Aggregation Game: Changing Solid-State Emission Using Different Counterions in Monoalkynylphosphonium Pt(II) Complexes.

Two series of heteroleptic monoalkynylphosphonium Pt(II) complexes decorated with 2,2':6',2''-terpyridine (terpy, N series) and 6-phenyl-2,2'-bipyridine (phbpy, C series) ligands, were prepared and characterized by spectroscopic methods. The complexes obtained exhibit triplet emission in solution, and the characteristics inside the series depend on the nature of the alkynylphosphonium ligand. The description of electronic transitions responsible for energy absorption and emission in discrete Pt(II) complexes was made on the basis of a detailed analysis of the results of DFT calculations, and has shown to involve MLCT, ILCT, and LLCT transitions. The complexes of both series exhibit triplet solid-state luminescence with parameters that also depend on the composition of the complexes, and the analysis of the experimental data indicates the realization of LC, MLCT, MMLCT, and MC transitions due to Pt⋯Pt metallophilic interactions and matrix rigidity. It was shown that the anion variation leads to a significant difference in the photophysical characteristics of the N complexes, which exhibit a smooth dependence of the luminescent properties on the anion size. Using quantum chemical modeling, it is demonstrated how the anion size influences the Pt⋯Pt distance in the solid state.

Cationic or Neutral: Dependence of Photophysical Properties of Bis-alkynylphosphonium Pt(II) Complexes on Ancillary Ligand.

A series of D-π-A alkynylphosphonium salts with different linker between donor and acceptor groups was used to synthesize two series of trans-bis-alkynylphosphonium Pt(II) complexes with different ancillary ligands (triphenylphosphine, P series, and cyanide, CN series). The nature of the ancillary ligand manages the overall charge and emission properties of the complexes obtained. In addition, the variation of the linker in alkynylphosphonium ligands allows fine-tuning the luminescence wavelength. Dicationic series P is unstable in solution under UV excitation, whereas in the solid state, these complexes are the first example of phosphorescent trans-phosphine-bis-alkynyl Pt(II) compounds. Neutral series CN demonstrates bright emission in solution, including dual emission for 2CN complex with biphenyl linker in alkynylphosphonium ligands. However, in the solid state for the CN series drastic decrease in the emission quantum yield compared to the P series was observed. DFT calculations reveal the complicated emission nature for the both P and CN series with various contributions of 3ILCT, 3LLCT and 3MLCT states. However, in the naphthyl-containing derivatives 3P and 3CN, the dominating 3LC character with some admixture of CT states is postulated.

Alkynylphosphonium Pt(II) Complexes: Synthesis, Characterization, and Features of Photophysical Properties in Solution and in the Solid State.

A series of heteroleptic bis-alkynyl-diimine mononuclear Pt(II) complexes with alkynylphosphonium and di-tert-butyl-2,2'-bipyridine (dtbpy) ligands have been prepared and characterized by spectroscopic methods and single-crystal XRD. The Pt(II) complexes obtained in the present study demonstrate triplet emission in solution, which originates from 3MLCT/3LC states where the nature of the π-conjugated linker in the alkynylphosphonium ligand manages the contributions of each transition, and this conclusion is supported by DFT calculations. Additionally, the presence of the phosphonium group connected to alkynyl through the π-conjugated linker enhances nonlinear optical properties of the Pt(II) complexes increasing two-photon absorption cross section up to 400 GM. In the solid state, the Pt(II) complexes demonstrate emission that is attributed to 3MMLCT transitions due to the presence of Pt-Pt metallophilic interactions, and the reversible assembly and disassembly of these interactions by grinding and solvent treatment are responsible for the mechanochromic luminescence. It has been experimentally shown that stimuli-responsive emission of the Pt(II) complexes is the result of a "monomer/dimer" transformation; this conclusion is confirmed by DFT calculations for discrete complexes and different dimers with or without Pt-Pt interactions.

Homoleptic Alkynylphosphonium Au(I) Complexes as Push-Pull Phosphorescent Emitters.

