DPPM-Bridged Binuclear Pt(II) Pincer Complexes: Chemistry, Structure, and Photophysics in Solution Revisited.

A series of luminescent binuclear ([dppm{Pt(NNC)}2]2+) and mononuclear ([PPh3Pt(NNC)]+) complexes containing pincer ligands were synthesized and characterized. Photophysical characteristics of both types of complexes were studied in dichloromethane solution. In the solid phase, the binuclear compounds adopt a syn configuration where the {Pt(NNC)} fragments are held together due to intramolecular Pt-Pt bonding and π-stacking of the pincer ligand aromatic systems. Analysis of the complexes' molecular structure in solution by multinuclear NMR spectroscopy showed that the stacked intramolecular configuration is retained in fluid media, which is in complete agreement with a considerable red shift of the emission wavelength due to formation of the intramolecular Pt-Pt bond, leading to the transformation of an emissive excited state to 3MMLCT. It was also found that triethylamine quenches the emission of both types of complexes; the mechanism of quenching is a combination of dynamic and static channels of excited-state deactivation. In the case of binuclear complexes, deprotonation of the dppm methylene bridge by triethylamine also contributes to the chromophore quenching. To explain the observed chemistry of binuclear complex interactions with Et3N, a chemical equilibrium scheme was suggested, which was confirmed by quantitative monitoring of the 31P signal variations as a function of triethylamine concentration.

Unusual Effects of the Metal Center Coordination Mode on the Photophysical Behavior of the Rhenium(I) and Rhenium(I)-Iridium(III) Complexes.

Binuclear transition-metal complexes based on conjugated systems containing coordinating functions are potentially suitable for a wide range of applications, including light-emitting materials, sensors, light-harvesting systems, photocatalysts, etc., due to energy-transfer processes between chromophore centers. Herein we report on the synthesis, characterization, photophysical, and theoretical studies of relatively rare rhenium(I) and rhenium(I)-iridium(III) dyads prepared by using the nonsymmetrical polytopic ligands (NN2 and NN3) with the strongly conjugated phenanthroline and imidazole-quinoline/pyridine coordinating fragments. Availability of these different diimine chelating functions and targeted synthetic procedures allowed one to obtain a series of mononuclear (Re and Ir) and binuclear (Re-Re and Re-Ir) metal complexes with various modes of {Re(CO)3Cl} and {Ir(NC)2} metal fragment coordination. The obtained compounds were characterized by 1D 1H and 2D (COSY and NOESY) NMR spectroscopy, mass spectrometry, elemental analysis, and X-ray diffraction crystallography. The photophysical study of the complexes (absorption, excitation and emission spectra, quantum yields, and excited-state lifetimes) showed that their emission parameters display strong dependence on the manner of metal center coordination to the diimine bidentate functions. The mononuclear complexes with an unoccupied imidazole-quinoline/pyridine fragment [Re(NN2), Re(NN3), and Ir(NC2)2(NN2)] or those containing a coordinated {Ir(NC)2} fragment in this position [Ir(NC2)2(NN1) and Re(NN2)Ir(NC1)2-Re(NN2)Ir(NC4)2] exhibit moderate-to-intense phosphorescence (quantum yields vary from 3% to 56% in a degassed solution), whereas the complexes containing a {Re(CO)3Cl} moiety in the imidazole-quinoline/pyridine position [Re2(NN2), Re2(NN3), and Ir(NC2)2(NN2)Re] demonstrate a strong reduction in the phosphorescence efficiency with a quantum yield of ≪0.1%. Quenching of the phosphorescence in the latter types of emitters is discussed in terms of a strong decrease in the radiative rate constants for these complexes compared to their analogues mentioned above, while the nonradiative constants remain nearly unchanged. Theoretical density functional theory (DFT) and time-dependent DFT (TD DFT) calculations, including evaluation of the radiative rate constants for the couple of structurally analogous complexes with and without a {Re(CO)3Cl} moiety coordinated to the imidazole-quinoline/pyridine chelating function, confirmed the observed trend in the variation of the emission intensity.

