganese(II,III) tert-butylphosphonate cluster: Crystal structure and magnetic behaviour. Polyhedron 2012, 36 (1) , 92-96.
    42. Yan-Qiong Sun, Jin Hu, Han-Hui Zhang, Yi-Ping Chen. Hydrothermal syntheses, structures and characterizations of two luminescent cadmium(II) complexes with p-xylenediphosphonic acid and N-donor ligands. Journal of Solid State Chemistry 2012, 186 , 189-194.
    43. Vadapalli Chandrasekhar, Atanu Dey, Tapas Senapati, E. Carolina Sañudo. Distorted cubic tetranuclear vanadium(iv) phosphonate cages: double-four-ring (D4R) containing transition metal ion phosphonate cages. Dalton Trans. 2012, 41 (3) , 799-803.
    44. Franz A. Mautner, Saskia Speed, M. Salah El Fallah, Ramon Vicente. Three new dinuclear manganese(II) complexes with bis(μ-phosphinato)-bridges. Polyhedron 2011, 30 (18) , 3067-3072.
    45. Suni Qin, Zilu Chen, Dongcheng Liu, Wanyun Huang, Fupei Liang. A 1D copper(II) chain featuring novel hexanuclear secondary building blocks: Synthesis, crystal structure and magnetic property. Inorganic Chemistry Communications 2011, 14 (5) , 784-787.
    46. Shuhong Cao, Nian Dong, Jingwen Chen. Synchronous fluorescence determination of phytic acid in FOODSTUFFS and urine based on replacement reaction. Phytochemical Analysis 2011, 22 (2) , 119-123.
    47. Zhaoqiong Jiang, Hua Lu, Di Wu, Xiangge Zhou, Zhen Shen, Nagao Kobayashi. Color difference caused by chirality. Inorganic Chemistry Communications 2011, 14 (1) , 13-16.
    48. Chen-I. Yang, Yu-Tang Song, Yung-Jie Yeh, Yen-Hsiang Liu, Tien-Wen Tseng, Kuang-Lieh Lu. A flexible tris-phosphonate for the design of copper and cobalt coordination polymers: unusual cage array topology and magnetic properties. CrystEngComm 2011, 13 (7) , 2678.
    49. Peng-Fei Wang, Deng-Ke Cao, Song-Song Bao, Hao-Jun Jin, Yi-Zhi Li, Tian-Wei Wang, Li-Min Zheng. Co3(2-OOCC6H4PO3)2(H2O)3·H2O: A layered metal phosphonate showing reversible dehydration–rehydration behavior and ferrimagnetism. Dalton Transactions 2011, 40 (6) , 1307.
    50. Vadapalli Chandrasekhar, Tapas Senapati, Atanu Dey, Sakiat Hossain. Molecular transition-metal phosphonates. Dalton Transactions 2011, 40 (20) , 5394.
    51. Kandasamy Gopal, Floriana Tuna, Richard E. P. Winpenny. Octa- and hexametallic iron(iii)–potassium phosphonate cages. Dalton Transactions 2011, 40 (45) , 12044.
    52. Fei-Yan Yi, Qi-Pu Lin, Tian-Hua Zhou, Jiang-Gao Mao. Novel copper(II) sulfonate–arsonates with discrete cluster, 1D chain and layered structures. Journal of Molecular Structure 2010, 984 (1-3) , 416-423.
    53. Vadapalli Chandrasekhar, Palani Sasikumar, Tapas Senapati, Atanu Dey. Dinuclear metal phosphonates and -phosphates. Inorganica Chimica Acta 2010, 363 (12) , 2920-2928.
    54. Jane Nelson. Copper. Annual Reports Section "A" (Inorganic Chemistry) 2010, 106 , 235.
    55. Mei Wang, Da-Qiang Yuan, Cheng-Bing Ma, Ming-Jian Yuan, Ming-Qiang Hu, Na Li, Hui Chen, Chang-Neng Chen, Qiu-Tian Liu. The use of phosphonates for constructing 3d–4f clusters at high oxidation states: synthesis and characterization of two unusual heterometallic CeMn complexes. Dalton Transactions 2010, 39 (31) , 7276.
    56. Vadapalli Chandrasekhar, Loganathan Nagarajan. A hexadecameric copper(II) phosphonate. Dalton Transactions 2009, 35 (34) , 6712.