Photophysical and DFT Studies of Cationic Ag(I) Complexes with Thiosemicarbazides Derived from p-Toluenesulfohydrazide

被引:5
作者
Borges, Alice P. [1 ]
Gaspari, Ana P. S. [2 ]
Oliveira, Carolina G. [3 ]
de Sousa, Sinval F. [4 ]
da Silva, Roberto S. [2 ]
Deflon, Victor M. [3 ]
Machado, Antonio E. H. [4 ]
Patrocinio, Antonio O. T. [4 ]
Maia, Pedro I. S. [1 ]
机构
[1] Univ Fed Triangulo Mineiro, Dept Chem, Av Dr Randolfo Borges 1400, BR-38025440 Uberaba, MG, Brazil
[2] Univ Sao Paulo, FFCLRP, Dept Chem, Ave Cafe S-N, BR-14040903 Ribeirao Preto, SP, Brazil
[3] Univ Sao Paulo, Inst Quim Sao Carlos, Dept Mol Chem & Phys, Av Trabalhador Saocarlense,400, BR-12345678 Sao Carlos, SP, Brazil
[4] Univ Fed Uberlandia, Inst Quim, Lab Fotoquim & Cithornncia Mat, Av Joao Naves de Avila 2121, BR-38400902 Uberlandia, MG, Brazil
来源
CHEMISTRYSELECT | 2018年 / 3卷 / 07期
基金
巴西圣保罗研究基金会;
关键词
Luminescence; Silver(I) complexes; States diagram; TDDFT; Thiosemicarbazones; GOLD(III) COMPLEXES; CRYSTAL-STRUCTURES; ANTIMICROBIAL ACTIVITY; SILVER(I) CLUSTER; LIGAND; ANTIBACTERIAL; CYTOTOXICITY; DERIVATIVES; ANTIFUNGAL; COPPER(I);
D O I
10.1002/slct.201800079
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Reactions of p-toluenesulfohydrazide with R-isothiocyanates afford new ligands containing both the sulfonamide and thiosemicarbazide moieties (L-R: R=cyclohexyl (Cy) or phenyl (Ph)). L-R reacts with AgNO3 in EtOH in a 2:1M ratio leading to formation of colourless Ag(I) complexes of general formula [Ag(L-R)(2)]NO3. The crystal structure of a representative complex was determined by crystallographic studies and shows the Ag(I) coordinated by two thiosemicarbazide ligands in a S-monodentate coordination mode along with a significant interaction with a nitrate counter-ion in a bent geometry. Photophysical studies show that both the free ligands and complexes are essentially non-luminescent at room temperature. At 77K and glassy media, the silver complexes exhibit a luminescence band in the visible-light region. Besides, experimental and theoretical analyses suggest the population of the triplet state of these complexes after electronic excitation at around 250nm. Overall, it was verified that the observed emission of the Ag(I) complexes can be attributed to (MLCT)-M-3 radiative decay and that the silver complex with L-Ph shows a higher intensity emission than the complex with L-Cy.
引用
收藏
页码:2108 / 2114
页数:7
相关论文
共 41 条
[1]   Synthesis, a case of isostructural packing, and antimicrobial activity of silver(I) quinoxaline nitrate, silver(I)(2,5-dimethylpyrazine) nitrate and two related silver aminopyridine compounds [J].
Abu-Youssef, Morsy A. M. ;
Langer, Vratislav ;
Ohrstrom, Lars .
DALTON TRANSACTIONS, 2006, (21) :2542-2550
[2]   Synthesis, Crystal Structure, Quantum Chemical Calculations, DNA Interactions, and Antimicrobial Activity of [Ag(2-amino-3-methylpyridine)2]NO3 and [Ag(pyridine-2-carboxaldoxime)NO3] [J].
Abu-Youssef, Morsy A. M. ;
Soliman, Saied M. ;
Langer, Vratislav ;
Gohar, Yousry M. ;
Hasanen, Ahmed A. ;
Makhyoun, Mohamed A. ;
Zaky, Amira H. ;
Ohrstrom, Lars R. .
INORGANIC CHEMISTRY, 2010, 49 (21) :9788-9797
[3]   Synthesis, crystal structures, antimicrobial, antifungal and antituberculosis activities of mixed ligand silver(I) complexes [J].
Altaf, Muhammad ;
Stoeckli-Evans, Helen ;
Cuin, Alexandre ;
Sato, Daisy Nakamura ;
Pavan, Fernando Rogerio ;
Fujimura Leite, Clarice Queico ;
Ahmad, Saeed ;
Bouakka, Mohammed ;
Mimouni, Mostafa ;
Khardli, Fatima Zahra ;
Ben Hadda, Taibi .
POLYHEDRON, 2013, 62 :138-147
[4]   Functionalized thiosemicarbazone clusters of copper(I) and silver(I) [J].
Ashfield, LJ ;
Cowley, AR ;
Dilworth, JR ;
Donnelly, PS .
INORGANIC CHEMISTRY, 2004, 43 (14) :4121-4123
[5]   Factors involved in the nuclearity of silver thiosemicarbazone clusters:: Cocrystallization of two different sized tetranuclear silver(I) clusters derived from a phosphinothiosemicarbazone ligand [J].
Castineiras, Alfonso ;
Pedrido, Rosa .
INORGANIC CHEMISTRY, 2008, 47 (13) :5534-5536
[6]   Synthesis, characterization and DFT calculations of a novel hexanuclear silver(I) cluster-complex containing 4-ethyl-5-pyridin-2-yl-2,4-dihydro-[1,2,4]triazol-3-thione as a result from the cyclization of 2-pyridinformamide N-4-ethylthiosemicarbazone [J].
Castineiras, Alfonso ;
Garcia-Santos, Isabel ;
Dehnen, Stefanie ;
Sevillano, Paloma .
POLYHEDRON, 2006, 25 (18) :3653-3660
[7]   Luminescent complexes of silver(I) with pyridylbis(3-hexamethyleneiminyl thiosemicarbazone): effect of the counterion on the nuclearity [J].
Castineiras, Alfonso ;
Fernandez-Hermida, Nuria ;
Garcia-Santos, Isabel ;
Luis Perez-Lustres, Jose ;
Rodriguez-Gonzalez, Iria .
DALTON TRANSACTIONS, 2012, 41 (13) :3787-3796
[8]   A Convenient Mode to Stabilize MI Metal Ions by Using Thiosemicarbazones [J].
Castineiras, Alfonso ;
Pedrido, Rosa ;
Perez-Alonso, Gael .
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2008, 32 (32) :5106-5111
[9]   Novel Fluorescent Cationic Silver Thiosemicarbazone Clusters Containing Different Eight-Membered Ag4S4 Metallacycles [J].
Castineiras, Alfonso ;
Pedrido, Rosa .
INORGANIC CHEMISTRY, 2009, 48 (11) :4847-4855
[10]   Ligands for molecular Imaging: The synthesis of bis(thiosemicarbazone) ligands [J].
Christlieb, Martin ;
Dilworth, Jonathan R. .
CHEMISTRY-A EUROPEAN JOURNAL, 2006, 12 (24) :6194-6206