Pyrazolate-Bridged NHC Cyclometalated [Pt2] Complexes and [Pt2Ag(PPh3)]+ Clusters in Electroluminescent Devices.

The ionic transition metal complexes (iTMCs) [{Pt(C∧C*)(µ-Rpz)}2Ag(PPh3)]X (HC∧C* = 1-(4-(ethoxycarbonyl)phenyl)-3-methyl-1H-imidazole-2-ylidene, X = ClO4/PF6; Rpz = pz 1a/2a, 4-Mepz 1b/2b, and 3,5-dppz 1c/2c) were prepared from the neutral [{Pt(C∧C*)(µ-Rpz)}2] (Rpz = pz A, 4-Mepz B, and 3,5-dppz C) and fully characterized. The "Ag(PPh3)" fragment is in between the two square-planar platinum units in an "open book" disposition and bonded through two Pt-Ag donor-acceptor bonds, as shown by X-ray diffraction (dPt-Ag ∼ 2.78 Å, 1a-1c). 195Pt{1H} and 31P{1H} NMR confirmed that these solid-state structures remain in solution. Photoluminescence studies and theoretical calculations on 1a, were performed. The diphenylpyrazolate derivatives show the highest photoluminescence quantum yield (PLQY) in the solid state. Therefore, 2c and its neutral precursor C were selected as active materials on light-emitting devices. OLEDs fabricated with C showed a turn-on voltage of 3.2 V, a luminance peak of 21,357 cd m-2 at 13 V, and a peak current efficiency of 28.8 cd A-1 (9.5% EQE). They showed a lifetime t50 of 15.7 h. OLEDs using 2c showed a maximum luminance of 114 cd m-2, while LECs exhibited a maximum luminance of 20 cd m-2 and a current efficiency of around 0.2 cd A-1, with a t50 value of 50 min.

NIR-II Emission from Cyclometalated Dinuclear Pt(III) Complexes.

Half-lantern Pt(II) dinuclear complexes [{Pt(C∧Npz)(µ-S∧NR)}2] (HC∧Npz = 1-naphthalen-2-yl-1H-pyrazole; R = H, HS∧N: 2-mercaptopyrimidine 1; R = CF3, HS∧NF: 4-(trifluoromethyl)-2-mercaptopyrimidine 2) were selectively obtained as single isomers with the C∧N groups in an anti-arrangement and rather short metallophilic interactions (dPt-Pt = 2.8684(2) Å for 2). They reacted with haloforms in the air and sunlight to obtain the corresponding oxidized diplatinum(III) derivatives [{Pt(C∧Npz)(µ-S∧NR)X}2] (X = Cl (1-Cl), Br (1-Br), I (1-I, 2-I)). The single-crystal X-ray structures exhibit Pt-Pt distances typical for the existence of a metal-metal bond, which evidence fairly well the influence of the axial ligand (X). The reactions of 1 and 2 with CHI3 in the dark afforded mixtures of [IPt(C∧Npz)(µ-S∧N)2Pt(C∧Npz)CHI2] and 1-I or 2-I, with the former being the major species under an Ar atmosphere, while the reactions of 1 with CHBr3 and CHCl3 need light to occur. These Pt2(III,III) complexes display low-energy absorptions and emissions that strongly depend on the axial ligand. In the solid state, they show a broad NIR emission ranging from 985 to 1070 nm at RT that suffers a hypsochromic shift when cooling down to 77 K. The photoemissive behavior of the dinuclear Pt(II) and Pt(III) systems is disclosed with the aid of density functional theory calculations.

High-Valent Pyrazolate-Bridged Platinum Complexes: A Joint Experimental and Theoretical Study.

Complexes [{Pt(C^C*)(µ-pz)}2] (HC^C*A = 1-(4-(ethoxycarbonyl)phenyl)-3-methyl-1H-imidazol-2-ylidene 1a, HC^C*B = 1-phenyl-3-methyl-1H-imidazol-2-ylidene 1b) react with methyl iodide (MeI) at room temperature in the dark to give compounds [{PtIV(C^C*)Me(µ-pz)}2(µ-I)]I (C^C*A 2a, C^C*B 2b). The reaction of 1a with benzyl bromide (BnBr) in the same conditions afforded [Br(C^C*A)PtIII(µ-pz)2PtIII(C^C*A)Bn] (5a), which by heating in BnBr(l) became [{PtIV(C^C*A)Bn(µ-pz)}2(µ-Br)]Br (6a). Experimental investigations and density functional theory (DFT) calculations on the mechanisms of these reactions from 1a revealed that they follow a SN2 pathway in the two steps of the double oxidative addition (OA). Based on the DFT investigations, species such as [(C^C*A)PtIII(µ-pz)2PtIII(C^C*A)R]X (RX = MeI Int-Me, BnBr Int-Bn) and [(C^C*A)PtII(µ-pz)2PtIV(C^C*A)(R)X] (RX = MeI Int'-Me, BnBr Int'-Bn) were proposed as intermediates for the first and the second OA reactions, respectively. In order to put the mechanisms on firmer grounds, Int-Me was prepared as [(C^C*A)PtIII(µ-pz)2PtIII(C^C*A)Me]BF4 (3a') and used to get [I(C^C*A)PtIII(µ-pz)2PtIII(C^C*A)Me](4a), [(C^C*A)PtII(µ-pz)2PtIV(C^C*A)(Me)I](Int'-Me), and [{PtIV(C^C*)Me(µ-pz)}2(µ-I)]BF4 (2a'). The single-crystal X-ray structures of 2a, 2b, 3a', and 5a along with the mono- and bi-dimensional 1H and 195Pt{1H} NMR spectra of all the named species allowed us to compare structural and spectroscopic data for high-valent complexes with the same core [{Pt(C^C*)(µ-pz)}2] but different oxidation states.

