Terpyridine isomerism as a tool for tuning red-to-NIR emissive properties in heteronuclear gold(I)-thallium(I) complexes.

The polymeric linear chain [AuTl(C6Cl5)2]n reacts with three terpyridine-type ligands substituted with thiophene groups containing N-donor centres in different relative positions (L1, L2 and L3), leading to the Au(I)/Tl(I) complexes [AuTl(C6Cl5)2(L1)]n (1), [{AuTl(C6Cl5)2}2(L2)]n (2) and [AuTl(C6Cl5)2(L3)]n (3). X-Ray diffraction studies reveal that L1 acts as a chelate, while L2 and L3 act as bridging ligands, resulting in different coordination indexes for the thallium(I) centre. These structural differences strongly influence their optical properties, and while compounds 2 and 3 emit near the limit of the visible range, complex 1 emits in the infrared region. DFT calculations have also been carried out in order to determine the origin of the electronic transitions responsible for their optical properties.

Heteronuclear Gold(I)-Copper(I) Complexes with Thia- and Mixed Thia-Aza Macrocyclic Ligands: Synthesis, Structures and Optical Properties.

The reactivity of the heterometallic polynuclear complexes [{Au(R)2 }2 Cu2 (MeCN)2 ]n (R=C6 F5 , C6 Cl5 ) with the thioether crowns 1,4,7-trithiacyclononane (L1, [12]aneS3 ), 1,4,8,11-tetrathiacyclododecane (L2, [14]aneS4 ), 1,4,7,10,13,16,19,22-octathiacyclotetracosane (L3, [24]aneS8 ), and the quinoline functionalized pendant arm derivatives of the 12-membered mixed-donor macrocycles 1-aza-,4,7,10-trithiacyclododecane ([12]aneNS3 ) and 1,7-diaza-4,10-dithiacyclododecane ([12]aneN2 S2 ), L4 and L5, respectively, was investigated in THF solution. While with L4 and L5 only ionic compounds of general formulation [Cu(L)][Au(R)2 ] were isolated and structurally characterized (none of them featuring Au⋅⋅⋅Cu interactions), with L1-L3, beside similar ionic compounds, some heteronuclear complexes of general formulation [{Au(R)2 }{Cu(L)}] and featuring Au⋅⋅⋅Cu interactions were also obtained. All of them display rather unusual non-classical C-H⋅⋅⋅Au hydrogen interactions. The complexes display in the solid state different optical properties related to their structures, which have been studied experimentally and theoretically via TD-DFT calculations. In particular, all compounds of the type [{Au(R)2 }{Cu(L)}] featuring Au⋅⋅⋅Cu metallophilic interactions display luminescence in the solid state both at room temperature (RT) and at 77 K. On the contrary, ionic compounds of general formulation [Cu(L)][Au(R)2 ], except [Cu(L4)][Au(C6 F5 )2 ], are not luminescent.

Vapochromic behaviour of a gold(I)-lead(II) complex as a VOC sensor.

The reaction among [Au2Ag2(C6F5)4(OEt2)2]n, PbCl2 and terpyridine leads to the polymeric complex [{Au(C6F5)2}2{Pb(terpy)}]n (1). Its crystal structure reveals potential voids close to the lead centres large enough to hold different molecules. The availability of these free sites allows complex 1 to act as a VOC sensor. Thus, when 1 is exposed to different solvent vapours such as acetonitrile, toluene or THF, variations in its solid appearance and its photophysical properties are observed as a consequence of the formation of the new polymorphs [{Au(C6F5)2}2{Pb(terpy)(CH3CN)2}]n (2), [{Au(C6F5)2}2{Pb(terpy)}]n·Tol (3) and [{Au(C6F5)2}2{Pb(terpy)(THF)}]n·THF (4). Each polymorph displays a different emission energy depending on its structure and the presence of metallophilic interactions. In addition, the reversible solvent molecule exchange allows the tuning of the luminescence emissions in the greenish yellow-red range. DFT and TD-DFT calculations were performed to explain the origin of the luminescence of all these complexes.

Switching On/Off of a Solvent Coordination in a Au(I)-Pb(II) Complex: High Pressure and Temperature as External Stimuli.

