Abstract
A new Cu(II) dinuclear complex, Cu2L2 (1) was afforded employing the potentially pentatentate Schiff base precursor H2L, a refluxed product of o-vanillin and diethylenetriamine in methanol. Complex 1 was systematically characterized by FTIR, UV–Vis, emission and EPR spectrometry. The single crystal X-ray diffraction analysis of 1 reveals that the copper atom exhibits a distorted square planar geometry, comprising two pairs of phenolato-O and imine-N donors from two different H2L ligands. The temperature dependent magnetic interpretation agrees with the existence of weak antiferromagnetic interactions between the bridging dinuclear Cu(II) ions. A considerable body of experimental evidence has been accumulated to elucidate the magneto-structural relationship in this dinuclear Cu(II) complex by DFT computation. Both the ligand and complex 1 exhibit anti-mycobacterial activity and considerable efficacy on M. tuberculosis H37Ra (ATCC 25177) and M. tuberculosis H37Rv (ATCC 25618) strains. The practical applicability of the ligand and complex 1 has been examined in living cells (African Monkey Vero Cells). The MTT assay proves the non-toxicity of the probe up to 100 mg mL−1.
Graphical abstract
A new homometallic dinuclear Cu(II) complex is afforded with a tetradentate Schiff base precursor. EPR interpretation and temperature dependent magnetic studies show that complex 1 has weak antiferromagnetic coupling and DFT computation is governed to explain the magneto-structural correlation.
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Beer PD, Gale PA (2001) Angew Chem Int Ed 40:486–516
Robson R (2000) J Chem Soc Dalton Trans 21(21):3735–3744. doi:10.1039/b003591m
Song Y, Massera C, Roubeau O, Gamez P, Manotti-Lanfredi AM, Reedijk J (2004) Inorg Chem 43:6842–6847
Saalfrank RW, Demleitner B(1999) Transition metals in supramolecular chemistry. In: Sauvage JP (ed) Perspectives in supramolecular chemistry, vol 5. Wiley, New york, p 1
Blake AJ, Champness NR, Hubberstey P, Withersby MA, Schroder M (1999) Coord Chem Rev 183:117–138
Thompson LK, Mandal SK, Tandon SS, Bridson JN, Park MK (1996) Inorg Chem 35:3117–3125
Nanda KK, Thompson LK, Bridson JN, Nag K (1994) J Chem Soc Chem Commun. doi:10.1039/c39940001337
Mohanta S, Nanda KK, Thompson LK, Florke U, Nag K (1998) Inorg Chem 37:1465–1472
Ruiz E, Cano J, Alvarez S, Alemany P (1998) J Am Chem Soc 120:11122–11129
Manca G, Cano J, Ruiz E (2009) Inorg Chem 48:3139–3144
Lin P-H, Burchell TJ, Ungur L, Chibotaru LF, Wernsdorfer W, Murugesu M (2009) Angew Chem Int Ed 48:9489–9492
Kahn O (ed) (1996) Magnetism: a supramolecular function NATO ASI Series C, vol 484. Kluwer Academic Publishers, Dordrecht
Journaux Y, Kahn O, Zarembowitch J, Galy J, Jaud J (1983) J Am Chem Soc 105:7585–7591
Kahn O, Galy J, Journaux Y, Moregenstern-Badarau I (1982) J Am Chem Soc 104:2165–2176
Ohba M, Tamaki H, Matsumoto N, Okawa H (1993) Inorg Chem 32:5385–5390
Kahn O (1993) Molecular magnetism. VCH, Weinheim
Mastropaolo D, Powers DA, Potenza JA, Schugar HJ (1976) Inorg Chem 15:1444–1451
Zhang G, Yang G, Ma JS (2006) Cryst Growth Des 6:375–381
Hodgson DJ (1975) Prog Inorg Chem 19:173–178
Whittaker JW (1994) Metalloenzymes involving amino acid residue related radicals. In: Sigel H, Sigel A (eds), vol 30 Marcel Dekker, New York, p 315
Solomon EI, Sundaram UM, Machonkin TE (1996) Chem Rev 96:2563–2606
Berends HP, Stephan DW (1987) Inorg Chem 26:749–754
Nishida Y, Shimo H, Maehara H, Kida S (1985) J Chem Soc Dalton Trans 1985:1945–1951
