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Rhenium(I) di- and tri-carbonyl complexes of the form fac-[Re(CO)3(L,L′-Bid)X] and [Re(CO)2(L,L′-Bid)X2], where X = aqua (H2O), methanol (CH3OH), triphenylphosphine (PPh3), 1,3,5-triaza-7-phosphaadamantane (PTA), tricyclohexylphosphine (PCy3) and L,L′-Bid = O,O′ bidentate ligands (tropolone = TropH and 3-hydroxyflavone = FlavH) and N,O bidentate ligands (8-hydroxyquinoline = QuinH, 5,7-chloro-8-hydroxyquinoline = diCl-QuinH and quinoline-2,4-dicarboxylic acid = QuinH2), were synthesized and unambiguously characterized by 1H-, 13C-and 31P-NMR, IR, UV/Vis and micro-analysis. The crystal structures of four complexes, namely fac-[Re(CO)3(QuinH)(H2O)]·H2O (5), fac-[Re(CO)3(Quin)(PPh3)] (11), fac-[Re(CO)3(diCl-Quin)(PPh3)] (12) and [Re(CO)2(Trop)(PPh3)2]·2C6H5CH3 (20) were obtained. Re–P bonding distances for 11 and 12 are 2.4948(8) and 2.4908(8) Å, respectively, indicating the effect of the electron-withdrawing substituents of the diCl-Quin− ligand. The second-order rate constants for the substitutions of methanol at 25.1 °C in fac-[Re(CO)3(L,L′-Bid)(CH3OH)] (L,L′-Bid = Trop, Flav and QuinH) type complexes by different entering phosphine ligands (PPh3, PCy3, and PTA) varied between 7.23(7) × 10−5 and 1.32(3) × 10−3 M−1 s−1 and were found to depend on the coordinated bidentate ligand (in general k1 (QuinH) < k1 (Trop) < k1 (Flav)). The toxicity of fac-[Re(CO)3(QuinH)(PTA)], fac-[Re(CO)3(Trop)(PTA)], fac-[Re(CO)3(Trop)(PPh3)] and fac-[Re(CO)3(Flav)(PPh3)] on the cervical cancer HeLa and epithelial RPE-1 cell lines was then evaluated. Complex fac-[Re(CO)3(Flav)(PPh3)] (16) and fac-[Re(CO)3(Trop)(PPh3)] (13) displayed the highest cytotoxicity with IC50 values of 12.21 ± 0.17 μM and 13.35 ± 0.94 μM, respectively in HeLa cells. Interestingly, a small selectivity towards cancer over non-cancerous cells was observed for these compounds (IC50 = 18.41 ± 3.16 μM and >25 μM in RPE-1 cells). [ABSTRACT FROM AUTHOR]

A series of novel silver(i) 2,2′:6′,2′′-terpyridine (tpy), 4′-(4-methylphenyl)-2,2′:6′:2′′-terpyridine (tpy-Ph-Me) and 1,10-phenanthroline-5,6-dione (dione) derivatives containing PTA (1,3,5-triaza-7-phosphaadamantane) or 1,3,5-triaza-7-phosphaadamantane-7-sulfide (PTA=S) have been synthesized and fully characterized. Two types of complexes have been obtained, monocationic [Ag(tpy)(PTA)](NO3) (1), [Ag(tpy-Ph-Me)(PTA)](NO3) (2), [Ag(dione)(PTA=S)](BF4) (4) and [Ag(dione)2](PF6) (5) and neutral [Ag(dione)(PTA=S)(NO3)] (3). The solid-state structures of four complexes have been determined by single-crystal X-ray diffraction. Complexes 1 and 2 are luminescent at room temperature and 77 K while 5 shows emission only at 77 K. Compounds 3 and 4 are not emissive. Furthermore, representative light-stable and water-soluble 1 and 3 were evaluated for their cytotoxic activities on the normal human dermal fibroblast (NHDF) cell line and their antitumor activity using the human lung carcinoma (A549), epithelioid cervix carcinoma (HeLa) and human breast adenocarcinoma (MCF-7) cell lines. Interactions between the complexes and human serum albumin (HSA) using UV-Vis, fluorescence and circular dichroism spectroscopy (CD) were also investigated. [ABSTRACT FROM AUTHOR]