The benzonitrile solvate {[{Au(C6F5)2}2{Pb(terpy)}]·NCPh}n (1) (terpy = 2,2':6',2″-terpyridine) displays reversible reorientation and coordination of the benzonitrile molecule to lead upon external stimuli. High-pressure X-ray diffraction studies between 0 and 2.1 GPa reveal a 100% of conversion without loss of symmetry, which is totally reversible upon decompression. By variable-temperature X-ray diffraction studies between 100 and 285 K, a partial coordination is achieved.

Silver-Based Terpyridine Complexes as Antitumor Agents.

Silver complexes bearing substituted terpyridine or tetra-2-pyridinylpyrazine ligands have been prepared and structurally characterised. The study of the anticancer properties of silver complexes with this type of ligands is scarce, despite the possibilities of combining the properties of the metal and the ability of the ligands for DNA binding. Here, the antiproliferative activity, stability, CT-DNA binding, and mechanism of cell death of these types of derivatives are studied. High cytotoxicity against different tumour cells was observed, and, more important, a great selectivity index has been detected between tumour cells and healthy lymphocytes T for some of these compounds. The CT-DNA interaction study has shown that these derivatives are able to interact with CT-DNA by moderate intercalation. Furthermore, cell death studies indicate that these derivatives promote the apoptosis by a mitochondrial pathway.

A "gold standard" computational proof for the existence of gold(III) aurophilicity.

The existence of aurophilic gold(III)⋯gold(III) interactions has for a long time been neglected due to structural arguments and comparison with the aurophilicity of gold(I) compounds. We show with calculations at the CCSD(T) level of theory that the [AuIII(CH3)3(NH3)]2 dimer has a metallophilic dispersion interaction between the gold(III) atoms of 10.5 kJ mol-1. The aurophilic interaction is illustrated by topological QTAIM calculations and IRI analysis.

Synthesis and Structural Characterization of Phosphanide Gold(III)/Gold(I) Complexes and Their Thallium(III) and Gold(III) Precursors.

In this paper, we describe a series of diphenylphosphane and diphenylphosphanide gold(III) and gold(III)/gold(I) complexes containing 3,5-C6Cl2F3 as aryl ligands at gold that have been synthesized due to the arylating and oxidant properties of the new polymeric thallium(III) complex [TlCl(3,5-C6Cl2F3)2]n (1). Its reaction with [Au(3,5-C6Cl2F3)(tht)] (tht = tetrahydrothiophene) produces the gold(III) complex [Au(3,5-C6Cl2F3)3(tht)] (2), which allows the synthesis of the diphenylohosphane derivative [Au(3,5-C6Cl2F3)3(PPh2H)] (3). Its treatment with acetylacetonate gold(I) derivatives leads to two novel AuIII/AuI phosphanido-bridged complexes, [PPN][Au(3,5-C6Cl2F3)3(µ-PPh2)AuCl] (4) and [PPN][{(3,5-C6Cl2F3)3Au(µ-PPh2)}2Au] (5). All these complexes have been characterized, and the crystal structures of 1, 2, 4 and 5 have been established by single crystal X-ray diffraction methods, showing a novel polymeric arrangement in 1.

Spontaneous in situ generation of photoemissive aurophilic oligomers in water solution based on the 2-thiocytosine ligand.

Complexes [Au(S-2-thiocytosinate)(PMe3)] (2, 2-thiocytosine = 4-amino-2-mercaptopyrimidine) and [Au(S-2-thiocytosine)(PMe3)](CF3CO2) (3) have been prepared by the reaction of [Au(acac)(PMe3)] (1, acac = acetylacetonate) or [Au(OCOCF3)(PMe3)] with 2-thiocytosine, respectively. The equimolecular mixture of complexes 1 and 3 also produces [{Au(PMe3)}2(µ-S,N 1-2-thiocytosinate)](CF3CO2) (4), which features two distinct [Au(PMe3)]+ groups coordinated to the S and N1 atoms of the heterocycle. Complex 4 experiences a ligand redistribution process in water solution that liberates [Au(PMe3)2](CF3CO2) and a brightly coloured and luminescent species of [Au n (µ-S,N 1-2-thiocytosinate) n ] stoichiometry, presumably as a tetraauracycle (n = 4).

Computational prediction of Au(I)-Pb(II) bonding in coordination complexes and study of the factors affecting the formation of Au(I)-E(II) (E = Ge, Sn, Pb) covalent bonds.