Chameleonic Photo- and Mechanoluminescence in Pyrazolate-Bridged NHC Cyclometalated Platinum Complexes.

DFT investigations on the ground (GS) and the first triplet (T1) excited state potential energy surfaces (PES) were performed on a new series of platinum-butterfly complexes, [{Pt(C∧C*)(µ-Rpz)}2] (Rpz: pz, 1; 4-Mepz, 2; 3,5-dmpz, 3; 3,5-dppz, 4), containing a cyclometalated NHC in their wings. The geometries of two close-lying local minima corresponding to butterfly spread conformers, 1s-4s, and butterfly folded ones, 1f-4f, with long and short Pt-Pt separations, respectively, were optimized in the GS and T1 PES. A comparison of the GS and T1 energy profiles revealed that an opposite trend is obtained in the relative stability of folded and spread conformers, the latter being more stabilized in their GS. Small ΔG (s/f) along with small-energy barriers in the GS support the coexistence of both kinds of conformers, which influence the photo- and mechanoluminescence of these complexes. In 5 wt % doped PMMA films in the air, these complexes exhibit intense sky-blue emissions (PLQY: 72.0-85.9%) upon excitation at λ ≤ 380 nm arising from 3IL/MLCT excited states, corresponding to the predominant 1s-4s conformers. Upon excitation at longer wavelengths (up to 450 nm), the minor 1f-4f conformers afford a blue emission as well, with PLQY still significant (40%-60%). In the solid state, the as-prepared powder of 4 exhibits a greenish-blue emission with QY ∼ 29%, mainly due to 3IL/3MLCT excited states of butterfly spread molecules, 4s. Mechanical grinding resulted in an enhanced and yellowish-green emission (QY ∼ 51%) due to the 3MMLCT excited states of butterfly folded molecules, 4f, in such a way that the mechanoluminescence has been associated with an intramolecular structural change induced by mechanical grinding.

Structural Insights into the Vapochromic Behavior of Pt- and Pd-Based Compounds.

Anionic complexes having vapochromic behavior are investigated: [K(H2O)][M(ppy)(CN)2], [K(H2O)][M(bzq)(CN)2], and [Li(H2O)n][Pt(bzq)(CN)2], where ppy = 2-phenylpyridinate, bzq = 7,8-benzoquinolate, and M = Pt(II) or Pd(II). These hydrated potassium/lithium salts exhibit a change in color upon being heated to 380 K, and they transform back into the original color upon absorption of water molecules from the environment. The challenging characterization of their structure in the vapochromic transition has been carried out by combining several experimental techniques, despite the availability of partially ordered and/or impure crystalline material. Room-temperature single-crystal and powder X-ray diffraction investigation revealed that [K(H2O)][Pt(ppy)(CN)2] crystallizes in the Pbca space group and is isostructural to [K(H2O)][Pd(ppy)(CN)2]. Variable-temperature powder X-ray diffraction allowed the color transition to be related to changes in the diffraction pattern and the decrease in sample crystallinity. Water loss, monitored by thermogravimetric analysis, occurs in two stages, well separated for potassium Pt compounds and strongly overlapped for potassium Pd compounds. The local structure of potassium compounds was monitored by in situ pair distribution function (PDF) measurements, which highlighted changes in the intermolecular distances due to a rearrangement of the crystal packing upon vapochromic transition. A reaction coordinate describing the structural changes was extracted for each compound by multivariate analysis applied to PDF data. It contributed to the study of the kinetics of the structural changes related to the vapochromic transition, revealing its dependence on the transition metal ion. Instead, the ligand influences the critical temperature, higher for ppy than for bzq, and the inclination of the molecular planes with respect to the unit cell planes, higher for bzq than for ppy. The first stage of water loss triggers a unit cell contraction, determined by the increase in the b axis length and the decrease in the a (for ppy) or c (for bzq) axis lengths. Consequent interplane distance variations and in-plane roto-translations weaken the π-stacking of the room-temperature structure and modify the distances and angles of Pt(II)/Pd(II) chains. The curve describing the intermolecular Pt(II)/Pd(II) distances as a function of temperature, validated by X-ray absorption spectroscopy, was found to reproduce the coordinate reaction determined by the model-free analysis.