A series of compounds P1-P4 bearing terminal alkynyl sites connected with a phosphonium group via different π-conjugated linkers have been synthesized. The compounds themselves are efficient push-pull emitters and exhibit bright fluorescence in blue and near-UV regions. P1-P4 were used as alkynyl ligands to obtain a series of homoleptic bis-alkynyl Au(I) complexes 1-4. The complexes demonstrate bright phosphorescence and dual emission with dominating phosphorescence (2-4). Terphenyl derivative complex 3 exhibits warm white emission in DMSO solution and pure white emission in PMMA films. Time-dependent density functional theory calculations have shown that the T1 excited state has a hybrid MLCT/ILCT nature with a dominant contribution of charge transfer across a ligand-centered "D-π-A" system. The variation of linker allows tuning the effect of intermolecular charge transfer and thus changing the electronic and photophysical properties of the organogold "D-π-A" system. The results presented unambiguously display the advances of the conception of organometallic "D-π-A" construction.

Post-Functionalization of Organometallic Complexes via Click-Reaction.

CuAAC (Cu catalyzed azide-alkyne cycloaddition) click-reaction is a simple and powerful method for the post-synthetic modification of organometallic complexes of transition metals. This approach allows the selective introduction of additional donor sites or functional groups to the periphery of the ligand environment. This is especially important if a metalloligand with free donor sites, which are of the same nature as the primary site for the coordination of the primary metal, has to be created. The concept of post-synthetic modification of organometallic complexes by click-reaction is relatively recent and the currently available experimental material does not yet allow us to identify trends and formulate recommendations to address specific problems. In the present study, we have applied the CuAAC reaction for the post-synthetic modification of diimine mononuclear complexes Re(I), Pt(II) and Ir(III) with C≡C bonds at the periphery of the ligand environment and demonstrated that click-chemistry is a powerful tool for the tunable chemical post-synthetic modification of coordination compounds.

So Close, Yet so Different: How One Donor Atom Changes Significantly the Photophysical Properties of Mononuclear Cu(I) Complexes.

The manipulation of the photophysical properties of molecular emitters can be realized by composing the close environment of the metal center with the "heavier pnictogen atom" effect. Replacing a nitrogen atom with a heavier phosphorus atom in otherwise isostructural molecular systems results in a significant change of the photophysical parameters. Herein, we report on the synthesis of four pairs of novel phosphinine-based and isostructural diimine-based Cu(I) complexes, which feature peculiar photophysical properties, and show how these parameters depend on the "heavier pnictogen atom" effect. The obtained Cu(I) complexes show triplet luminescence with MLCT character, which was investigated by means of spectroscopic and computational methods. It has been found that the photophysical properties of the coordination compounds show a dependency on the rigidity of the ancillary phosphine ligand in an unexpected manner. Replacing the nitrogen atom with a heavier phosphorus atom in otherwise isostructural molecular systems results in a significant change in emission energy and especially in the lifetime of the excited state. The results obtained demonstrate an efficient approach to the design of emissive molecular materials, which allows the construction of luminescent complexes with controlled photophysical properties.

The Tail Wags the Dog: The Far Periphery of the Coordination Environment Manipulates the Photophysical Properties of Heteroleptic Cu(I) Complexes.

In this work we show, using the example of a series of [Cu(Xantphos)(N^N)]+ complexes (N^N being substituted 5-phenyl-bipyridine) with different peripheral N^N ligands, that substituents distant from the main action zone can have a significant effect on the physicochemical properties of the system. By using the C≡C bond on the periphery of the coordination environment, three hybrid molecular systems with -Si(CH3)3, -Au(PR3), and -C2HN3(CH2)C10H7 fragments were produced. The Cu(I) complexes thus obtained demonstrate complicated emission behaviour, which was investigated by spectroscopic, electrochemical, and computational methods in order to understand the mechanism of energy transfer. It was found that the -Si(CH3)3 fragment connected to the peripheral C≡C bond changes luminescence to long-lived intra-ligand phosphorescence, in contrast to MLCT phosphorescence or TADF. The obtained results can be used for the design of new materials based on Cu(I) complexes with controlled optoelectronic properties on the molecular level, as well as for the production of hybrid systems.

Just Add the Gold: Aggregation-Induced-Emission Properties of Alkynylphosphinegold(I) Complexes Functionalized with Phenylene-Terpyridine Subunits.

