New palladium and platinum complexes with bioactive 3,5-diacetyl-1,2,4- triazol bis(4-cyclohexyl thiosemicarbazone) ligand: Chemistry, antiproliferative activity and preliminary toxicity studies

Dalton Transactions 41.40 (2012): 12538-12547. Reproduced by permission of The Royal Society of ChemistryThe preparation and characterization of the new 3,5-diacetyl-1,2,4-triazol bis(4-cyclohexyl thiosemicarbazone) ligand, H5L1, is described. Treatment of H5L1 with K2PtCl 4 gave the dinuclear complex [Pt(H3L1)] 2, 1, but using MCl2(PPh3)2 where M = Pd or Pt, mononuclear complexes 2 and 3, of general formula [M(H 3L1)PPh3], were obtained. Subsequent reaction of the [Pd(H3L1)PPh3] complex with PdCl 2(PPh3)2 yielded a new dinuclear complex [(PPh3)Pd(H2L1)PdCl], 4. All compounds have been characterized by elemental analysis and FAB+ spectrometry and by IR and NMR spectroscopy. The molecular structures of mononuclear complexes 2 and 3 and dinuclear complex 4 have been determined by X-ray crystallography. The new compounds synthesized have been evaluated for antiproliferative activity in vitro against NCI-H460, HepG2, MCF-7, A2780 and A2780cisR human cancer cell lines. The cytotoxicity data suggest that the H5L1 ligand and [Pt(H3L1)]2, complex 1, may be endowed with important cytotoxic properties since they are capable of not only circumventing cisplatin resistance in A2780cisR but also exhibit antiproliferative activity in NCI-H460. The interactions of these compounds with calf thymus DNA were investigated by UV-vis absorption and a nephrotoxic study, in LLC-PK1 cells, has also been carried outWe are grateful to Ministerio de Economía y Competitividad, Instituto de Salud Carlos III (PI080525 and PI1100659), of Spain for financial suppor

A convergent growth approach to electroactive ferrocene rich carbosilane- and siloxane-based dendrons, dendrimers, and dendronized polymers

The construction of the first members of a novel family of structurally well-defined, ferrocenyl rich, dendritic macromolecules based on carbosilane skeletons and siloxane linkages has been achieved via a convergent growth approach. Starting from triferrocenylvinylsilane Fc3SiCHvCH2 (1) (Fc = Fe(η5 -C5H4)(η5 - C5H5) as the key monomer, the sequential utilization of platinum-catalyzed hydrosilylation and alkenylation steps with Grignard reagents (allylmagnesium bromide) can be applied to prepare three different branched structures: multiferrocenyl-terminated dendrons 2 and 3, dendrimers 4 and 5, and dendronized polymers 7n–9n. All of the dendritic metallomacromolecules have been thoroughly characterized using a combination of elemental analysis, multinuclear (1 H, 13C, 29Si) NMR spectroscopy, FT-IR and MALDI-TOF mass spectrometry, to establish their chemical structures and properties. The molecular structures of G1- dendron 3 and dendrimer 4, containing six and nine ferrocenyl units, respectively, have been successfully determined by single-crystal X-ray analysis, compound 4 being the branched multiferrocenyl-containing siloxane with the highest number of Fc substituents whose structure has been reported so far. Electrochemical studies (using cyclic voltammetry (CV) and square wave voltammetry (SWV) performed in dichloromethane solution with [PF6] − and [B(C6F5)]4− as supporting electrolyte anions of different coordinating abilities) reveal that all the macromolecular compounds obtained exhibit a three-wave redox pattern, suggesting appreciable electronic interactions between the silicon-bridged triferrocenyl moieties as they are successively oxidized. In addition, dendrimer 5 and dendronized polymers 7n–9n, with 12 and 4 < n < 14 ferrocenyl units, respectively, linked in threes around the periphery, undergo remarkable oxidative precipitation in CH2Cl2/[n-Bu4N][PF6] and are able to form chemically modified electrodes with stable electroactive filmsWe thank the Ministerio de Ciencia e Innovación (MICINN) of Spain for its financial support through projects PGC2018- 094644-B-C21 and PID2021-125207NB-C3

Unexpected formation of a silicon-centered spirocyclic oligosiloxane bearing eight pendant ferrocene units