Cyclometalated platinum(II) complexes with acyclic diaminocarbene ligands for OLED application.

A novel series of cyclometalated platinum(II) complexes bearing acyclic diaminocarbene (ADC) ancillary ligands were designed and prepared. Their photophysical properties were systematically studied through experimental and theoretical investigations. All complexes exhibit green phosphorescence with a quantum efficiency of up to 45% in 2 wt% doped PMMA film at room temperature. The complexes are used as light-emitting dopants for organic light-emitting diode (OLED) fabrication. The devices displayed a green emission with a maximum current efficiency of 2.9 cd A-1 and a luminance of 2700 cd m-2. These results show that these cyclometalated platinum(II) complexes can be used as efficient green emitting components of OLED devices.

Investigation of the N

A series of bis-metalated phosphorescent [(N^C)2Ir(bipyridine)]+ complexes with systematic variations in the structure and electronic characteristics of the N^C ligands were synthesized and characterized by using elemental analysis, mass spectrometry, NMR spectroscopy and X-ray crystallography. Investigation of the complexes' spectroscopic properties together with DFT and TD DFT calculations revealed that metal-to-ligand charge transfer (MLCT) and intraligand (LC) transition play key roles in the generation of emissive triplet states. According to the results of theoretical studies, the 3LC excited state is more accurate to consider as an intraligand charge transfer process (ILCT) between N- and C-coordinated moieties of the N^C chelate. This hypothesis is completely in line with the trends observed in the experimental absorption and emission spectra, which display systematic bathochromic shifts upon insertion of electron-withdrawing substituents into the N-coordinated fragment. An analogous shift is induced by expansion of the aromatic system of the C-coordinated fragment and insertion of polarizable sulfur atoms into the aromatic rings. These experimental and theoretical findings extend the knowledge of the nature of photophysical processes in complexes of this type and provide useful instruments for fine-tuning of their emissive characteristics.

Rhenium(I) Block Copolymers Based on Polyvinylpyrrolidone: A Successful Strategy to Water-Solubility and Biocompatibility.

A series of diphosphine Re(I) complexes Re1-Re4 have been designed via decoration of the archetypal core {Re(CO)2(N^N)} through the installations of the phosphines P0 and P1 bearing the terminal double bond, where N^N = 2,2'-bipyridine (N^N1), 4,4'-di-tert-butyl-2,2'-bipyridine (N^N2) or 2,9-dimethyl-1,10-phenanthroline (N^N3) and P0 = diphenylvinylphosphine, and P1 = 4-(diphenylphosphino)styrene. These complexes were copolymerized with the corresponding N-vinylpyrrolidone-based Macro-RAFT agents of different polymer chain lengths to give water-soluble copolymers of low-molecular p(VP-l-Re) and high-molecular p(VP-h-Re) block-copolymers containing rhenium complexes. Compounds Re1-Re4, as well as the copolymers p(VP-l-Re) and p(VP-h-Re), demonstrate phosphorescence from a 3MLCT excited state typical for this type of chromophores. The copolymers p(VP-l-Re#) and p(VP-h-Re#) display weak sensitivity to molecular oxygen in aqueous and buffered media, which becomes almost negligible in the model physiological media. In cell experiments with CHO-K1 cell line, p(VP-l-Re2) and p(VP-h-Re2) displayed significantly reduced toxicity compared to the initial Re2 complex and internalized into cells presumably by endocytic pathways, being eventually accumulated in endosomes. The sensitivity of the copolymers to oxygen examined in CHO-K1 cells via phosphorescence lifetime imaging microscopy (PLIM) proved to be inessential.

Hybrid Inorganic-Organic Complexes of Zn, Cd, and Pb with a Cationic Phenanthro-diimine Ligand.