A series of organometallic complexes containing an alkynylphosphinegold(I) fragment and a phenylene-terpyridine moiety connected together by flexible linker have been prepared using the specially designed terpyridine ligands. The compounds were studied crystallographically to reveal that all of them contain a linearly coordinated Au(I) atom and a free terpyridine moiety. The different orientations of the molecules relative to each other in the solid state determine the multiple noncovalent interactions such as antiparallel ππ stacking, CH-π, and CH-Au, but no aurophilic interactions are realized. The organometallic Au(I) complexes obtained show fluorescence in the solution and dual singlet-triplet emission in the solid state. This means that their photophysical behavior is determined by both intermolecular lattice-defined interactions and Au(I) atom introduction. Density functional theory computational analysis supported the assignment of emission to intraligand electronic transitions only inside the phenylene-terpyridine part with no Au(I) involved. In addition, a study of the nature of the excited states for the "dimer" with an antiparallel orientation of the terpyridine fragment showed that this orientation leads to the generation of abstracted singlet and triplet states, lowering their energy in comparison with the monomer complex. Thus, the complexes obtained can be qualified as examples of Au(I)-containing organometallic aggregation-induced-emission luminogens.

Keep it tight: a crucial role of bridging phosphine ligands in the design and optical properties of multinuclear coinage metal complexes.

Copper subgroup metal ions in the +1 oxidation state are classical candidates for aggregation via non-covalent metal-metal interactions, which are supported by a number of bridging ligands. The bridging phosphines, soft donors with a relatively labile coordination to coinage metals, serve as convenient and essential components of the ligand environment that allow for efficient self-assembly of discrete polynuclear aggregates. Simultaneously, accessible and rich modification of the organic spacer of such P-donors has been used to generate many fascinating structures with attractive photoluminescent behavior. In this work we consider the development of di- and polynuclear complexes of M(i) (M = Cu, Ag, Au) and their photophysical properties, focusing on the effect of phosphine bridging ligands, their flexibility and denticity.

Hexavanadate-Organogold(I) Hybrid Compounds: Synthesis by the Azide-Alkyne Cycloaddition and Density Functional Theory Study of an Intriguing Electron Density Distribution.

The fully oxidized Lindqvist-type hexavanadate compounds decorated by phosphine-derivatized Au(I) moieties oriented in a transoid fashion (n-Bu4N)2[V6O13{(OCH2)3CCH2(N3C2C6H5)AuP(C6H4OMe)3}2] (POMNAu) and (n-Bu4N)2[V6O13{(OCH2)3CCH2OCH2(C2N3H)AuP(C6H4OMe)3}2] (POMCAu) have been prepared by azide-alkyne cycloaddition reactions and characterized by various techniques, including NMR, IR, and UV/vis spectroscopy and electrospray ionization mass spectrometry. Electronic structure calculations unveil the potential of these model hybrid junctions for application in controlled charge-transport experiments on substrate surfaces.

Luminescence behaviour of Au(I)-Cu(I) heterobimetallic coordination polymers based on alkynyl-tris(2-pyridyl)phosphine Au(I) complexes.

A set of alkynyl-tris(2-pyridyl)phosphine Au(i) complexes was synthesized and characterized. Free coordination functions on the ligand environment periphery, namely 'scorpionate' PPy3 and the C[triple bond, length as m-dash]C bond, allowed these ditopic metalloligands to be selectively linked to 1D coordination polymers by reaction with Cu(i), which used both Cu-(N-PPy3) and Cu-(η2-C[triple bond, length as m-dash]C) coordination modes. Single-crystal and powder XRD, NMR, and XPS techniques were used to characterize the coordination polymers obtained. Heterobimetallic Au(i)-Cu(i) coordination polymers demonstrate triplet photoluminescence which was studied by spectroscopic and computational methods to understand the pathway of energy transfer inside the chain of linked chromophore centres. The intriguing feature of the electronic structure of heterobimetallic supramolecular assemblies is the 'long-distance' electronic transition involving PhC2 and PPy3 ligands located at a distance of more than 1 nm from each other. Thus, the assembly of a heterobimetallic coordination polymer from relatively simple 'building blocks' retains the block-wise nature of the electronic structure, but the photophysical properties of the polymer are fundamentally different from the properties of discrete organometallic components.