Controllable Synthesis and Luminescence Behavior of Tetrahedral Au@Cu4 and Au@Ag4 Clusters Supported by tris(2-Pyridyl)phosphine.

We report herein a family of polynuclear complexes, [Au@Ag4(Py3P)4]X5 and [Au@Cu4(Py3P)4]X5 [X = NO3, ClO4, OTf, BF4, SbF6], containing unprecedented Au-centered Ag4 and Cu4 tetrahedral cores supported by tris(2-pyridyl)phosphine (Py3P) ligands. The [Au@Ag4]5+ clusters are synthesized via controlled substitution of the central Ag(I) ion in all-silver [Ag@Ag4]5+ precursors by the reaction with Au(tht)Cl, while the [Au@Cu4]5+ cluster is assembled through the treatment of a pre-organized [Au(Py3P)4]+ metallo-ligand with 4 equiv of a Cu(I) source. The structure of the Au@M4 clusters has been experimentally and theoretically investigated to reveal very weak intermolecular Au-M metallophilic interactions. At ambient temperature, the designed compounds emit a modest turquoise-to-yellow luminescence with microsecond lifetimes. Based on the temperature-dependent photophysical experiments and DFT/TD-DFT computations, the emission observed has been assigned to an MLCT or LLCT type depending on composition of the cluster core.

Ditopic Phosphide Oxide Group: A Rigidifying Lewis Base to Switch Luminescence and Reactivity of a Disilver Complex.

Heterodentate phosphines containing anionic organophosphorus groups remain virtually unexplored ligands in the coordination chemistry of coinage metals. A hybrid phosphine-phosphine oxide (o-Ph2PC6H4)2P(O)H (HP3O) readily forms the disilver complex [Ag2(P3O)2] (1) upon deprotonation of the (O)P-H fragment. Due to the electron-rich nature, the anionic phosphide oxide unit in 1 takes part in efficient intermolecular hydrogen bonding, which has an unusual and remarkably strong impact on the photoluminescence of 1, changing the emission from red (644 nm) to green-yellow (539 nm) in the solid. The basicity of the R2(O)P- group and its affinity for both inter- and intramolecular donor-acceptor interactions allow converting 1 into hydrohalogenated (2, 3) and boronated (4) derivatives, which reveal a gradual hypsochromic shift of luminescence, reaching the wavelength of 489 nm. Systematic variable-temperature analysis of the excited state properties suggests that thermally activated delayed fluorescence is involved in the emission process. The long-lived excited states for 1-4, the energy of which is largely regulated by means of the phosphide oxide unit, are potentially suitable for triplet energy transfer photocatalysis. With the highest T1 energy among 1-4, complex 4 demonstrates excellent photocatalytic activity in a [2+2] cycloaddition reaction, which has been realized for the first time for silver(I) compounds.

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 .

Photophysics and Excited State Dynamics of Cyclometalated [M(Phbpy)(CN)] (M = Ni, Pd, Pt) Complexes: A Theoretical and Experimental Study.

Cyclometalated complexes [M(Phbpy)(CN)] (HPhbpy = 6-phenyl-2,2'-bipyridine) of the group 10 metals (Ni, Pd, and Pt) bearing a carbanionic -C∧N∧N pincer ligand were synthesized and studied in a combined experimental and computational DFT approach. All three complexes were crystallographically characterized showing closely packed dimers with head-to-tail stacking and short metal-metal contacts in the solid state. The computational models for geometries, excited states, and electronic transitions addressed both monomeric (Ni-mono, Pd-mono, and Pt-mono) and dimeric (Ni-dim, Pd-dim, and Pt-dim) entities. Photophysical properties and excited state dynamics of all title complexes were investigated in solution and in the solid at 298 and 77 K. [Ni(Phbpy)(CN)] and [Pd(Phbpy)(CN)] are virtually nonemissive in solution at 298 K, whereas [Pt(Phbpy)(CN)] shows phosphorescence in CH2Cl2 (DCM) solution (λem = 562 nm) stemming from a mixed 3MLCT/ILCT (metal-to-ligand charge transfer/intraligand charge transfer) state. At 77 K in a glassy frozen DCM:MeOH matrix, [Pd(Phbpy)(CN)] shows a remarkable emission (λem = 571 nm) with a photoluminescence quantum yield reaching almost unity, whereas [Ni(Phbpy)(CN)] is again nonemissive. Calculations on the monomeric models M-mono show that low-lying metal-centered states (MC, i.e., d-d* configuration) with dissociative character quench the photoluminescence. In the solid state, the complexes [M(Phbpy)(CN)] show defined photoluminescence bands (λem = 561 nm for Pd and 701 nm for Pt). Calculations on the dimeric models M-dim shows that the axial M···M interactions alter the photophysical properties of Pd-dim and Pt-dim toward MMLCT (metal-metal-to-ligand charge transfer) excited states with Pd-dim showing temperature-dependent emission lifetimes, suggesting thermally activated delayed fluorescence, whereas Pt-dim displayed phosphorescence with excimeric character. The metal-metal interactions were analyzed in detail with the quantum theory of atoms in molecules approach.