The phosphonium-decorated phenanthro-imidazolyl pyridine ligand, LP+Br, readily reacts with zinc(II) and cadmium(II) bromides to give inorganic-organic zero-dimensional compounds [LP+ZnBr2]2[ZnBr4] (1) and [(LP+)2Cd2Br4][CdBr4] (2), respectively, upon crystallization. These salts are moderately fluorescent in the solid state under ambient conditions (λem = 458 nm, Φem = 0.11 for 1; λem = 460 nm, Φem = 0.13 for 2). Their emission results from spin-allowed electronic transitions localized on the organic component with the negligible effect of [MBr4]2- and MBr2 units. Contrary to ionic species 1 and 2, lead(II) bromide affords a neutral and water-stable complex [(LP+)2Pb3Br8] (3), showing weak room-temperature phosphorescence arising from spin-orbit coupling due to the heavy atom effect. The emission, which is substantially enhanced for the amorphous sample of 3 (λem = 575 nm, Φem = 0.06), is assigned to the intraligand triplet excited state, which is a rare phenomenon among Pb(II) molecular materials.

Functionalizing Collagen with Vessel-Penetrating Two-Photon Phosphorescence Probes: A New In Vivo Strategy to Map Oxygen Concentration in Tumor Microenvironment and Tissue Ischemia.

The encapsulation and/or surface modification can stabilize and protect the phosphorescence bio-probes but impede their intravenous delivery across biological barriers. Here, a new class of biocompatible rhenium (ReI ) diimine carbonyl complexes is developed, which can efficaciously permeate normal vessel walls and then functionalize the extravascular collagen matrixes as in situ oxygen sensor. Without protective agents, ReI -diimine complex already exhibits excellent emission yield (34%, λem   = 583 nm) and large two-photon absorption cross-sections (σ2   = 300 GM @ 800 nm) in water (pH 7.4). After extravasation, remarkably, the collagen-bound probes further enhanced their excitation efficiency by increasing the deoxygenated lifetime from 4.0 to 7.5 µs, paving a way to visualize tumor hypoxia and tissue ischemia in vivo. The post-extravasation functionalization of extracellular matrixes demonstrates a new methodology for biomaterial-empowered phosphorescence sensing and imaging.

Modulation of Metallophilic and π-π Interactions in Platinum Cyclometalated Luminophores with Halogen Bonding.

Luminescent cyclometalated complexes [M(C^N^N)CN] (M=Pt, Pd; HC^N^N=pyridinyl- (M=Pt 1, Pd 5), benzyltriazolyl- (M=Pt 2), indazolyl- (M=Pt 3, Pd 6), pyrazolyl-phenylpyridine (M=Pt 4)) decorated with cyanide ligand, have been explored as nucleophilic building blocks for the construction of halogen-bonded (XB) adducts using IC6 F5 as an XB donor. The negative electrostatic potential of the CN group afforded CN⋅⋅⋅I noncovalent interactions for platinum complexes 1-3; the energies of XB contacts are comparable to those of metallophilic bonding according to QTAIM analysis. Embedding the chromophore units into XB adducts 1-3⋅⋅⋅IC6 F5 has little effect on the charge distribution, but strongly affects Pt⋅⋅⋅Pt bonding and π-stacking, which lead to excited states of MMLCT (metal-metal-to-ligand charge transfer) origin. The energies of these states and the photoemissive properties of the crystalline materials are primarily determined by the degree of aggregation of the luminophores via metal-metal interactions. The adduct formation depends on the nature of the metal and the structure of the metalated ligand, the variation of which can yield dynamic XB-supported systems, exemplified by thermally regulated transition 3↔3⋅⋅⋅IC6 F5 .

Supramolecular Construction of Cyanide-Bridged ReI Diimine Multichromophores.