We have studied computationally the Au-M (M = Ge, Sn, Pb) bonding trends in a series of model systems [(PH3)3Au-(MCl3)] (M = Ge (4), Sn (5), Pb (6)). For this, we have fully optimized the model systems at the MP2 level of theory, computing the Au-M bonding energy at the equilibrium distances applying the counterpoise (cp) correction to the basis-set superposition error (BSSE) and performing a natural energy decomposition analysis (NEDA). Furthermore, a topological analysis of the electron density using QTAIM, ELF and DORI tools was performed. In order to provide further insights on the possibility of predicting the existence of Au(i)-Pb(ii) donor bonds, Density Functional Theory calculations using the pbe functional and including dispersion corrections (DFT-D3/pbe) were performed on three model systems, [(PR3)3Au-(PbCl3)] (R = CH3 (7), H (8), CF3 (9)). This study also includes the corresponding NEDA calculations and the topological analysis of the electron density, which provides information about the Au-Pb bond, but also about the supporting weak ligand-ligand interactions. Overall, the study provides information about the factors affecting the formation of stabilizing Au(i)-Pb(ii) covalent bonds.

Time-Dependent Molecular Rearrangement of [Au(N9-adeninate)(PTA)] in Aqueous Solution and Aggregation-Induced Emission in a Hydrogel Matrix.

An in-depth study of the molecular rearrangement of the complex [Au(N9-adeninate)(PTA)] (1), promoted in aqueous solution, is presented. This complex, which has been previously described as forming dimers in its crystalline form, is also demonstrated as being able to assemble into an infinite AuI···AuI chain polymer. The structural motifs are tentatively related to the dramatic modification of the photoemissive properties of 1 in water solution at long times, with the aid of UV-vis and photoluminescence measurements, PGSE-NMR, and theoretical calculations. A subtle equilibrium in favor of aurophilically governed aggregates has been envisaged as the driving force of the molecular rearrangement. Furthermore, 1 has been explored as an additive of the hydrogel of [Au(N9-adeninate)(PMe3)] (2) for a further tuning of its photophysical properties without loss of the gel texture.

Rational Assembly of Metallophilic Gold(I)-Lead(II) and Gold(I)-Gold(I) Puzzle Pieces.

The assembly of two different building blocks, [{Au(C6 F5 )2 }{PbCl(terpy)}] (terpy=2,2':6':2''-terpyridine) and [{Au(C6 F5 )2 }2 {Pb(terpy)}]n , acting as terminal or central pieces, respectively, gives rise to a decanuclear complex built via metallophilic and π-stacking interactions in which the number of AuI ⋅⋅⋅AuI and AuI ⋅⋅⋅PbII contacts is finely controlled.

Perhalophenyl Three-Coordinate Gold(I) Complexes as TADF Emitters: A Photophysical Study from Experimental and Computational Viewpoints.

We report the synthesis of novel perhalophenyl three-coordinated gold(I) complexes using 1,2-bis(diphenylphosphino)benzene (dppBz) as the chelating ligand and [AuR(tht)] (R = C6F5, C6Cl2F3, C6Cl5) as the perhalophenyl-gold(I) source, leading to [AuR(dppBz)] (R = C6F5 (1), C6Cl2F3 (2), C6Cl5 (3)) complexes. The solid-state structures of compounds 2 and 3 consist of discrete three-coordinated Au(I) complexes, which show a distorted trigonal planar geometry for the gold center with dissimilar Au-P distances. The distorted structural arrangement is closely related to its photophysical properties. The studied complexes display very intense emissions at room temperature (RT) and at 77 K in the solid state. Studies of the emissive properties of the complexes at different temperatures suggest that the emissions are phosphorescent at 77 K and exhibit thermally activated delayed fluorescence (TADF) at RT. First-principle calculations of the photophysical processes yielded rate constants for intersystem crossing and reverse intersystem crossing that are in excellent agreement with experimental data.

Metallophilic Au(i)M(i) interactions (M = Tl, Ag) in heteronuclear complexes with 1,4,7-triazacyclononane: structural features and optical properties.

