Dual Fluorescence and Phosphorescence Emissions from Dye-Modified (NCN)-Bismuth Pincer Thiolate Complexes.

We report the synthesis, characterization, and photophysical properties of four new dye-modified (NCN)Bi pincer complexes with two mercaptocoumarin or mercaptopyrene ligands. Their photophysical properties were probed by UV/vis spectroscopy, photoluminescence (PL) studies, and time-dependent density functional theory (TD-DFT) calculations. Absorption spectra of the complexes are dominated by mixed pyrene or coumarin π → π*/n(pS) → pyrene or coumarin π* transitions. While unstable toward reductive elimination of the corresponding disulfide under irradiation at room temperature, the complexes provide stable emissions at 77 K. Under these conditions, coumarin complexes 2 and 4 exhibit exclusively green phosphorescence at 508 nm. In contrast, the emissive properties of pyrene complexes 1 and 3 depend on the excitation wavelength and on sample concentration. Irradiation into the lowest-energy absorption band exclusively triggers red phosphorescence from the pyrenyl residues at 640 nm. At concentrations c < 1 µM, excitation into higher excited electronic states results in blue pyrene fluorescence. With increasing c (1-100 µM), the emission profile changes to dual fluorescence and phosphorescence emission, with a steady increase of the phosphorescence intensity, until at c ≥ 1 mM only red phosphorescence ensues. Progressive red-shifts and broadening of steady-state excitation spectra with increasing sample concentration suggest the presence of static excimers, as we observe it for concentrated solutions of pyrene. Crystalline and powdered samples of 1 indeed show intermolecular association through π-stacking. TD-DFT calculations on model dimers and a tetramer of 1 support the idea of aggregation-induced intersystem crossing (AI-ISC) as the underlying reason for this behavior.

Ferrocenyl-Substituted Triazatruxenes: Synthesis, Electronic Properties, and the Impact of Ferrocenyl Residues on Directional On-Surface Switching on Ag(111).

We report on seven new ferrocenyl-(1, 3)- and ferrocenylethynyl-modified N,N',N″-triethyltriazatruxenes (EtTATs) 4-7 as well as the dodecyl counterpart 2 of compound 1 and their use as molecular switching units when deposited on a Ag(111) surface. Such functional units may constitute a new approach to molecule-based high-density information storage and processing. Besides the five compounds 1-3, 6, and 7, where the 3-fold rotational symmetry of the triazatruxene (TAT) template is preserved, we also included 2-ethynylferrocenyl-TAT 4 and 2,2'-di(ethynylferrocenyl)-TAT 5, whose mono- and disubstitution patterns break the 3-fold symmetry of the TAT core. Voltammetric studies indicate that the ferrocenyl residues of compounds 1-7 oxidize prior to the oxidation of the TAT core. We have noted strong electrostatic effects on TAT oxidation in the 2,2',2″-triferrocenyl-TAT derivatives 1 and 2 and the 3,3',3″-isomer 3. The oxidized complexes feature multiple electronic excitations in the near-infrared and the visible spectra, which are assigned to dδ/δ* transitions of the ferrocenium (Fc+) moieties, as well as TAT → Fc+ charge-transfer transitions. The latter are augmented by intervalence charge-transfer contributions Fc → Fc+ in mixed-valent states, where only a part of the available ferrocenyl residues is oxidized. EtTAT was previously identified as a directional three-level switching unit when deposited on Ag(111) and constitutes a trinary-digit unit for on-surface information storage. The symmetrically trisubstituted compound 6 retains this property, albeit at somewhat reduced switching rates due to the additional interaction between the ferrocenyl residues and the Ag surface. In particular, the high directionality at low bias and the inversion of the preferred sense of the on-surface rocking motion with either a clockwise or counterclockwise switching sense, depending on the identity of the surface enantiomer, are preserved. Unsymmetrical substitution in mono- and diferrocenylated 4 and 5 alters the underlying ratchet potential in a manner such that a two-state switching between the two degenerate surface conformations of 4 or a pronounced suppression of switching (5) is observed.

A Dibenzotetrathiafulvalene-Bridged Bis(alkenylruthenium) Complex and Its One- and Two-Electron-Oxidized Forms.