Holz RC, Brink JM, Gobena FT, O’Connor CJ (1994) Inorg Chem 33:6086–6092
Fondo M, Garcıa-Deibe AM, Sanmartın J, Bermejo MR, Lezama L, Rojo T (2003) Eur J Inorg Chem 2003(20):3703–3706. doi:10.1002/ejic.200300478
Fondo M, Garcıa-Deibe AM, Corbella M, Ribas J, LlamasSaiz A, Bermejo MR, Sanmartın J (2004) J Chem Soc Dalton Trans 3503–3507
Hay AS (1998) J Polym Sci Part A Polym Chem 36:505–511
Jazdzewski BA, Tolman WB (2000) Coord Chem Rev 200–202:633–685
Jazdzewski BA, Holland PL, Pink M, Young VG Jr, Spencer DJE, Tolman WB (2001) Inorg Chem 40:6097–6107 (and references therein)
Lall N, Sarma MD, Hazra B, Meyer JJ (2003) J Antimicrob Chemother 51:435–438
Banfi E, Mamolo MG, Zampieri D, Vio L, Bragadin CM (2001) J Antimicrob Chemother 48:705–711
Das K, Panda U, Datta A, Roy S, Mondal S, Massera C, Askun T, Celikboyun P, Garribba E, Sinha C, Anand K, Akitsu T, Kobayashi K (2015) New J Chem 39:7309
Eaten DF (1988) Pure Appl Chem 60:1107–1114
Stoyanov SR, Villegas JM, Rillema DP (2002) Inorg Chem 41:2941–2945
WINEPR SimFonia, version 1.25 (1996) Bruker Analytische Messtechnik GmbH, Karlsruhe
SADABS Bruker AXS (2004) Madison, Wisconsin; SAINT, Software Users Guide, Version 6.0; Bruker Analytical X-ray Systems, Madison 1999
Sheldrick GM (1999) SADABS v2.03: area-detector absorption correction. University of Göttingen, Germany
Altomare A, Burla MC, Camalli M, Cascarano GL, Giacovazzo C, Guagliardi A, Moliterni AGG, Polidori G, Spagna R (1999) J Appl Crystallogr 32:115–119
Sheldrick GM (2008) Acta Crystallogr A64:112–122
Farrugia LJ (1999) J Appl Crystallogr 32:837–838
van der Sluis P, Spek AL (1990) Acta Crystallogr Sect A 46:194–201
Nardelli M (1996) J Appl Crystallogr 29:296–300
Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785–789
Becke AD (1993) J Chem Phys 98:5648–5652
Lee C, Yang W, Parr RG (1988) Phys Rev B Cond Matter Mater Phys 37:785–789
Andrae D, Haeussermann U, Dolg M, Stoll H, Preuss H (1990) Theo Chim Acta 77:123–141
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery Jr JA, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, GillPMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2004) GAUSSIAN 03 Revision D 01. Gaussian Inc., Wallingford
Hay PJ, Wadt WR (1985) J Chem Phys 82:299–310
Bauernschmitt R, Ahlrichs R (1996) Chem Phys Lett 256:454–464
Casida MK, Jamorski C, Casida KC, Salahub DR (1998) J Chem Phys 108:4439–4449
Stratmann RE, Scuseria GE, Frisch MJ (1998) J Chem Phys 109:8218–8224
Cossi M, Rega N, Scalmani G, Barone V (2003) Comput Chem 24:669–681
O’Boyle NM, Tenderholt AL, Langner KM (2008) J Comput Chem 29:839–845
Becke AD (1988) Phys Rev A 38:3098–3100
Perdew JP (1986) Phys Rev B 33:8822–8824
Neese F (2013) ORCA—an ab initio, density functional, and semi-empirical program package, version 3.0. Max-Planck-Institute for Chemical Energy Conversion, Mülheim a. d. Ruhr
Bencini A, Gatteschi D (1990) Electron paramagnetic resonance of exchange coupled systems. Springer, Berlin
Heisenberg WZ (1926) Physik 38:411–426
Van Vleck JH (1932) The theory of electronic and magnetic susceptibilies. Oxford University, London
Noodleman L (1981) J Chem Phys 74:5737–5743
Noodleman L, Case DA (1992) Adv Inorg Chem 38:423–470
Noodleman L, Davidson ER (1986) Chem Phys 109:131–143
Becton BD (2002) Dickinson and Company Newsletter BD Bactec MGIT 960 SIRE kit now FDA-cleared for susceptibility testing of Mycobacterium tuberculosis. Microbiology News Ideas 13:4