Metal-Metal Cooperation in the Oxidation of a Flapping Platinum Butterfly by Haloforms: Experimental and Theoretical Evidence.

The model 1-DFT for the butterfly complex [{Pt(C∧C*)(µ-pz)}2] (1; HC∧C* = 1-(4-(ethoxycarbonyl)phenyl)-3-methyl-1H-imidazol-2-ylidene) shows two minima in the potential energy surface of the ground state in acetone solution: the butterfly-wing-spreading molecules 1-s, (dPt-Pt ≈ 3.20 Å) and the wing-folding molecules 1-f (dPt-Pt ≤ 3.00 Å). Both minima are very close in energy (ΔG° = 1.7 kcal/mol) and are connected through a transition state, which lies only 1.9 kcal/mol above 1-s and 0.2 kcal/mol above 1-f. These very low barriers support a fast interconversion process, resembling a butterfly flapping, and the presence of both conformers in acetone solution. However, the 1-f ratio is so low that it is undetectable in the excitation and emission spectra of 1 in 2-MeTHF of diluted solutions (10-5 M) at 77 K, while it is seen in more concentrated solutions (10-3 M). In acetone solution, 1 undergoes a [2c, 2e] oxidation by CHX3 (X = Cl, Br) in the sunlight to render the Pt2(III,III) compounds [{Pt(C∧C*)(µ-pz)X)}2] (X = Cl (2-Cl), Br (2-Br)). In concentrated solutions, 1 can react with CHCl3 under blue light to give 2-Cl and with CHBr3 in the dark, the latter rendering the compound [BrPt(C∧C*)(µ-pz)2Pt(C∧C*)CHBr2] (3-Br) or mixtures of 2-Br and 3-Br if the reaction is performed under an argon atmosphere or in the air, respectively. Mechanistic studies showed that in concentrated solutions the oxidation processes follow a radical mechanism being the MMLCT-based species 1-f, those which trigger the reaction of 1 with CHBr3 and CHCl3. In the ground state (S0f), it promotes the thermal oxidation of 1 by CHBr3 and in the first singlet excited state (S1f) the blue-light-driven photooxidation of 1 by CHCl3. Complexes, 2-Cl, 2-Br, and 3-Br were selectively obtained and fully characterized, showing Pt-Pt distances (ca. 2.6 Å) shorter than that of the starting complex, 1. They are, together with the analogous [{Pt(C∧C*)(µ-pz)I)}2] and [IPt(C∧C*)(µ-pz)2Pt(C∧C*)CHI2], the only dinuclear metal-metal-bonded PtIII(µ-pz)2PtIII compounds reported to date.

Highly Photoluminescent Blue Ionic Platinum-Based Emitters.

New cycloplatinated N-heterocyclic carbene (NHC) compounds with chelate diphosphines (P^P) as ancillary ligands: [Pt(R-C^C*)(P^P)]PF6 (R = H, P^P = dppm (1A), dppe (2A), dppbz (3A); R = CN, P^P = dppm (1B), dppe (2B), dppbz (3B)) have been prepared from the corresponding starting material [{Pt(R-C^C*)(µ-Cl)}2] (R = H, A, R = CN, B) and fully characterized. The new compound A has been prepared by a stepwise protocol. The photophysical properties of 1A-3A and 1B-3B have been widely studied and supported by the time-dependent-density functional theory. These compounds show an efficient blue (dppe, dppbz) or cyan (dppm) emission in PMMA films (5 wt %), with photoluminescence quantum yield (PLQY) ranging from 30% to 87% under an argon atmosphere. This emission has been assigned mainly to transitions from 3ILCT [π(NHC) → π*(NHC)] excited states with some 3LL'CT [π(NHC) → π*(P^P)] character. The electroluminescence of these materials in proof-of-concept solution-processed organic light-emitting diodes containing 3A and 3B as dopants was investigated. The CIE coordinates for devices based on 3A (0.22, 0.41) and 3B (0.24, 0.44) fit within the sky blue region.

A double rollover cycloplatinated(ii) skeleton: a versatile platform for tuning emission by chelating and non-chelating ancillary ligand systems.