We report on the synthesis of the new bis(alkenylruthenium) complex DBTTF-(ViRu)2 with a longitudinally extended, π-conjugated dibenzotetrathiafulvalene (DBTTF) bridge, characterized by multinuclear NMR, IR, and UV/vis spectroscopy, mass spectrometry, and single-crystal X-ray diffraction. Cyclic and square-wave voltammetry revealed that DBTTF-(ViRu)2 undergoes four consecutive oxidations. IR, UV/vis/near-IR, and electron paramagnetic resonance spectroscopy indicate that the first oxidation involves the redox-noninnocent DBTTF bridge, while the second oxidation is biased toward one of the peripheral styrylruthenium entities, thereby generating an electronically coupled mixed-valent state ({Ru}-CH═CH)•+-DBTTF•+-(CH═CH-{Ru}) [{Ru} = Ru(CO)Cl(PiPr3)2]. The latter is apparently in resonance with the ({Ru}-CH═CH)•+-DBTTF-(CH═CH-{Ru})•+ and ({Ru}-CH═CH)-DBTTF2+-(CH═CH-{Ru}) forms, which are calculated to lie within 19 kJ/mol. Higher oxidized forms proved too unstable for further characterization. The reaction of DBTTF-(ViRu)2 with the strong organic acceptors 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tetracyano-p-benzoquinodimethane (TCNQ), and F4TCNQ resulted in formation of the DBTTF-(ViRu)2•+ radical cation, as shown by various spectroscopic techniques. Solid samples of these compounds were found to be highly amorphous and electrically insulating.

Exploring Structure-Property Relations of B,S-Doped Polycyclic Aromatic Hydrocarbons through the Trinity of Synthesis, Spectroscopy, and Theory.

Polycyclic aromatic hydrocarbons (PAHs) are prominent lead structures for organic optoelectronic materials. This work describes the synthesis of three B,S-doped PAHs with heptacene-type scaffolds via nucleophilic aromatic substitution reactions between fluorinated arylborane precursors and 1,2-(Me3SiS)2C6H4/1,8-diazabicyclo[5.4.0]undec-7-ene (72-92% yield). All compounds contain tricoordinate B atoms at their 7,16-positions, kinetically protected by mesityl (Mes) substituents. PAHs 1/2 feature two/four S atoms at their 5,18-/5,9,14,18-positions; PAH 3 is a 6,8,15,17-tetrafluoro derivative of 2. For comparison, we also prepared the skewed naphtho[2,3-c]pentaphene-type isomer 4. The simultaneous presence of electron-accepting B atoms and electron-donating S atoms results in a redox-ambiphilic behavior; the radical cations [1•]+ and [2•]+ were characterized by electron paramagnetic resonance spectroscopy. Several low-lying charge-transfer states exist, some of which (especially S-to-B and Mes-to-B transitions) compete on the excited-state potential-energy surface. Consistent with the calculated state characters and oscillator strengths, this competition results in a spread of fluorescence quantum yields (2-27%). The optoelectronic properties of 1 change drastically upon addition of Ag+ ions: while the color of 1 in CH2Cl2 changes bathochromically from yellow to red (λmax from 463 to 486 nm; -0.13 eV), the emission band shifts hypsochromically from 606 to 545 nm (+0.23 eV), and the fluorescence quantum yield increases from 12 to 43%. According to titration experiments, higher order adducts [Agn1m]n+ are formed. As a suitable system for modeling Ag+ complexation, our calculations predict a dimer structure (n = m = 2) with Ag2S4 core, approximately linear S-Ag-S fragments, and Ag-Ag interaction. The computed optoelectronic properties of [Ag212]2+ agree well with the experimentally observed ones.

Electron-Rich Diruthenium Complexes with π-Extended Alkenyl Ligands and Their F4 TCNQ Charge-Transfer Salts.