An intriguing but rare silicon-centered spirocyclic compound, spiro[5.5]octaferrocenylpentasiloxane (4) featuring silicon fused six-membered ferrocenyl-functionalized siloxane rings, has been obtained during the thermally induced transformation of triferrocenylsilane Fc3Si–H (1) into triferrocenylsilanol Fc3Si–OH (2), when N,N-dimethylformamide (DMF) was used as a solvent in the presence of the metal carbonyl Mo(CO)6. The unexpected formation of the maximally ferrocenyl substituted silicon centered spirocyclic 4 involves the obtention, and subsequent condensation, of different ferrocenylsilanol intermediates. Spirocyclic silicate 4 has been characterized using a combination of MALDI-TOF mass spectrometry, elemental analysis, and single crystal X-ray diffraction analysi

Crystal structure dependence of the energy transfer from tb(III) to yb(III) in metal–organic frameworks based in bispyrazolylpyridines

Luminescent mixed lanthanide metal−organic framwork (MOF) materials have been prepared from two polyheterocyclic diacid ligands, 2,6-bis(3-carboxy-1-pyrazolyl)pyridine and 2,6- bis(4-carboxy-1-pyrazolyl)pyridine. The crystal structures of the two organic molecules are presented together with the structures for the MOFs obtained by hydrothermal synthesis either with Yb(III) or mixed Tb(III)/Yb(III) ions. Different coordination architectures result from each ligand, revealing also important differences between the lanthanides. The mixed lanthanide metal−organic frameworks also present diverse luminescent behavior; in the case of 2,6-bis(4-carboxy-1- pyrazolyl)pyridine, where no coordinated water is present in the metal environment, Tb(III) and Yb(III) characteristic emission is observed by excitation of the bispyrazolylpyridine chromophoreThe research leading to these results has received funding from ERCROS S.A. (Aranjuez, Spain

Structural study of the compounds formed in the reactions of FeCl3·6H2O with Ni(OH)2 in the presence of dithiolenes HSRSH (R = C6H2Cl2 or C6H4)

In our attempts to prepare coordination polymers by reaction of FeCl3·6H2O and Ni(OH)2 in the presence of dithiolenes HSC6H2X2SH (X = Cl or H), several ion pairs of compounds containing the anionic entity [Ni(SC6H2X2S)2]⁻ were obtained instead. It was also found that other species without dithiolene ligands were formed in these reactions, giving rise to different ion pairs and a tetrametallic cluster. The careful isolation of the different types of crystalline solids allowed the characterization of all of the resulting compounds by single crystal X-ray diffraction (SCXRD). In order to establish the amount of nickel and iron present in the crystals, complementary total reflection X-ray fluorescence (TXRF) analyses were performed. The eight different structural types that were obtained are described and compared with related ones found in the literaturaThis research was funded by the Spanish Ministerio de Economía y Competitividad, grand number (MAT2016-77608-C3-1-P) and Ministerio de Ciencia, Innovación y Universidades (PGC2018-094644-B-C21

Luminescent Thermochromism of 2D Coordination Polymers Based on Copper(I) Halides with 4-Hydroxythiophenol

This is the peer-reviewed version of the following article: Troyano, J., Perles, J., Amo‐Ochoa, P., Martínez, J. I., Concepción Gimeno, M., Fernández‐Moreira, V., ... & Delgado, S. (2016). Luminescent Thermochromism of 2D Coordination Polymers Based on Copper (I) Halides with 4‐Hydroxythiophenol. Chemistry–A European Journal, 22(50), 18027-18035., which has been published in final form at https://doi.org/10.1002/chem.201603675. This article may be used for non-commercial purposes in accordance with Wiley-VCH Terms and Conditions for Self-ArchivingSolvothermal reactions between copper(I) halides and 4-mercaptophenol give rise to the formation of three coordination polymers with general formula [Cu3X(HT)2]n(X=Cl, 1; Br, 2; and I, 3). The structures of these coordination polymers have been determined by X-ray diffraction at both room- and low temperature (110 K), showing a general shortening in Cu−S, Cu−X and Cu−Cu bond lengths at low temperatures. 1 and 2 are isostructural, consisting of layers in which the halogen ligands act as μ3-bridges joining two Cu1 and one Cu2 atoms whereas in 3 the iodine ligands is as μ4-mode but the layers are quasi-isostructural with 1 or 2. These compounds show a reversible thermochromic luminescence, with strong orange emission for 1 and 2, but weaker for 3 at room temperature, whereas upon cooling at 77 K 1 and 2 show stronger yellow emission, and 3 displays stronger green emission. DFT calculations have been used to rationalize these observations. These results suggest a high potential for this novel and promising stimuli-responsive materialsThis work was supported by MICINN (MAT2013-46753-C2-1-P). JIM acknowledges funding from the ERC-Synergy Program (Grant ERC-2013-SYG-610256 NANOCOSMOS) and computing resources from CTI-CSIC