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.

Re(I) Complexes as Backbone Substituents and Cross-Linking Agents for Hybrid Luminescent Polysiloxanes and Silicone Rubbers.

This study focuses on the synthesis of hybrid luminescent polysiloxanes and silicone rubbers grafted by organometallic rhenium(I) complexes using Cu(I)-catalyzed azido-alkyne cycloaddition (CuAAC). The design of the rhenium(I) complexes includes using a diimine ligand to create an MLCT luminescent center and the introduction of a triple C≡C bond on the periphery of the ligand environment to provide click-reaction capability. Poly(3-azidopropylmethylsiloxane-co-dimethylsiloxane) (N3-PDMS) was synthesized for incorporation of azide function in polysiloxane chain. [Re(CO)3(MeCN)(5-(4-ethynylphenyl)-2,2'-bipyridine)]OTf (Re1) luminescent complex was used to prepare a luminescent copolymer with N3-PDMS (Re1-PDMS), while [Re(CO)3Cl(5,5'-diethynyl-2,2'-bipyridine)] (Re2) was used as a luminescent cross-linking agent of N3-PDMS to obtain luminescent silicone rubber (Re2-PDMS). The examination of photophysical properties of the hybrid polymer materials obtained show that emission profile of Re(I) moiety remains unchanged and metallocenter allows to control the creation of polysiloxane-based materials with specified properties.

Binuclear Gold(I) Phosphine Alkynyl Complexes Templated on a Flexible Cyclic Phosphine Ligand: Synthesis and Some Features of Solid-State Luminescence.

A flexible bidentate cyclic phosphine, namely, 1,5-bis(p-tolyl)-3,7-bis(pyridin-2-yl)-1,5-diaza-3,7-diphosphacyclooctane (PNNP), was used as a template to construct a family of binuclear heteroleptic phosphine alkynyl complexes [PNNP(AuC2R)2], with R = Ph, C6H10OH, C5H8OH, (CH3)2COH, Ph2COH. All complexes obtained were characterized by CHN elemental analysis, NMR spectroscopy, and single-crystal X-ray analysis. It was found that the gold(I) complexes demonstrate a different organization of the crystal structure depending on the nature of the cocrystallized solvent (dichloromethane, acetone, and acetonitrile) because of formation of the supramolecular complexes through hydrogen bonding. These weak interactions appear to determine the conformation, packing, and spatial cooperation of flexible complex molecules that are reflected in the photophysical properties, which were carefully investigated in solution and in the solid state. The complexes demonstrate weak emission in solution at room temperature, and freezing results in blue shifting of the emission, which is accompanied by a significant increase in the luminescence intensity. Being isolated from dichloromethane, all gold(I) complexes exhibit green phosphorescence in the solid state, and the complexes with R = Ph and Ph2COH display substantial variation of their emission color after recrystallization from acetone and acetonitrile, respectively, which manifests itself as a significant bathochromic shift of up to 120 nm. The structural nonrigidity of the gold(I) complexes obtained and its impact on the properties of low-energy excited states were investigated in detail by density functional theory calculations, which indicate the significant role of the structural flexibility of the PNNP ligand in the formation of the low-energy excited states and confirm the impact of rotation of the functional groups in the coordination sphere on the emission properties of complexes.

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.

Oligophosphine-thiocyanate Copper(I) and Silver(I) Complexes and Their Borane Derivatives Showing Delayed Fluorescence.