The synthesis of dinuclear ruthenium alkenyl complexes with {Ru(CO)(Pi Pr3 )2 (L)} entities (L=Cl- in complexes Ru2 -3 and Ru2 -7; L=acetylacetonate (acac- ) in complexes Ru2 -4 and Ru2 -8) and with π-conjugated 2,7-divinylphenanthrenediyl (Ru2 -3, Ru2 -4) or 5,8-divinylquinoxalinediyl (Ru2 -7, Ru2 -8) as bridging ligands are reported. The bridging ligands are laterally π-extended by anellating a pyrene (Ru2 -7, Ru2 -8) or a 6,7-benzoquinoxaline (Ru2 -3, Ru2 -4) π-perimeter. This was done with the hope that the open π-faces of the electron-rich complexes will foster association with planar electron acceptors via π-stacking. The dinuclear complexes were subjected to cyclic and square-wave voltammetry and were characterized in all accessible redox states by IR, UV/Vis/NIR and, where applicable, by EPR spectroscopy. These studies signified the one-electron oxidized forms of divinylphenylene-bridged complexes Ru2 -7, Ru2 -8 as intrinsically delocalized mixed-valent species, and those of complexes Ru2 -3 and Ru2 -4 with the longer divinylphenanthrenediyl linker as partially localized on the IR, yet delocalized on the EPR timescale. The more electron-rich acac- congeners formed non-conductive 1 : 1 charge-transfer (CT) salts on treatment with the F4 TCNQ electron acceptor. All spectroscopic techniques confirmed the presence of pairs of complex radical cations and F4 TCNQ.- radical anions in these CT salts, but produced no firm evidence for the relevance of π-stacking to their formation and properties.

Reversible Multielectron Release from Redox-Active Three-Dimensional Molecular Barrels with Ruthenium-Alkenyl Moieties.

Three-dimensional molecular barrels Ru6-4 and Ru6-5 were synthesized in high yields from dinuclear ruthenium-vinyl clamps and tritopic triphenylamine-derived carboxylate linkers and characterized by multinuclear NMR spectroscopy including 1H-1H COSY and 1H DOSY measurements, high-resolution electrospray ionization mass spectrometry, and X-ray crystallography. The metal frameworks of the cages adopt the shape of twisted trigonal prisms, and they crystallize as racemic mixtures of interdigitating Δ- and Λ-enantiomers with a tight columnar packing in Ru6-4. Electrochemical studies and redox titrations revealed that the cages are able to release up to 11 electrons on the voltammetric timescale and that their cage structures persist up to the hexacation level. IR and UV-vis-near-infrared spectroelectrochemical studies confirm substituent-dependent intramolecular electronic communication within the π-conjugated 1,3-divinylphenylene backbone in the tricationic states, where all three divinylphenylene-bridged diruthenium clamps are present in mixed-valent radical cation states. The formation of 1:3 charge-transfer salts with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane as the electron acceptor is also demonstrated.

Tailoring Valence Tautomerism by Using Redox Potentials: Studies on Ferrocene-Based Triarylmethylium Dyes with Electron-Poor Fluorenylium and Thioxanthylium Acceptors.

Three new electrochromic ferrocenyl triarylmethylium dyes with fluorenylium (1 a+ , 1 b+ ) or thioxanthylium (1 c+ ) residues were selected in order to keep the intrinsic differences of redox potentials for ferrocene oxidation and triarylmethylium reduction small and to trigger valence tautomerism (VT). UV/Vis/NIR and quantitative EPR spectroscopy identified paramagnetic diradical isomers 1 a..+ -1 c..+ alongside diamagnetic forms 1 a+ -1 c+ , which renders these complexes magnetochemical switches. The diradical forms 1 a..+ -1 c..+ as well as the one-electron-reduced triarylmethyl forms of the complexes were found to dimerize in solution. For radical 1 a. , dimerization occurs on the timescale of cyclic voltammetry; this allowed us to determine the kinetics and equilibrium constant for this process by digital simulation. Mößbauer spectroscopy indicated that 1 a+ and 1 b+ retain VT even in the solid state. UV/Vis/NIR spectro-electrochemistry revealed the poly-electrochromic behaviour of these complexes by establishing the distinctly different electronic absorption profiles of the corresponding oxidized and reduced forms.

Voltammetry as a Tool to Monitor the Aggregation Behavior of a Zwitterionic Ferrocene Surfactant.