The reactions of labile [Re(diimine)(CO)3(H2O)]+ precursors (diimine = 2,2'-bipyridine, bpy; 1,10-phenanthroline, phen) with dicyanoargentate anion produce the dirhenium cyanide-bridged compounds [{Re(diimine)(CO)3}2CN)]+ (1 and 2). Substitution of the axial carbonyl ligands in 2 for triphenylphosphine gives the derivative [{Re(phen)(CO)2(PPh3)}2CN]+ (3), while the employment of a neutral metalloligand [Au(PPh3)(CN)] affords heterobimetallic complex [{Re(phen)(CO)3}NCAu(PPh3)]+ (4). Furthermore, the utilization of [Au(CN)2]-, [Pt(CN)4]2-, and [Fe(CN)6]4-/3- cyanometallates leads to the higher nuclearity aggregates [{Re(diimine)(CO)3NC} xM] m+ (M = Au, x = 2, 5 and 6; Pt, x = 4, 7 and 8; Fe, x = 6, 9 and 10). All novel compounds were characterized crystallographically. Assemblies 1-8 are phosphorescent both in solution and in the solid state; according to the DFT analysis, the optical properties are mainly associated with charge transfer from Re tricarbonyl motif to the diimine fragment. The energy of this process can be substantially modified by the properties of the ancillary ligands that allows to attain near-IR emission for 3 (λem = 737 nm in CH2Cl2). The Re-FeII/III complexes 9 and 10 are not luminescent but exhibit low energy absorptions, reaching 846 nm (10) due to ReI → FeIII transition.

Chromophore-Functionalized Phenanthro-diimine Ligands and Their Re(I) Complexes.

A series of diimine ligands has been designed on the basis of 2-pyridyl-1 H-phenanthro[9,10- d]imidazole (L1, L2). Coupling the basic motif of L1 with anthracene-containing fragments affords the bichromophore compounds L3-L5, of which L4 and L5 adopt a donor-acceptor architecture. The latter allows intramolecular charge transfer with intense absorption bands in the visible spectrum (lowest λabs 464 nm (ε = 1.2 × 104 M-1 cm-1) and 490 nm (ε = 5.2 × 104 M-1 cm-1) in CH2Cl2 for L4 and L5, respectively). L1-L5 show strong fluorescence in a fluid medium (Φem = 22-92%, λem 370-602 nm in CH2Cl2); discernible emission solvatochromism is observed for L4 and L5. In addition, the presence of pyridyl (L1-L5) and dimethylaminophenyl (L5) groups enables reversible alteration of their optical properties by means of protonation. Ligands L1-L5 were used to synthesize the corresponding [Re(CO)3X(diimine)] (X = Cl, 1-5; X = CN, 1-CN) complexes. 1 and 2 exhibit unusual dual emission of singlet and triplet parentage, which originate from independently populated 1ππ* and 3MLCT excited states. In contrast to the majority of the reported Re(I) carbonyl luminophores, complexes 3-5 display moderately intense ligand-based fluorescence from an anthracene-containing secondary chromophore and complete quenching of emission from the 3MLCT state presumably due to the triplet-triplet energy transfer (3MLCT → 3ILCT).

Linking ReI and PtII Chromophores with Aminopyridines: A Simple Route to Achieve a Complicated Photophysical Behavior.

The bifunctional aminopyridine ligands H2 N-(CH2 )n -4-C5 H4 N (n=0, L1; 1, L2; 2, L3) have been utilized for the preparation of the rhenium complexes [Re(phen)(CO)3 (L1-L3)]+ (1-3; phen=phenanthroline). Complexes 2 and 3 with NH2 -coordinated L2 and L3, respectively, were coupled with cycloplatinated motifs {Pt(ppy)Cl} and {Pt(dpyb)}+ (ppy=2-phenylpyridine, dpyb=dipyridylbenzene) to give the bimetallic species [Re(phen)(CO)3 (µ-L2/L3)Pt(ppy)Cl]+ (4, 6) and [Re(phen)(CO)3 (µ-L2/L3)Pt(dpyb)]2+ (5, 7). In solution, complexes 4 and 6 show 3 MLCT {Re}-based emission at 298 K, which changes to the 3 IL(ppy) state at 77 K. The photophysical properties of compounds 5 and 7 display a pronounced concentration dependence, presumably due to the formation of bimolecular aggregates. Analysis of the spectroscopic data, combined with TD-DFT simulations, suggest that unconventional heteroleptic {Re(phen)}⋅⋅⋅{Pt(dpyb)} π-π stacking operates as the driving force for ground-state association. The latter, together with intra- and intermolecular energy-transfer processes, determines the appearance of multiple emission bands and results in nonlinear relaxation kinetics of the excited states.