Described here is the synthesis and characterization of heteroleptic binuclear platinum(ii) complexes of the type [Pt2(µ-bpy-2H)(S^S)2] and [Pt2(µ-bpy-2H)(L)2(X)2], containing a 2,2'-bipyridine-based double rollover cycloplatinated core (Pt(µ-bpy-2H)Pt), in combination with the anionic S^S- chelate ligands di(ethyl)dithiocarbamate (dedtc) and O,O'-di(cyclohexyl)dithiophosphate (dcdtp) or non-chelating L/X ancillary ligands (PPh3/Me, t-BuNC/Me, PPh3/SCN and PPh3/N3). The new complexes were characterized using multinuclear (1H, 31P and 195Pt) NMR spectroscopy and some of them additionally using single crystal X-ray diffraction. The absorption and photoluminescence of the complexes show a strong dependence on the ancillary ligands. Upon excitation at 365 nm, in a CH2Cl2 rigid matrix (77 K), the complexes exhibit structured emission bands with λmax between 488 nm and 525 nm and vibrational spacing around 1350 cm-1, indicating the excited states centered on the cyclometalated ligand (3ILCT) with some mixing 3MLCT characteristics. In the case of the PPh3/N3 complex, a dual emission band (orange color) is observed in the solid state at 298 K for which the low energy band arises from an aggregation-induced emission (AIE). Upon lowering the temperature (77 K), thermochromism is observed (orange to yellow) which is accompanied by the intensification of the high energy band (ligand-centered structured band). Finally, in order to rationalize the obtained photophysical data, complete DFT (density functional theory) and TD-DFT (time-dependent DFT) calculations were performed on the selected complexes.

A Cyclometalated N-Heterocyclic Carbene: The Wings of the First Pt2 (II,II) Butterfly Oxidized by CHI3.

The X-ray study on a single crystal of the butterfly-like complex [{Pt(C^C*)(µ-pz)}2 ] (1), containing a cyclometalated N-heterocyclic carbene ligand as wings (HC^C*=1-(4-(ethoxycarbonyl)phenyl)-3-methyl-1H-imidazol-2-ylidene), showed three molecules in the asymmetric unit with intermetallic separations (Å) of 3.2294(4) (1A), 3.2834(4) (1B), and 3.1208(6) (1C). From the reaction of 1 with excess of CHI3 in the air and the sunlight, complex [{Pt(C^C*)(µ-pz)I)}2 ] (2) (dPt-Pt =2.6079(2) Å) was obtained as the major product, while [IPt(C^C*)(µ-pz)2 Pt(C^C*)CHI2 ] (3) (dPt-Pt =2.6324(3) Å) was obtained as the major product under argon atmosphere in the dark. Experimental and theoretical investigations showed that an easily accessible radical-like mechanism operates under thermal conditions, with dioxygen acting as an efficient radical (R. ) scavenger. The oxidation of a Pt2 (II,II) "butterfly" by CHI3 to give metal-metal bonded Pt2 (III,III) compounds is described now for the first time.

The Use of Cyclometalated NHCs and Pyrazoles for the Development of Fully Efficient Blue PtII Emitters and Pt/Ag Clusters.

New bis-pyrazole complexes [Pt(C^C*)(RpzH)2 ]X, containing a cyclometalated N-heterocyclic carbene ligand (HC^C*=1-(4-(ethoxycarbonyl)phenyl)-3-methyl-1H-imidazol-2-ylidene) were prepared as chloride (X=Cl- , RpzH: 3,5-Me2 pzH 1 a, 4-MepzH 2 a, pzH 3 a), perchlorate (X=ClO4- , 1 b-3 b), or hexafluorophosphate (X=PF6- , RpzH: 3,5-Me2 pzH 1 c) salts. The X-ray structure of 1 a showed that the Cl- anion is trapped by the cation through two N-H⋅⋅⋅Cl bonds. In solution of methanol, acetone and THF at RT, 1 a-3 a coexist in equilibrium with the corresponding [PtCl(C^C*)(RpzH)] (B) and RpzH species. In CH2 Cl2 , this equilibrium takes place just for 2 a and 3 a, but it is completely shifted to the left at 243 and 223 K for 2 a and 3 a, respectively. The low-lying absorption and emission bands were assigned to intraligand (ILCT) charge transfer on the NHC group. Quantum yield measurements in PMMA films revealed that 1 b, 2 b and 1 c are amongst the most efficient blue-light emitters, with values up to 100 %. Proton abstraction from the coordinated 3,5-Me2 pzH in 1 b by NEt3 and replacement by Ag+ afforded a neutral [Pt2 Ag2 ] cluster containing Pt→Ag dative bonds.

Heteroleptic Cycloplatinated N-Heterocyclic Carbene Complexes: A New Approach to Highly Efficient Blue-Light Emitters.