Amphiphiles are unique in their ability to self-assemble in aqueous solution into aggregates. The control of the self-organization of amphiphiles and the live monitoring of the ensuing structure changes by analytical methods are key challenges in this field. One way to gain control and to trigger the self-assembly/disassembly of amphiphiles is to introduce a redox-active constituent to the amphiphile structure, as is the case with metallosurfactants. In this work, we report a cyclic and square-wave voltammetric study on the multi-stimuli-responsive amphiphile 1-(Z)-heptenyl-1'-dimethylammoniummethyl-(3-sulfopropyl)ferrocene (1). We observe separate waves/peaks for molecules of 1 present as the monomer in its electrode-immobilized, its freely diffusing form, and its aggregated form. This allows for a direct monitoring of how the underlying equilibria depend on the concentration and time. Isothermal titration calorimetry indicates that aggregation is entropically and enthalpically favored. Our findings thus illustrate the utility of voltammetric methods for investigating self-assembly processes of redox-active amphiphiles and their redox switchability.

A "Pretender" Croconate-Bridged Macrocyclic Tetraruthenium Complex: Sizable Redox Potential Splittings despite Electronically Insulated Divinylphenylene Diruthenium Entities.

Careful optimization of the reaction conditions provided access to the particularly small tetraruthenium macrocycle 2Ru2Ph-Croc, which is composed out of two redox-active divinylphenylene-bridged diruthenium entities {Ru}-1,4-CH=CH-C6H4-CH=CH-{Ru} (Ru2Ph; {Ru} = Ru(CO)Cl(PiPr3)2) and two likewise redox-active and potentially non-innocent croconate linkers. According to single X-ray diffraction analysis, the central cavity of 2Ru2Ph-Croc is shielded by the bulky PiPr3 ligands, which come into close contact. Cyclic voltammetry revealed two pairs of split anodic waves in the weakly ion pairing CH2Cl2/NBu4BArF24 (BArF24 = [B{C6H3(CF3)2-3,5}4]- electrolyte, while the third and fourth waves fall together in CH2Cl2/NBu4PF6. The various oxidized forms were electrogenerated and scrutinized by IR and UV/Vis/NIR spectroscopy. This allowed us to assign the individual oxidations to the metal-organic Ru2Ph entities within 2Ru2Ph-Croc, while the croconate ligands remain largely uninvolved. The lack of specific NIR bands that could be assigned to intervalence charge transfer (IVCT) in the mono- and trications indicates that these mixed-valent species are strictly charge-localized. 2Ru2Ph-Croc is hence an exemplary case, where stepwise IR band shifts and quite sizable redox splittings between consecutive one-electron oxidations would, on first sight, point to electronic coupling, but are exclusively due to electrostatic and inductive effects. This makes 2Ru2Ph-Croc a true "pretender".

Increasing the Cytotoxicity of Ru(II) Polypyridyl Complexes by Tuning the Electronic Structure of Dioxo Ligands.

Due to the great potential expressed by an anticancer drug candidate previously reported by our group, namely, Ru-sq ([Ru(DIP)2(sq)](PF6) (DIP, 4,7-diphenyl-1,10-phenanthroline; sq, semiquinonate ligand), we describe in this work a structure-activity relationship (SAR) study that involves a broader range of derivatives resulting from the coordination of different catecholate-type dioxo ligands to the same Ru(DIP)2 core. In more detail, we chose catechols carrying either an electron-donating group (EDG) or an electron-withdrawing group (EWG) and investigated the physicochemical and biological properties of their complexes. Several pieces of experimental evidences demonstrated that the coordination of catechols bearing EDGs led to deep-red positively charged complexes 1-4 in which the preferred oxidation state of the dioxo ligand is the uninegatively charged semiquinonate. Complexes 5 and 6, on the other hand, are blue/violet neutral complexes, which carry an EWG-substituted dinegatively charged catecholate ligand. The biological investigation of complexes 1-6 led to the conclusion that the difference in their physicochemical properties has a strong impact on their biological activity. Thus, complexes 1-4 expressed much higher cytotoxicities than complexes 5 and 6. Complex 1 constitutes the most promising compound in the series and was selected for a more in depth biological investigation. Apart from its remarkably high cytotoxicity (IC50 = 0.07-0.7 µM in different cancerous cell lines), complex 1 was taken up by HeLa cells very efficiently by a passive transportation mechanism. Moreover, its moderate accumulation in several cellular compartments (i.e., nucleus, lysosomes, mitochondria, and cytoplasm) is extremely advantageous in the search for a potential drug with multiple modes of action. Further DNA metalation and metabolic studies pointed to the direct interaction of complex 1 with DNA and to the severe impairment of the mitochondrial function. Multiple targets, together with its outstanding cytotoxicity, make complex 1 a valuable candidate in the field of chemotherapy research. It is noteworthy that a preliminary biodistribution study on healthy mice demonstrated the suitability of complex 1 for further in vivo studies.