1,4,7-Triazacyclononane (TACN) has been used for the first time to support Au(i)M [M = Tl(i), Ag(i)] metallophilic interactions in the formation of heteronuclear gold(i) complexes having luminescence properties. The compounds {[{Au(C6Cl5)2}Tl(TACN)]2}n (1), [{Au(C6F5)2}Tl(TACN)] (2), [{Au(C6Cl5)2}Ag(TACN)] (3), and [{Au(C6F5)2}{Ag(TACN)}2Au(C6F5)2] (4) have been synthesized by reacting TACN and the polymeric starting organometallic gold(i) compounds [{Au(C6X5)2}M]n (M = Ag(i), Tl(i); X = Cl, F) in a 1 : 1 molar ratio, in THF. 1, 3 and 4 have also been structurally characterized and their optical properties explained on the basis of their structural features with the support of TD-DFT calculations.

Zigzag vs Helicoidal Gold-Silver 1D Chains: Influence of Subtle Interactions in the Spatial Arrangement of Supramolecular Systems.

The reaction of 4'-(2-thienyl)-2,2':6',2,2''-terpyridine (S-terpy) with the heterometallic complexes [Au2Ag2R4(OEt2)2]n (R = C6F5, C6Cl5) leads to the compounds [{Au(C6X5)2}Ag(S-terpy)]n (X = F (1), Cl (2)). The X-ray diffraction analysis of the complexes shows an alternating disposition of the metals -Au-Ag-Au-Ag- in 1D infinite polymeric chains. Despite the fact of having the same metallic sequence, the spatial arrangement observed for both complexes is very different, since for [{Au(C6F5)2}Ag(S-terpy)]n (1) the metals adopt a zigzag disposition, whereas an helicoidal distribution of the interacting metals is observed for the complex [{Au(C6Cl5)2}Ag(S-terpy)]n (2). These different arrangements are related to the perhalophenyl ligands present in the complexes, which appear with different spatial dispositions, being staggered in the case of C6F5 (1) and almost eclipsed in the case of C6Cl5 (2). In order to explain the reasons for these different structural arrangements, we performed a DFT-D3 computational analysis and a subsequent study of the qualitative characterization of the noncovalent interactions (NCIs) in real space.

Structural and Luminescence Properties of Heteronuclear Gold(I)/Thallium(I) Complexes Featuring Metallophilic Interactions Tuned by Quinoline Pendant Arm Derivatives of Mixed Donor Macrocycles.

Reaction of the heterometallic complex [{Au(C6F5)2}Tl]n with the quinoline pendant arm derivatives L1 and L2 of the mixed donor macrocycles [12]aneNS2O and PhenNS2 affords the new Au(I)/Tl(I) complexes [{Au(C6F5)2}Tl(L1)] (1), [{Au(C6F5)2}Tl(L2)] (2), [{Au(C6F5)2Tl}{Au(C6F5)2Tl(L1)}]2 (3), and [{Au(C6F5)2Tl}{Au(C6F5)2Tl(L2)}]n (4) depending on the reaction molar ratios used. These complexes present different optical properties strictly related to their structural features and to the presence of Au(I)···Tl(I) metallophilic interactions, which are finely tuned by the coordinating quinoline moiety and have been studied experimentally and theoretically via TD-DFT calculations.

Balancing ionic and H-bonding interactions for the formation of Au(i) hydrometallogels.

The ionic complex [Au(9N-adenine)(PMe3)](CF3CO2) (1) displays a supramolecular structure built up through ionic, π-stacking, C-HO, C-HN and C-HAu interactions. Ab initio calculations permit the characterization of the nature of these interactions. Complex 1 is luminescent in the solid state at 77 K. This complex forms a hydrometallogel consisting of straight molecular nanowires, which is responsive to thermal and mechanical stimuli. The gel has also been studied by rheological oscillatory experiments.

Temperature-assisted formation of reversible metallophilic Au-Ag interaction arrays.

A temperature-controlled self-assembly process in a solution of [Ag(terpy)]nn+ and [Au(C6F5)2]- units has been performed. For this, the crystallisation of the complex [{Au(C6F5)2}Ag(terpy)]n under the same experimental conditions, changing only the temperature, allows the synthesis of polymorphs [{Au(C6F5)2}2Ag2(terpy)2]n (2a) at 298 K and [{Au(C6F5)2}Ag(terpy)]n (2b) at 280 K. The X-ray diffraction studies previously reported for 2a revealed a polymeric structure with an unusual + + - - + + - - charge sequence, whereas for polymorph 2b, a more classical + - + - disposition has been obtained. The conversion of one polymorph into the other can be achieved by simple dissolution of one of them and by recrystallisation at the corresponding temperature. The mechanism of the formation of each polymorph is proposed in view of their 1H NMR, 1H-PGSE NMR and molar conductivity measurements.