New heteroleptic compounds of platinum(II)-containing cyclometalated N-heterocyclic carbenes, [PtCl(R-C^C*)(PPh3)] [R-CH^C*-κC* = 3-methyl-1-(naphthalen-2-yl)-1H-imidazol-2-ylidene (R-C = Naph; 1A), 1-[4-(ethoxycarbonyl)phenyl]-3-methyl-1H-imidazol-2-ylidene (R = CO2Et; 1B), and [Pt(R-C^C*)(py)(PPh3)]PF6 (py = pyridine; R-C = Naph, 2A; R = CO2Et, 2B], have been prepared and fully characterized. All of them were obtained as the trans-(C*,PPh3) isomer in high yields. The selectivity of their synthesis has been explained in terms of the degree of transphobia (T) of pairs of ligands in trans positions. X-ray diffraction studies on both 2A and 2B revealed that only in 2A, containing a C^C* with a more extended π system, do the molecules assemble themselves into head-to-tail pairs through intermolecular π···π contacts. The photophysical properties of 2A and 2B and those of the related compounds [Pt(NC-C^C*)(PPh3)L]PF6 [NC-CH^C*-κC* = 1-(4-cyanophenyl)-3-methyl-1H-imidazol-2-ylidene; L = pyridine (py; 2C), 2,6-dimethylphenylisocyanide (CNXyl; 3C), and 2-mercapto-1-methylimidazole (MMI; 4C)] have been examined to analyze the influence of the R substituent on R-C^C* (R-C = Naph; R = CO2Et, CN) and that of the ancillary ligands (L) on them. Experimental data and time-dependent density functional theory calculations showed the similarity of the electronic features associated with R-C^C* (R = CN, CO2Et) and their difference with respect to R-C^C* (R-C = Naph). All of the compounds are very efficient blue emitters in poly(methyl methacrylate) films under an argon atmosphere, with QY values ranging from 68% (2B) to 93% (2C). In the solid state, the color of the emission changes to yellowish-orange for compounds 2A (λmax = 600 nm) and 3C (λmax = 590 nm) because of the formation of aggregates through intermolecular π···π interactions. 2C and 3C were chosen to fabricate fully solution-processed electroluminescent devices with blue-light (2C), yellow-orange-light (3C), and white-light (mixtures of 2C and 3C) emission from neat films of the compounds as emitting layers.

White Light Emission from Planar Remote Phosphor Based on NHC Cycloplatinated Complexes.

We report on the generation of bright white luminescence through solid-state illumination of remote phosphors based on novel cycloplatinated N-heterocyclic carbene (NHC) compounds. Following a stepwise protocol we got the new NHC compound [{Pt(µ-Cl)(C(∧)C*)}2] (4) (HC(∧)C*-κC* = 1-(4-(ethoxycarbonyl)phenyl)-3-methyl-1H-imidazol-2-ylidene), which was used together with the related ones 4a (HC(∧)C*-κC*= 1-(4-cyanophenyl)-3-methyl-1H-imidazol-2-ylidene) and 4b (HC(∧)C*-κC*= 3-methyl-1-(naphthalen-2-yl)-1H-imidazol-2-ylidene) as starting materials for the synthesis of the new ionic derivatives [Pt(R-C(∧)C*) (CNR')2]PF6 (R = -COOEt, R' = t-Bu (5), Xyl (6); R = -CN, R' = t-Bu (7), Xyl (8); R(∧)C = Naph, R' = t-Bu (9), Xyl (10)). The X-ray structures of 6 and 8-10 have been determined. The photophysical properties of these cationic compounds have been studied and supported by the time-dependent-density functional theory (TD-DFT) calculations. The compounds 5, 8, and 9 have been revealed as the most efficient emitters in the solid state with quantum yields of 41%, 21%, and 40%, respectively. White-light remote-phosphors have been prepared just by stacking different combinations of these compounds and [Pt(bzq) (CN) (CN(t)Bu)] (R1) as blue (5, 8), yellow (9), and red (R1) components onto the same substrate. The CCT (correlated color temperature) and the CRI (color rendering index) of the emitted white-light have been tuned by accurately controlling the individual contributions.

Exploring the Transphobia Effect on Heteroleptic NHC Cycloplatinated Complexes.

The synthesis of 1-(4-cyanophenyl)-1H-imidazol (1) has been carried out by an improved method. Then its corresponding imidazolium iodide salt, 2, has been used to prepare the N-heterocyclic carbene (NHC) cycloplatinated compound [{Pt(µ-Cl)(C^C*)}2] (4) (HC^C*-κC* = 1-(4-cyanophenyl)-3-methyl-1H-imidazol-2-ylidene) following a step-by-step protocol. The intermediate complex [PtCl(η(3)-2-Me-C3H4) (HC^C*-κC*)] (3) has also been isolated and characterized. Using 4 as precursor, several heteroleptic complexes of stoicheometry [PtCl(C^C*)L] (L = PPh3 (5), pyridine (py, 6), 2,6-dimethylphenyl isocyanide (CNXyl, 7), and 2-mercapto-1-methylimidazole (MMI, 8)) and [Pt(C^C*)LL']PF6 (L = PPh3, L' = py (9), CNXyl (10), and MMI (11)) have been synthesized. Complexes 6-8 were obtained as a mixture of cis- and trans-(C*,L) isomers, while trans-(C*,L) isomer was the only one observed for complexes 5 and 9-11. Their geometries have been discussed in terms of the degree of transphobia (T) of pairs of trans ligands and supported by theoretical calculations. The trans influence of the two σ Pt-C bonds present in these molecules, Pt-C(Ar) and Pt-C*(NHC), has been compared from the J(Pt-P) values observed in the new complex [Pt(C^C*)(dppe)]PF6 (dppe = 1, 2-bis(diphenylphosphino)ethane, 12).