The flexibility of CuI chains and the functionality of pyrazine-2-thiocarboxamide keys to obtaining new Cu(I)-I coordination polymers with potential use as photocatalysts for organic dye degradation

This research focuses on two interesting aspects in the synthesis of new coordination polymers (CPs) taking advantage of the lability of coordination bonds. The first is the use of multifunctional and flexible building blocks, such as pyrazine-2-thiocarboxamide (Pyrtca) and CuI, and the second is the modification of the synthetic conditions to expand the amount of different crystalline phases. This means that starting from the same building blocks, we can increase the number of compounds obtained and diversify their final properties, as well as their possible applications. Furthermore, Cu(I)-halogen coordination polymers have been extensively studied for a long time due to their interesting optoelectronic properties. However, despite being usually semiconductors, research related to their possible behavior as photocatalysts is almost non-existent. In this work, we present five compounds, four coordination compounds with formulas [CuI(Pyrtca)]n (CP1), [Cu3I3(Pyrtca)7] (2) [Cu2I2(Pyrtca)]n (CP4 and CP4′) and a transformation of the starting ligand to a cationic imidazole derivative (compound 3) where copper iodine serves as a catalyst. All the compounds have been characterized by different techniques including single-crystal X-ray diffraction. The antibacterial behavior of CP1 against E. Coli DH5, E. Coli BL21, and C. glabrata (CECT 1448), as well as their optoelectronic properties, are also discussed in the work. The value of the band gap obtained (1.91 eV) for the two-dimensional coordination polymer of formula [Cu2I2(Pyrtca)]n (CP4) allows us to study its behavior as a photocatalyst in the degradation of persistent dyes in water with interesting results, achieving a total degradation of Methylene Blue and Rhodamine B in 40 min under UV–visible lightThis work was supported by the Spanish Ministerio de Ciencia e Innovación (Agencia Estatal de Investigación) (MCIN/AEI/10.13039/501100011033; PID2019- 108028GB-C22 and TED2021-131132B-C22

Using phosphine ligands with a biological role to modulate reactivity in novel platinum complexes

Three platinum complexes with cis and trans configuration cis-[Pt(TCEP) 2 Cl 2 ], cis-[Pt(tmTCEP) 2 Cl 2 ] and trans-[Pt(TCEP) 2 Cl 2 ], where TCEP is tris(2-carboxyethyl)phosphine, have been synthesized and fully characterized by usual techniques including single-crystal X-ray diffraction for trans-[Pt(TCEP) 2 Cl 2 ] and cis-[Pt(tmTCEP) 2 Cl 2 ]. Here, we also report on an esterification process of TCEP, which takes place in the presence of alcohols, leading to a platinum complex coordinated to an ester tmTCEP (2-methoxycarbonylethyl phosphine) ligand. The stability in solution of the three compounds and their interaction with biological models such as DNA (pBR322 and calf thymus DNA) and proteins (lysozyme and RNase) have also been studied.This work was supported by Spanish MINECO: CTQ2015-68779R and CTQ2015-70371-RED

Taming C60 fullerene: Tuning intramolecular photoinduced electron transfer process with subphthalocyanines

Two subphthalocyanine-C60 conjugates have been prepared by means of the 1,3-dipolar cycloaddition reaction of (perfluoro) or hexa(pentylsulfonyl) electron deficient subphthalocyanines to C60. Comprehensive assays regarding the electronic features-in the ground and excited state-of the resulting conjugates revealed energy and electron transfer processes upon photoexcitation. Most important is the unambiguous evidence-in terms of time-resolved spectroscopy-of an ultrafast oxidative electron transfer evolving from C60 to the photoexcited subphthalocyanines. This is, to the best of our knowledge, the first case of an intramolecular oxidation of C60 within electron donor-acceptor conjugates by means of only photoexcitationFinancial support from the MICINN and MEC, Spain (CTQ- 2011-24187/BQU and PRI-PIBUS-2011-1128) is acknowledged. D.M.G. appreciates funding by the DFG (GU 517/14-1) and “Solar Technologies Go Hybrid” – an initiative of the Bavarian State Ministry for Science, Research, and Ar