The series of chelating phosphine ligands, which contain bidentate P2 (bis[(2-diphenylphosphino)phenyl] ether, DPEphos; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, Xantphos; 1,2-bis(diphenylphosphino)benzene, dppb), tridentate P3 (bis(2-diphenylphosphinophenyl)phenylphosphine), and tetradentate P4 (tris(2-diphenylphosphino)phenylphosphine) ligands, was used for the preparation of the corresponding dinuclear [M(µ2-SCN)P2]2 (M = Cu, 1, 3, 5; M = Ag, 2, 4, 6) and mononuclear [CuNCS(P3/P4)] (7, 9) and [AgSCN(P3/P4)] (8, 10) complexes. The reactions of P4 with silver salts in a 1:2 molar ratio produce tetranuclear clusters [Ag2(µ3-SCN)(t-SCN)(P4)]2 (11) and [Ag2(µ3-SCN)(P4)]22+ (12). Complexes 7-11 bearing terminally coordinated SCN ligands were efficiently converted into derivatives 13-17 with the weakly coordinating -SCN:B(C6F5)3 isothiocyanatoborate ligand. Compounds 1 and 5-17 exhibit thermally activated delayed fluorescence (TADF) behavior in the solid state. The excited states of thiocyanate species are dominated by the ligand to ligand SCN → π(phosphine) charge transfer transitions mixed with a variable contribution of MLCT. The boronation of SCN groups changes the nature of both the S1 and T1 states to (L + M)LCT d,p(M, P) → π(phosphine). The localization of the excited states on the aromatic systems of the phosphine ligands determines a wide range of luminescence energies achieved for the title complexes (λem varies from 448 nm for 1 to 630 nm for 10c). The emission of compounds 10 and 15, based on the P4 ligand, strongly depends on the solid-state packing (λem = 505 and 625 nm for two crystalline forms of 15), which affects structural reorganizations accompanying the formation of electronically excited states.

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.

Improvement of the Photophysical Performance of Platinum-Cyclometalated Complexes in Halogen-Bonded Adducts.

Three groups of luminescent platinum complexes [Pt(C^N)(L)(Y)] [C^N=benzothienyl-pyridine (1), bezofuryl-pyridine (2), phenyl-pyridine (3); L/Y=DMSO/Cl (a), PPh3 /Cl (b), PPh3 /CN (c)] have been probed as halogen-bond (XB) acceptors towards iodofluorobenzenes (IC6 F5 and I2 C6 F4 ). Compounds 1 a and 2 a (L/Y=DMSO/Cl) afford the adducts 1 a⋅⋅⋅I2 C6 F4 and 2 a⋅⋅⋅I2 C6 F4 , which feature I⋅⋅⋅Sbtpy /I⋅⋅⋅πbtpy and I⋅⋅⋅ODMSO /I⋅⋅⋅Cl short contacts, respectively. The phosphane-cyanide derivatives 1 c and 2 c (L/Y=PPh3 /CN) co-crystallise with both IC6 F5 and I2 C6 F4 . None of the phpy-based species 3 a-3 c participated in XB interactions. Although the native complexes are rather poor luminophores in the solid state (Φem =0.023-0.089), the adducts exhibit an up to 10-fold increase of the intensity with a minor alteration of the emission energy. The observed gain in the quantum efficiency is mainly attributed to the joint influence of non-covalent interactions (halogen/hydrogen bonding, π-π stacking), which govern the crystal-packing mode and diminish the radiationless pathways for the T1 →S0 transition by providing a rigid environment around the chromophore.

Luminescence Thermochromism of Gold(I) Phosphane-Iodide Complexes: A Rule or an Exception?

A series of gold(I) iodide complexes 1-11 have been prepared from di-, tri-, and tetraphosphane ligands. Crystallographic studies reveal that the di- (1-7) and tetrametallic (11) compounds feature linearly coordinated gold(I) ions with short aurophilic contacts. Their luminescence behavior is determined by the combined influence of the phosphane properties, metal-metal interaction, and intermolecular lattice-defined interactions. The proposed variable contribution of 3 (X+M)-centered (X=halogen; M=metal) and 3 XLCT (halogen to ligand charge transfer) electronic transitions into the lowest lying excited state, which is influenced by supramolecular packing, is presumably responsible for the alteration of room-temperature emission color from green (λ=545 nm, for 11) to near-IR (λ=698 nm, for 2). Dinuclear compounds 6 and 7 exhibit distinct luminescence thermochromism with a blueshift up to 5750 cm-1 upon cooling. Such dramatic change of emission energy is assigned to the presence of two coupled triplet excited states of 3 ππ* and 3 (X+M)C/3 XLCT nature, the presence of which depends on both molecular structure and the crystal lattice arrangement.