Selective turn-off phosphorescent and colorimetric detection of mercury(II) in water by half-lantern platinum(II) complexes.

The platinum(ii) half-lantern dinuclear complexes [{Pt(bzq)(µ-C7H4NS2-κN,S)}2] () and [{Pt(bzq)(µ-C7H4NOS-κN,S)}2] () [bzq = benzo[h]quinolinate, C7H4NS2 = 2-mercaptobenzothiazolate, C7H4NOS = 2-mercaptobenzoxazolate] in solution of DMSO-H2O undergo a dramatic color change from yellowish-orange to purple and turn-off phosphorescence in the presence of a small amount of Hg(2+), being discernible by the naked-eye and by spectroscopic methods. Other metal ions as Ag(+), Li(+), Na(+), K(+), Ca(2+), Mg(2+), Ba(2+), Pb(2+), Cd(2+), Zn(2+) and Tl(+) were tested and, even in a big excess, showed no interference in the selective detection of Hg(2+) in water. Job's plot analysis indicated a 1 : 1 stoichiometry in the complexation mode of Hg(2+) by /. The phosphorescence quenching attributed to the formation of [/ : Hg(2+)] complexes showed binding constants of K = 1.13 × 10(5) M(-1) () and K = 1.99 × 10(4) M(-1) (). The limit of detection has been also evaluated. In addition, dried paper test strips impregnated in DMSO solutions of and can detect concentration of Hg(2+) in water as low as 1 × 10(-5) M for and 5 × 10(-5) M for , making these complexes good candidates to be used as real-time Hg(2+) detectors. The nature of the interaction of the Pt2 half-lantern complex with the Hg(2+) cation, has been investigated by theoretical calculations.

Stepwise strategy to cyclometallated Pt(II) complexes with N-heterocyclic carbene ligands: a luminescence study on new ß-diketonate complexes.

The imidazolium salt 3-methyl-1-(naphthalen-2-yl)-1H-imidazolium iodide (2) has been treated with silver(I) oxide and [{Pt(µ-Cl)(η(3)-2-Me-C3H4)}2] (η(3)-2-Me-C3H4 = η(3)-2-methylallyl) to give the intermediate N-heterocyclic carbene complex [PtCl(η(3)-2-Me-C3H4)(HCC*-κC*)] (3) (HCC*-κC* = 3-methyl-1-(naphthalen-2-yl)-1H-imidazol-2-ylidene). Compound 3 undergoes regiospecific cyclometallation at the naphthyl ring of the NHC ligand to give the five-membered platinacycle compound [{Pt(µ-Cl)(CC*)}2] (4). Chlorine abstraction from 4 with ß-diketonate Tl derivatives rendered the corresponding neutral compounds [Pt(CC*)(L-O,O')] {L = acac (HL = acetylacetone) 5, phacac (HL = 1,3-diphenyl-1,3-propanedione) 6, hfacac (HL = hexafluoroacetylacetone) 7}. All of the compounds (3-7) were fully characterized by standard spectroscopic and analytical methods. X-ray diffraction studies were performed on 5-7, revealing short Pt-Pt and π-π interactions in the solid-state structure. The influence of the R-substituents of the ß-diketonate ligand on the photophysical properties and the use of the most efficient emitter, 5, as phosphor converter has also been studied.

Luminescent benzoquinolate-isocyanide platinum(II) complexes: effect of Pt⋠⋠⋠Pt and π⋠⋠⋠π interactions on their photophysical properties.

The neutral compounds [Pt(bzq)(CN)(CNR)] (R = tBu (1), Xyl (2), 2-Np (3); bzq = benzoquinolate, Xyl = 2,6-dimethylphenyl, 2-Np = 2-napthyl) were isolated as the pure isomers with a trans-C(bzq),CNR configuration, as confirmed by (13)C{(1)H} NMR spectroscopy in the isotopically marked [Pt(bzq)((13)CN)(CNR)] (R = tBu (1'), Xyl (2'), 2-Np (3')) derivatives (δ(13)C(CN) ≈ 110 ppm; (1) J(Pt,(13)C) ≈ 1425 Hz]. By contrast, complex [Pt(bzq)(C≡CPh)(CNXyl)] (4) with a trans-N(bzq),CNR configuration, has been selectively isolated from [Pt(bzq)Cl(CNXyl)] (trans-N(bzq),CNR) using Sonogashira conditions. X-ray diffraction studies reveal that while 1 adopts a columnar-stacked chain structure with Pt-Pt distances of 3.371(1) Šand significant π⋅⋅⋅π interactions (3.262 Å), complex 2 forms dimers supported only by short Pt⋅⋅⋅Pt (3.370(1) Å) interactions. In complex 4 the packing is directed by weak bzq⋅⋅⋅Xyl and bzq⋅⋅⋅C≡E (C, N) interactions. In solid state at room temperature, compounds 1 and 2 both show a bright red emission (ϕ = 42.1% 1, 57.6% 2). Luminescence properties in the solid state at 77 K and concentration-dependent emission studies in CH(2)Cl(2) at 298 K and at 77 K are also reported for 1-4.