Stimuli-Responsive Solvatochromic Au(I)-Ag(I) Clusters: Reactivity and Photophysical Properties Induced by the Nature of the Solvent.

Reaction of the heterometallic polymer [Au2Ag2(C6Cl5)4(OEt2)2] n with 4 equiv of pyridazine leads to the new discrete complex [Au2Ag2(C6Cl5)4(µ2-C4H4N2)2(C4H4N2)2] (1). Complex 1 is solvoluminescent, leading to drastic structural changes, depending on the coordination ability of the chosen solvent. Thus, the reaction of complex 1 with acetonitrile leads to a new Au(I)-Ag(I) complex of stoichiometry [Au2Ag2(C6Cl5)4(µ2-C4H4N2)2(NCMe)2] n·2CH3CN(2), while if the reaction is carried out with a noncoordinating solvent such as dichloromethane, complex [Au2Ag2(C6Cl5)4(C4H4N2)2] n·CH2Cl2 (3) is obtained. Furthermore, when complexes 1, 2, and 3 are exposed to tetrahydrofuran, different results are obtained. In the case of complex 1, the metallic core disposition remains and THF is incorporated as a crystallization solvent in [Au2Ag2(C6Cl5)4(µ2-C4H4N2)2(C4H4N2)2]·2THF (1·THF). On the other hand, reaction of complexes 2 or 3 with THF gives rise to a mixture of the corresponding polymeric complex [Au2Ag2(C6Cl5)4(THF)2] n, in which pyridazine ligands are displaced, together with a polymorph of complex 1·THF. All these complexes are luminescent in solid state displaying different emission energies depending on their structural disposition as well as on the presence of the metallophilic interactions. These subtle changes in the cluster structures, only based on the solvent used, lead to spectacular reversible changes in the emissive behavior of the complexes, allowing the tuning of the luminescent emissions in a wide range. DFT and TD-DFT calculations support the experimental photophysical studies.

Influence of the Number of Metallophilic Interactions and Structures on the Optical Properties of Heterometallic Au/Ag Complexes with Mixed-Donor Macrocyclic Ligands.

The reactivity of the polymeric gold(I)/silver(I) compound [Au2Ag2(C6F5)4(OEt2)2] n toward the 12-membered mixed-donor macrocyclic ligands 1,7-diaza-4,10-dithiacyclododecane (L1), 1-aza-4,7,10-trithiacyclododecane (L2), N-quinolinylmethyl-1-aza-4,7,10-trithiacyclododecane (L3), and N, N'-bis(quinolinylmethyl)-1,7-diaza-4,10-dithiacyclododecane (L4) was studied. The reactions were carried out using different molar ratios depending on the coordination properties of the ligands, which were modified by changing the donor atoms present in the macrocyclic framework (sulfur or nitrogen) or by linking one or two methylquinoline pendant-arms at the secondary nitrogen atom(s). X-ray diffraction analysis of the new complexes obtained show a nuclearity that increases on increasing the number of donor atoms in the ligands. The rich structural diversity observed determines different optical responses when the complexes are irradiated with UV-vis light in the solid state and in THF solution. The study of the optical properties reveals that in complexes for which the luminescence is due to metal-metal interactions, higher emission wavelengths are observed as the number of these metallophilic contacts increases, while the luminescence of ionic complexes has its origin in the macrocyclic ligands. TD-DFT calculations were carried out to verify the origin of these interesting structural-optical property relationships.

Dispersive Forces and Dipole Moment Increase as Driving Forces for the Formation of an Unprecedented Metallophilic Heterotrimetallic System.

The crystal structure of the polymeric complex [Au5 Ag2 Tl3 (C6 F5 )10 (L1 )2 ]n (L1 =1-aza-4,10-dithia-7-oxacyclododecane) displays heterotrimetallic Ag⋅⋅⋅Au⋅⋅⋅Tl moieties and is held by unsupported metallophilic interactions. This complex emits at 500 nm in the solid state. Ab initio calculations show that the large thermodynamic stability that helps the formation of this heterotrimetallic system arises from the combination of dispersive forces and a very large dipole moment in the supramolecular arrangement.