NCCLS (2003). National Committee for Clinical Laboratory Standards (NCCLS). Susceptibility testing of mycobacteria, nocardiae, and other aerobic actinomycetes; approved standard. NCCLS document M24-A [ISBN 1-56238 500-3]. NCCLS, Pennsylvania
Collins L, Franzblau, SG (1997) Antimicrob Agents Chemother 41:1004–1009
Jimenez-Arellanes A, Meckes M, Ramirez R, Torres J, Luna-Herrera J (2003) Phytother Res 17:903–908
Battu GR, Kumar BM (2010) Willd Pharmacognosy J 2:456–463
Bag P, Chattopadhyay D, Mukherjee H, Ojha D, Mandal N, Chawla MS, Chatterjee T, Das G, Chakraborti S (2012) Virol J 9:98–109
Banerjee D, Mandal SM, Das A, Hegde ML, Bhakat KK (2011) J Biol Chem 286:6006–6016
Nakamoto K (1997) Infrared and raman spectra of inorganic and coordination compounds, parts A and B, 5th edn. Wiley, New York
Quintero-Tellez G, Alvarez CMG, Bernès S, Alcantara-Flores JL, Reyes-Ortega Y (2008) Acta Crystallogr Sect E64:m631
McKenzie ED, Selvey SJ (1985) Inorg Chim Acta 101:127
Benetollo F, di Bernardo P, Tamburini S, Vigato PA, Zanonato P (2008) Inorg Chem Commun 11:246
Lever ABP (1984) Inorganic electronic spectroscopy, 2nd edn. Elsevier, New York
Chang JH, Choi YM, Shin Y-K (2001) Bull Korean Chem Soc 22:527–533
Thakurta S, Roy P, Rosair G, Gómez-García CJ, Garribba E, Mitra S (2009) Polyhedron 28:695–702
Kállay C, Cattari M, Sanna D, Várnagy K, Süli-Vargha H, Csámpai A, Sóvágó I, Micera G (2004) New J Chem 28:727–734
Hathaway BJ, Billing DE (1970) Coord Chem Rev 5:143–207
Garribba E, Micera G (2006) J Chem Ed 83:1229–1232
Maki AH, Mc Garvey BR (1958) J Chem Phys 29:35–38
Hasty EF, Colburn TJ, Hendrikson DN (1973) Inorg Chem 12:2414–2421
Klement R, Stock F, Elias H, Paulus H, Pelikán P, Valko M, Mazúr M (1999) Polyhedron 18:3617–3628
Thakurta S, Chakraborty J, Rosair G, Tercero J, El Fallah MS, Garribba E, Mitra S (2008) Inorg Chem 47:6227–6235
Thakurta S, Rizzoli C, Butcher RJ, Gómez-García CJ, Garribba E, Mitra S (2010) Inorg Chim Acta 363:1395–1403
Ray A, Mitra S, Khalaji AD, Atmani C, Cosquer N, Triki S, Clemente-Juan JM, Cardona-Serra S, Gomez-Garcia CJ, Butcher RJ, Garribba E, Xu D (2010) Inorg Chim Acta 363:3580–3588
Peisach J, Blumberg WE (1974) Arch Biochem Biophys 165:691–708
Jeffery JC, Maher JP, Otter CA, Thornton P, Ward MD (1995) J Chem Soc Dalton Trans 819–824
van Albada G, Mutikainen I, Smeets WJJ, Spek AL, Turpeinen U, Reedijk J (2002) Inorg Chim Acta 327:134–139
Alves WA, de Almeida Santos RH, Paduan-Filho A, Becerra CC, Borin AC, Ferriera AMDC (2004) Inorg Chim Acta 357:2269–2278
Pradeep CP, Das SK (2009) Polyhedron 28:630–636
Saha S, Sasmal A, Choudhury CR, Gomez-Garcia CJ, Garribba E, Mitra S (2014) Polyhedron 69:262–269
Bertini I, Canti G, Grassi R, Scozzafava A (1980) Inorg Chem 19:2198–2200
Trias J, Jarlier V, Benz R (1992) Science 258:1479–1481
Trias J, Benz R (1994) Mol Microbiol 14:283–286
Acknowledgements
KD and CS would like to thank the Council of Scientific and Industrial Research (CSIR, Sanction No. 01(2731)/13/EMR-II,) New Delhi, India to carry out the present study. A.F. thanks the DGICYT of Spain (projects CTQ2014-57393-C2-1-P and CONSOLIDER INGENIO 2010 CSD2010-00065, FEDER funds) for financial support. We thank the CTI (UIB) for computational facilities.
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Das, K., Patra, C., Sen, C. et al. EPR interpretation, magnetism and biological study of a Cu(II) dinuclear complex assisted by a schiff base precursor. J Biol Inorg Chem 22, 481–495 (2017). https://doi.org/10.1007/s00775-016-1428-x
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DOI: https://doi.org/10.1007/s00775-016-1428-x