New dicyano cyclometalated compounds containing Pd(II)-Tl(I) bonds as building blocks in 2D extended structures: synthesis, structure, and luminescence studies.

New mixed metal complexes [PdTl(C^N)(CN)(2)] [C^N = 7,8-benzoquinolinate (bzq, 3); 2-phenylpyridinate (ppy, 4)] have been synthesized by reaction of their corresponding precursors (NBu(4))[Pd(C^N)(CN)(2)] [C^N = bzq (1), ppy (2)] with TlPF(6). Compounds 3 and 4 were studied by X-ray diffraction, showing the not-so-common Pd(II)-Tl(I) bonds. Both crystal structures exhibit 2-D extended networks fashioned by organometallic "PdTl(C^N)(CN)(2)" units, each one containing a donor-acceptor Pd(II)-Tl(I) bond, which are connected through additional Tl···N≡C contacts and weak Tl···π (bzq) contacts in the case of 3. Solid state emissions are red-shifted compared with those of the precursors and have been assigned to metal-metal'-to-ligand charge transfer (MM'LCT [d/s σ*(Pd,Tl) → π*(C^N)]) mixed with some intraligand ((3)IL[π(C^N) → π*(C^N)]) character. In diluted solution either at room temperature or 77 K, the Pd-Tl bond is no longer retained as confirmed by mass spectrometry, NMR, and UV-vis spectroscopic techniques.

Highly luminescent half-lantern cyclometalated platinum(II) complex: synthesis, structure, luminescence studies, and reactivity.

The half-lantern compound [{Pt(bzq)(µ-C(7)H(4)NS(2)-κN,S)}(2)]·Me(2)CO (1) was obtained by reaction of equimolar amounts of potassium 2-mercaptobenzothiazolate (KC(7)H(4)NS(2)) and [Pt(bzq)(NCMe)(2)]ClO(4). The Pt(II)···Pt(II) separation in the neutral complex [{Pt(bzq)(µ-C(7)H(4)NS(2)-κN,S)}(2)] is 2.910 (2) Å, this being among the shortest observed in half-lantern divalent platinum complexes. Within the complex, the benzo[h]quinoline (bzq) groups lie in close proximity with most C···C distances being between 3.3 and 3.7 Å, which is indicative of significant π-π interactions. The reaction of 1 with halogens X(2) (X(2) = Cl(2), Br(2), or I(2)) proceeds with a two-electron oxidation to give the corresponding dihalodiplatinum(III) complexes [{Pt(bzq)(µ-C(7)H(4)NS(2)-κN,S)X}(2)] (X = Cl 2, Br 3, I 4). Their X-ray structures confirm the retention of the half-lantern structure and the coordination mode of the bzq and the bridging ligand µ-C(7)H(4)NS(2)-κN,S. The Pt-Pt distances (Pt-Pt = 2.6420(3) Å 2, 2.6435(4) Å 3, 2.6690(3) Å 4) are shorter than that in 1 because of the Pt-Pt bond formation. Time dependent-density functional theory (TD-DFT) studies performed on 1 show a formal bond order of 0 between the metal atoms, with the 6p(z) contribution diminishing the antibonding character of the highest occupied molecular orbital (HOMO) and being responsible for an attractive intermetallic interaction. A shortening of the Pt-Pt distance from 2.959 Å in the ground state S(0) to 2.760 Å in the optimized first excited state (T(1)) is consistent with an increase in the Pt-Pt bond order to 0.5. In agreement with TD-DFT calculations, the intense, structureless, red emission of 1 in the solid state and in solution can be mainly attributed to triplet metal-metal-to-ligand charge transfer ((3)MMLCT) [dσ*(Pt-Pt) → π*(bzq)] excited states. The high quantum yields of this emission measured in toluene (44%) and solid state (62%) at room temperature indicate that 1 is a very efficient and stable (3)MMLCT emitter, even in solution. The high luminescence quantum yield of its red emission, added to its neutral character and the thermal stability of 1, make it a potential compound to be incorporated as phosphorescent dopant in multilayer organic light-emitting devices (OLEDs).

Pt-Ag clusters and their neutral mononuclear Pt(II) starting complexes: structural and luminescence studies.