Geodesic-Planar Conjugates: Substituted Buckybowls-Synthesis, Photoluminescence and Electrochemistry.

C-C cross coupling products of bowl-shaped as-indaceno[3,2,1,8,7,6-pqrstuv]picene (Idpc) and different planar arenes and ethynyl-arenes were synthesized. Photoluminescence as well as electrochemical properties of all products were investigated and complemented by time-dependent quantum chemical calculations. UV/Vis spectroelectrochemistry investigations of the directly linked (Idpc)2 indicated the absence of any intramolecular charge-transfer transition of intermittently formed (Idpc)2 .- . All coupling products showed fluorescence. Ferrocene-1-yl-Idpc was structurally characterized by X-ray diffraction and is a rare example of a ferrocene-containing buckybowl exhibiting luminescence.

Redox-Induced Hydrogen Bond Reorientation Mimicking Electronic Coupling in Mixed-Valent Diruthenium and Macrocyclic Tetraruthenium Complexes.

We present the coordination-driven self-assembly of three tetranuclear metallacycles containing intracyclic NH2, OH, or OMe functionalities through the combination of various isophthalic acid building blocks with a divinylphenylene diruthenium complex. All new complexes of this study were characterized by means of nuclear magnetic resonance spectroscopy, ultrahigh-resolution ESI mass spectrometry, cyclic and square wave voltammetry and, in two cases, X-ray diffraction. The hydroxy functionalized macrocycle 4-BOH and the corresponding half-cycle 2-OH stand out, as their intracyclic OH···O hydrogen bonds stabilize their mixed-valent one- (2-OH, 4-BOH) and three-electron-oxidized states (4-BOH). Despite sizable redox splittings between all one-electron waves, the mixed-valent monocations and trications do not exhibit any intervalence charge-transfer band, assignable to through-bond electronic coupling, but nevertheless display distinct IR band shifts of their charge-sensitive Ru(CO) tags. We ascribe these seemingly contradicting observations to a redox-induced shuffling of the OH···O hydrogen bond(s) to the remaining, more electron-rich, reduced redox site.

Mixed-Valent Ruthenocene-Vinylruthenium Conjugates: Valence Delocalization Despite Chemically Different Redox Sites.

Ruthenocene-vinylruthenium conjugates Rc/Rc*-CH═CH-Ru(CO)(L)(P iPr3)2 (Rc = (η5-C5H5)Ru(η5-C5H4); Rc* = (η5-C5Me5)Ru(η5-C5H4); L = Cl or κ O, O' -acetylacetonato) have been prepared and investigated in their neutral, mono-, and dioxidized states by cyclic voltammetry, IR and UV/vis/NIR spectroelectrochemistry, and EPR spectroscopy. Their corresponding radical cations are (almost) completely delocalized mixed-valent systems as indicated by the low half-widths, the absence of solvatochromism, and the low-energy cutoff of their IVCT bands in the near-infrared (NIR) and their IR and EPR spectroscopic signatures. The degree of electronic coupling even exceeds that of their ferrocene analogs despite comparable differences between the intrinsic half-wave potentials of the vinylruthenium and the metallocenyl entities and substantially smaller half-wave potential splittings, Δ E1/2, in the ruthenocene congeners. All experimental results are backed by quantum chemical calculations.

Macrocyclic Triruthenium Complexes Having Electronically Coupled Mixed-Valent States.

5-Ethynyl-2-furancarboxylic acid and 3-ethynylbenzoic acid self-assemble with [HRu(CO)Cl(PiPr3 )2 ] to form macrocyclic C3 -symmetric triangular triruthenium alkenyl complexes [{Ru(CO)(PiPr3 )2 (CH=CHArCOO)}3 ] (Ar=C6 H4 : 1-B, Ar=C4 H2 O: 1-F), which were characterized by multinuclear NMR spectroscopy, high-resolution ESI mass spectrometry, and, in the case of 1-B, by X-ray crystallography. Electrochemical studies indicate that the macrocycles are oxidized in three consecutive one-electron steps. The mixed-valent states obtained by electrochemical or chemical oxidation show signs of valence delocalization, which makes these complexes rare examples of molecule-based conductive loops with through-bond charge delocalization.