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).

Heterometallic Cluster-Capped Tetrahedral Assemblies with Postsynthetic Modification of the Metal Cores.

Combining the star-shaped alkynyl ligands with low-nuclearity gold-copper triphosphane clusters produces 3D metallocage aggregates, which demonstrate room temperature phosphorescence in solution (max Φem =0.6). Their luminescence mainly originates from cluster-localized metal-to-ligand charge transfer excited state. These supramolecular assemblies can be easily converted into the isostructural gold-silver congeners by the direct exchange of the metal ions. Such modification of the terminal metal cores switches the emission to the intraligand (alkyne) electronic transitions of the triplet manifold, that represents an unusual optical functionality among the metallocycle/metallocage complexes.

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.

Gold(I) Alkynyls Supported by Mono- and Bidentate NHC Ligands: Luminescence and Isolation of Unprecedented Ionic Complexes.

Reactions of NHC·HX (NHC = 1-benzyl-3-methylbenzimidazol-2-ylidene, X = Br-, PF6-) and (AuC≡CR)n (R = Ph, C3H6OH) in the presence of Cs2CO3 initially afford compounds of the general formula [(NHC)2Au]2[(RC2)2Au]X, which can be isolated by crystallization. With increased reaction time, only the expected mononuclear complexes of the type [NHCAuC≡CR] are produced. The crystal structure of [(NHC)2Au]2[(PhC2)2Au]PF6 reveals an unprecedented triple-decker array upheld by a remarkably short (2.9375(7) Å) unsupported Au···Au···Au contact. The mononuclear complex [NHCAuC≡CPh] was found to crystallize as three distinct polymorphs and a pseudopolymorph, which depending on the intermolecular Au···Au distances emit blue, green, or yellow light. Two synthetic approaches were employed for the preparation of a series of dinuclear NHC-ligated Au(I) alkynyl complexes of the general formula [NHC-(CH2)n-NHC(AuC≡CR)2], where NHC = N-benzylbenzimidazol-2-ylidene, R = Ph, C3H6OH, C6H10OH, and n = 1-3. In solution, the complexes with aliphatic substituents on the alkynyl fragment are nonemissive, whereas their phenyl-bearing congeners demonstrate characteristic metal-perturbed 3[IL(C≡CPh)] emission. In the solid state, a clear correlation between intermolecular aurophilic interactions and luminescence was established, including their role in the luminescent thermochromism of the phenylalkynyl complexes. The relationship between the Au···Au distance and emission energy was found to be inverse: i.e., the shorter the aurophilic contact, the higher the emission energy. We tentatively attribute this behavior to a smaller extent of excited-state distortion for a structure with a shorter Au···Au separation.

A model electrode of well-defined geometry prepared by direct laser-induced decoration of nanoporous templates with Au-Ag@C nanoparticles.

We present an original type of model electrode system consisting of bimetallic Au-Ag nanoparticles embedded in an amorphous carbon matrix with an extremely well-defined geometry of parallel, straight, cylindrical macropores. The samples are prepared in one step by direct laser deposition of the metal/carbon composite onto the inner walls of a porous 'anodic' alumina matrix serving as a template. The coating is homogeneous from top to bottom of the pores, and the amount of material deposited can be tuned by the duration of the deposition procedure. As a test system, we demonstrate that a bimetallic Ag-Au@C system is catalytically active for the electrochemical oxidation of glucose in alkaline solution, the anodic reaction of a direct glucose fuel cell. Furthermore, the electrocatalytic current density increases with the amount of Ag-Au@C NPs deposited, up to a point at which the pores are clogged with it. This type of model system allows for the systematic study of geometric effects in fuel cell electrodes. It can be generalized to a number of different nanoparticle compositions, and thereby, to various electrocatalytic reactions.

Supramolecular Au(I)-Cu(I) Complexes as New Luminescent Labels for Covalent Bioconjugation.