The mononuclear complexes [Pt(bzq)(S^S)] [S^S = pyrrolidinedithiocarbamate (pdtc 1), dimethyldithiocarbamate (dmdtc 2)] were prepared by reaction of [Pt(bzq)(NCMe)(2)]ClO(4) with an equimolecular amount of [NH(4)(pdtc)] and [Na(dmdtc)·2H(2)O] respectively in MeOH. Reactions of 1 and 2 with AgClO(4) in 1 : 1 and 2 : 1 molar ratios rendered the heteropolinuclear compounds [{Pt(bzq)(S^S)Ag}(2)](ClO(4))(2) (S^S = pdtc 3, dmdtc 4) and [{Pt(bzq)(S^S)}(2)Ag](ClO(4)) (S^S = pdtc 5, dmdtc 6) respectively. The X-ray studies on single crystals of 3 and 4 showed that both consist of tetranuclear [Pt(2)Ag(2)] clusters with the Pt-Ag and the Ag-Ag distances in the range of those corresponding to Pt-Ag dative bonds and argentophilic interactions. In 3 the tetranuclear [Pt(2)Ag(2)] clusters are connected into infinite polymeric chains by Pt···Pt metallophilic interactions (Pt···Pt = 3.1890(7) Å). The X-ray study on a single crystal of 5 showed that it is a polymer based on trinuclear [Pt(2)Ag] clusters containing two unsupported Pt-Ag dative bonds and connected by Ag-S bonds in such a way that the "Pt-Ag-S-Pt-Ag-S" atoms draw a zigzag polymeric chain. TD-DFT calculations carried out for 1 indicate that the lowest energy absorption band in CH(2)Cl(2) can be described as a mixture of (1)MLCT, (1)IL and (1)L'LCT transitions. Powdered samples of 1 at 298 K and 77 K show a green-yellow emission band coming mainly from a (3)LC excited state. However complex 2 shows "luminescence thermochromism": the colour of its luminescence changes from green-yellow at 77 K to orange-red at 298 K. The emission of the Pt-Ag clusters, 3-6, in the solid state, are due to excimeric (3)ππ and/or (3)MMLCT (dσ* →π*) low-lying excited states, indicating that the presence of silver in the clusters makes the "Pt(bzq)(S^S)" fragments interact to a large extent through Pt···Pt and/or π-π interactions. Solid 3 is a highly selective vapochromic compound towards acetonitrile although this behaviour is not fully reversible.

Structural and luminescence studies on pi...pi and Pt...Pt interactions in mixed chloro-isocyanide cyclometalated platinum(II) complexes.

[Pt(bzq)Cl(CNR)] [bzq = benzoquinolinate; R = tert-butyl ((t)Bu 1), 2-6-dimethylphenyl (Xyl 2), 2-naphthyl (2-Np 3)] complexes have been synthesized and structurally and photophysically characterized. 1 was found to co-crystallize in two distinct pseudopolymorphs: a red form, which exhibits an infinite 1D-chain ([1](infinity)) and a yellow form, which contains discrete dimers ([1](2)), both stabilized by interplanar pi...pi (bzq) and short Pt...Pt bonding interactions. Complex 3, generated through the unexpected garnet-red double salt isomer [Pt(bzq)(CN-2-Np)(2)][Pt(bzq)Cl(2)] 4, crystallizes as yellow Pt...Pt dimers ([3](2)), while 2 only forms pi...pi (bzq) contacting dimers. Their electronic absorption and luminescence behaviors have been investigated. According to Time-Dependent Density Functional Theory (TD-DFT) calculations, the lowest-lying absorption (CH(2)Cl(2)) has been attributed to combined (1)ILCT and (1)MLCT/(1)ML'CT (L = bzq, L' = CNR) transitions, the latter increasing from 1 to 3. In solid state, while the yellow form [1](2) exhibits a green (3)MLCT unstructured emission only at 77 K, the 1-D form [1](infinity) displays a characteristic low-energy red emission (672 nm, 298 K; 744 nm, 77 K) attributed to a mixed (3)MMCT [d(sigma*)-->p(sigma)]/(3)MMLCT [dsigma*(M(2))-->sigma(pi*)(bzq)] excited state. However, upon exposure to standard atmospheric conditions, [1](infinity) shows an irreversible change to an orange-ochre solid, whose emissive properties are similar to those of the crude 1. Complexes 2 and 3 (77 K) exhibit a structured emission from discrete fragments ((3)LC/(3)MLCT), whereas the luminescence of the garnet-red salt 4 is dominated by a low energy emission (680 nm, 298 K; 730 nm, 77 K) arising from a (3)MMLCT excited state. Solvent (CH(2)Cl(2), toluene, 2-MeTHF and CH(3)CN) and concentration-dependent emission studies at 298 K and at 77 K are also reported for 1-3. In CH(2)Cl(2) solution, the low phosphorescent emission band is ascribed to bzq intraligand charge transfer (3)ILCT mixed with metal-to-ligand (L = bzq, L' = CNR) charge transfer (3)MLCT/(3)ML'CT character with the Pt to CNR contribution increasing from 1 to 3, according to computational studies.