Electrochemical, Spectroelectrochemical, Mößbauer, and EPR Spectroscopic Studies on Ferrocenyl-Substituted Tritylium Dyes.

Four monoferrocenyl tritylium derivatives with donor-substituted (OMe, NMe2 ) aryl rings are reported, along with their spectroscopic and electrochemical properties. All the complexes show a one-electron reduction and a quasi-reversible ferrocene oxidation at a very positive potential. Small quadrupole splittings, ΔEQ , in Mößbauer spectra agree with highly electron-deficient ferrocenes. Comparison of the experimental half-wave potentials for ferrocene oxidation, E1/2 (Fc/Fc+ ), with those estimated from established correlations of E1/2 (Fc/Fc+ ) with ΔEQ indicates that the E1/2 values of the anisyl-substituted congeners FcOMe+ and FcMeOMe+ are affected by Coulombic repulsion between the positive charges at the Fe ion and the neighboring methylium site. Electronic spectra are recorded and interpreted with the aid of quantum chemical calculations. UV/Vis spectroelectrochemical measurements as well as chemical reduction provide insight into the redox-induced color changes upon ferrocene oxidation or upon reduction to the neutral trityl radicals. The neutral radicals reversibly form EPR-silent dimers. This process is studied by temperature-dependent EPR spectroscopy, and thermodynamic data for their dimerization are determined. Experimental and quantum chemical data suggest that the dimers assume classical hexaarylethane structures as opposed to normal or "offset" Jacobson-Nauta-type structures.

Cobaltocenylidene: A Mesoionic Metalloceno Carbene, Stabilized in a Gold(III) Complex.

Oxidative addition of cobaltoceniumdiazonium bis(hexafluoridophosphate) with (pseudo)halide aurates gave gold(III) complexes containing zwitterionic cobaltoceniumide as a ligand. Its selenium derivative, cobaltoceniumselenolate, was obtained by an electrophilic aromatic substitution reaction of iodocobaltocenium iodide with Na2 Se. Spectroscopic and structural data in combination with DFT calculations showed that this cobaltocenylidene species is a mesoionic carbene quite different from common N-heterocyclic carbenes. Its ligand properties (TEP, singlet-triplet gap, nucleophilicity, π-acidity, Brønsted basicity) are in part comparable to those of cyclic (amino)(alkyl/aryl)carbenes. Electrochemistry data showed that the mesoionic cobaltoceniumides are more electron-rich than their parent ferrocenes. The reversible reduction of the tricyanido gold complex appears 50 mV negative of the cobaltocenium/cobaltocene couple, whereas that of the selenide derivative is shifted cathodically by 550 mV.

Redox-Active N-Heterocyclic Germylenes and Stannylenes with a Ferrocene-1,1'-diyl Backbone.

We describe ferrocene-based N-heterocyclic germylenes and stannylenes of the type [Fe{(η5 -C5 H4 )NR}2 E:] (1 RE; E=Ge, Sn; R=neopentyl (Np), mesityl (Mes), trimethylsilyl (TMS)), which constitute the first examples of redox-functionalised N-heterocyclic tetrylenes (NHTs). These compounds are thermally stable and were structurally characterised by means of X-ray diffraction studies, except for the neopentyl-substituted stannylene 1 NpSn, the decomposition of which afforded the aminoiminoferrocene [fc(NHCH2 tBu)(N=CHtBu)] (2) and the spiro tin(IV) compound (1 Np)2 Sn (3). DFT calculations show that the HOMO of the NHTs of our study is localised on the ferrocenylene backbone. A one-electron oxidation process affords ions of the type 1 RE+. . In contrast to the NHC system 1 RC, the localised ferrocenium-type nature of the oxidised form does not compromise the fundamental tetrylene character of 1 RE+. .

Manipulation and Assessment of Charge and Spin Delocalization in Mixed-Valent Triarylamine-Vinylruthenium Conjugates.