Two new supramolecular organometallic complexes, namely, [Au6Cu2(C2C6H4CHO)6(PPh2C6H4PPh2)3](PF6)2 and [Au6Cu2(C2C6H4NCS)6(PPh2C6H4PPh2)3](PF6)2, with highly reactive aldehyde and isothiocyanate groups have been synthesized and characterized using X-ray crystallography, ESI mass spectrometry, and NMR spectroscopy. The compounds obtained demonstrated bright emission in solution with the excited-state lifetime in microsecond domain both under single- and two-photon excitation. The luminescent complexes were found to be suitable for bioconjugation in aqueous media. In particular, they are able to form the covalent conjugates with proteins of different molecular size (soybean trypsin inhibitor, human serum albumin, rabbit anti-HSA antibodies). The conjugates demonstrated a high level of the phosphorescent emission from the covalently bound label, excellent solubility, and high stability in physiological media. The highest quantum yield, storage stability, and luminance were detected for bioconjugates formed by covalent attachment of the aldehyde-bearing supramolecular Au(I)-Cu(I) complex. The measured biological activity of one of the labeled model proteins clearly showed that introduced label did not prevent the biorecognition and specific protein-protein complex formation that was extremely important for the application of the conjugates in biomolecular detection and imaging.

Aurophilicity in Action: Fine-Tuning the Gold(I)-Gold(I) Distance in the Excited State To Modulate the Emission in a Series of Dinuclear Homoleptic Gold(I)-NHC Complexes.

The solution-state emission profiles of a series of dinuclear Au(I) complexes 4-6 of the general formula Au2(NHC-(CH2)n-NHC)2Br2, where NHC = N-benzylbenzimidazol-2-ylidene and n = 1-3, were found to be markedly different from each other and dependent on the presence of excess bromide. The addition of excess bromide to the solutions of 4 and 6 leads to red shifts of ca. 60 nm, and in the case of 5, which is nonemissive when neat, green luminescence emerges. A detailed computational study undertaken to rationalize the observed behavior revealed the determining role aurophilicity plays in the photophysics of these compounds, and the formation of exciplexes between the complex cations and solvent molecules or counterions was demonstrated to significantly decrease the Au-Au distance in the triplet excited state. A direct dependence of the emission wavelength on the strength of the intracationic aurophilic contact allows for a controlled manipulation of the emission energy by varying the linker length of a diNHC ligand and by judicial choice of counterions or solvent. Such unique stimuli-responsive solution-state behavior is of interest to prospective applications in medical diagnostics, bioimaging, and sensing. In the solid, the investigated complexes are intensely phosphorescent and, notably, 5 and 6 exhibit reversible luminescent mechanochromism arising from amorphization accompanied by the loss of co-crystallized methanol molecules. The mechano-responsive properties are also likely to be related to changes in bromide coordination and the ensuing alterations of intramolecular aurophilic interactions. Somewhat surprisingly, the photophysics of NHC ligand precursors 2 and 3 is related to the formation of ground-state associates with bromide counterions through hydrogen bonding, whereas 1 does not appear to bind its counterions.

Solid-State and Solution Metallophilic Aggregation of a Cationic [Pt(NCN)L](+) Cyclometalated Complex.

The noncovalent intermolecular interactions (π-π stacking, metallophilic bonding) of the cyclometalated complexes [Pt(NCN)L](+)X(-) (NCN = dipyridylbenzene, L = pyridine (1), acetonitrile (2)) are determined by the steric properties of the ancillary ligands L in the solid state and in solution, while the nature of the counterion X(-) (X(-) = PF6(-), ClO4(-), CF3SO3(-)) affects the molecular arrangement of 2·X in the crystal medium. According to the variable-temperature X-ray diffraction measurements, the extensive Pt···Pt interactions and π-stacking in 2·X are significantly temperature-dependent. The variable concentration (1)H and diffusion coefficients NMR measurements reveal that 2·X exists in the monomeric form in dilute solutions at 298 K, while upon increase in concentration [Pt(NCN)(NCMe)](+) cations undergo the formation of the ground-state oligomeric aggregates with an average aggregation number of ∼3. The photoluminescent characteristics of 1 and 2·X are largely determined by the intermolecular aggregation. For the discrete molecules the emission properties are assigned to metal perturbed IL charge transfer mixed with some MLCT contribution. In the case of oligomers 2·X the luminescence is significantly red-shifted with respect to 1 and originates mainly from the (3)MMLCT excited states. The emission energies depend on the structural arrangement in the crystal and on the complex concentration in solution, variation of which allows for the modulation of the emission color from greenish to deep red. In the solid state the lability of the ligands L leads to vapor-induced reversible transformation 1 ↔ 2 that is accompanied by the molecular reorganization and, consequently, dramatic change of the photophysical properties. Time-dependent density functional theory calculations adequately support the models proposed for the rationalization of the experimental observations.