Triarylamine-vinylruthenium conjugates (4-RC6H4)2N{C6H4-4-CH═CHRu(CO)Cl(PiPr3)2}, with R = CHO (1-CHO), C(═O)Me (1-Ac), COOMe (1-E), and Me (1-Me), have been prepared and investigated in their neutral, mono- and dioxidized states by cyclic voltammetry, IR, and UV/vis/near-infrared spectroelectrochemistry, electron paramagnetic resonance spectroscopy, and quantum-chemical calculations. Electron-withdrawing substituents at the triarylamine moiety shift the charge and spin density toward the more electron-rich vinylruthenium site in comparison to the 4-OMe-substituted triarylamine-vinylruthenium conjugate 1-OMe. A more asymmetric charge distribution changes the intense vibrationally structured intervalence charge-transfer (IVCT) band of completely delocalized, mixed-valent (MV) 1-OMe+ to a weaker, highly asymmetric, nonsolvatochromic band with significantly smaller bandwidth at the low-energy side. The temperature dependence of the IVCT band of the formyl derivative 1-CHO+ proves that vibrational coupling of the IVCT transition to a symmetrical vibration is the underlying reason for band skewing. All of our results indicate that the MV radical cations remain electronically strongly coupled despite an increasingly stronger bias of the highest occupied molecular orbital to the vinylruthenium entity. Moreover, the dications of these complexes were found to be paramagnetic, which makes them rare examples of compounds that combine strong electronic coupling in the cationic MV state with paramagnetism of the dications.

Directing Energy Transfer in Panchromatic Platinum Complexes for Dual Vis-Near-IR or Dual Visible Emission from σ-Bonded BODIPY Dyes.

We report on the platinum complexes trans-Pt(BODIPY)(8-ethynyl-BODIPY)(PEt3)2 (EtBPtB) and trans-Pt(BODIPY)(4-ethynyl-1,8-naphthalimide)(PR3)2 (R = Et, EtNIPtB-1; R = Ph, EtNIPtB-2), which all contain two different dye ligands that are connected to the platinum atom by a direct σ bond. The molecular structures of all complexes were established by X-ray crystallography and show that the different dye ligands are in either a coplanar or an orthogonal arrangement. π-stacking and several CH···F and short CH···π interactions involving protons at the phosphine substituents lead to interesting packing motifs in the crystal. The complexes feature several strong absorptions (ε = 3.2 × 105-5.5 × 105 M-1 cm-1) that cover the regime from 350 to 480 nm (EtNIPtB-1 and EtNIPtB-2) or from 350 to 580 nm (EtBPtB). Besides the typical absorption bands of both kinds of attached dyes, they also feature an intense band near 400-420 nm, which is assigned by time-dependent density functional theory calculations to a higher-energy transition within the ethynyl-BODIPY (EtB) ligand or to charge transfer between the BODIPY (B) and naphthalimide (NI) chromophores. All complexes show dual fluorescence and phosphorescence emission from either the B (EtNIPtB-1 and EtNIPtB-2) or EtB (EtBPtB) ligand with a maximum phosphorescence quantum yield of 41% for EtNIPtB-1. The latter seems to be the highest reported value for room temperature phosphorescence from a BODIPY dye. The complete quenching of the emission from the chromophore absorbing at the higher energy and the appearance of the corresponding absorption bands in the fluorescence and phosphorescence excitation spectra indicate complete and rapid energy transfer to the chromophore with the lower-energy excited state, i.e., EtNI → B in EtNIPtB-1 and EtNIPtB-2 and B → EtB in EtBPtB. The latter process was further investigated by transient absorption spectroscopy, indicating that energy transfer is complete within 0.6 ns. EtNIPtB-1 catalyzes the photooxidation of 1,5-dihydroxynaphthalene with photogenerated 1O2 to Juglone at a much faster rate than methylene blue but with only modest quantum yields of 37% and with the onset of photodegradation after 60 min.

Ferrocene- and Biferrocene-Containing Macrocycles towards Single-Molecule Electronics.

Cyclic multiredox centered systems are currently of great interest, with new compounds being reported and developments made in understanding their behavior. Efficient, elegant, and high-yielding (for macrocyclic species) synthetic routes to two novel alkynyl-conjugated multiple ferrocene- and biferrocene-containing cyclic compounds are presented. The electronic interactions between the individual ferrocene units have been investigated through electrochemistry, spectroelectrochemistry, density functional theory (DFT), and crystallography to understand the effect of cyclization on the electronic properties and structure.