Person: Winter, Rainer F.
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1,4-Divinylphenylene-bridged diruthenium complexes with 2-hydroxypyridine- and 2- or 8-hydroxyquinoline-olate ligands
Linker permethylation as a means to foster valence tautomerism and thwart dimerization in ferrocenyl-triarylmethylium cations
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.
Charge and Spin Delocalization in Mixed-Valent Vinylruthenium–Triarylamine-Conjugates with Planarized Triarylamines
Organic binary charge-transfer compounds of 2,2′ : 6′,2′′ : 6′′,6-trioxotriphenylamine and a pyrene-annulated azaacene as donors
Three binary charge-transfer (CT) compounds resulting from the donor 2,2′ : 6′,2′′ : 6′′,6-trioxotriphenylamine (TOTA) and the acceptors F4TCNQ and F4BQ and of a pyrene-annulated azaacene (PAA) with the acceptor F4TCNQ are reported. The identity of these CT compounds are confirmed by single-crystal X-ray diffraction as well as by IR, UV-vis-NIR and EPR spectroscopy. X-ray diffraction analysis reveals a 1 : 1 stoichiometry for TOTA·F4TCNQ, a 2 : 1 donor : acceptor ratio in (TOTA)2·F4BQ, and a rare 4 : 1 stoichiometry in (PAA)4·F4TCNQ, respectively. Metrical parameters of the donor (D) and acceptor (A) constituents as well as IR spectra indicate full CT in TOTA·F4TCNQ, partial CT in (TOTA)2·F4BQ and only a very modest one in (PAA)4·F4TCNQ. Intricate packing motifs are present in the crystal lattice with encaged, π-stacked (F4TCNQ-)2 dimers in TOTA·F4TCNQ or mixed D/A stacks in the other two compounds. Their solid-state UV-vis-NIR spectra feature CT transitions. The CT compounds with F4TCNQ are electrical insulators, while (TOTA)2·F4BQ is weakly conducting.
Synthesis and crystal structures of rhodium acetate paddle‐wheel complexes with anchor group‐functionalized and hydrogen bond‐supported axial ligands
We report the synthesis and X-ray structures of four Rh 2 (O 2 Ac) 4 (L Ax ) 2 (OAc = acteate, CH 3 COO - ) paddle-wheel complexes ( C1 - C4 ) with methylthio-modified axial ligands L Ax derived from benzamidine ( L1 ), anilinopyrimidine ( L2 ) or isothiourea ( L3 , L4 ) that are capable of forming N‑H×××O hydrogen bonds to the equatorially bridging acetate ligands. This was done with the aim to suppress dissociation of the axial ligands and to make the complexes amenable to single-molecule conductance measurements in a scanning tunneling microscope break-junction (STM-BJ) setup. The characteristic spectroscopic features (NMR, IR, vis), crystal structures, the hydrogen-bonding motifs and a DFT-based screening of their frontier molecular orbitals are presented. Our calculations suggest that hydrogen-bonding stabilizes axial ligand binding by 20kJ/mol to 30 kJ/mol and that the HOMO of the rhodium paddle-wheels is closer to the Au Fermi level than the LUMO, so that the rhodium paddle-wheels are expected to constitute hole conductors.
Tetraruthenium Macrocycles with Laterally Extended Bis(alkenyl)quinoxaline Ligands and Their F4TCNQ•− Salts
We report on the tetraruthenium macrocycles Ru4-5 and -6 with a π-conjugated pyrene-appended 5,8-divinylquinoxaline ligand and either isophthalate or thiophenyl-2,5-dicarboxylate linkers and their charge-transfer salts formed by oxidation with two equivalents of F4TCNQ. Both macrocyclic complexes were characterized by NMR spectroscopy, mass spectrometry, cyclic and square-wave voltammetry, and by IR, UV–vis–NIR, and EPR spectroscopy in their various oxidation states.
Single-molecule conductance studies on quasi- and metallaaromatic dibenzoylmethane coordination compounds and their aromatic analogs
The ability to predict the conductive behaviour of molecules, connected to macroscopic electrodes, represents a crucial prerequisite for the design of nanoscale electronic devices. In this work, we investigate whether the notion of a negative relation between conductance and aromaticity (the so-called NRCA rule) also pertains to quasi-aromatic and metallaaromatic chelates derived from dibenzoylmethane (DBM) and Lewis acids (LAs) that either do or do not contribute two extra dπ electrons to the central resonance-stabilised β-ketoenolate binding pocket. We therefore synthesised a family of methylthio-functionalised DBM coordination compounds and subjected them, along with their truly aromatic terphenyl and 4,6-diphenylpyrimidine congeners, to scanning tunneling microscope break-junction (STM-BJ) experiments on gold nanoelectrodes. All molecules share the common motif of three π-conjugated, six-membered, planar rings with a meta-configuration at the central ring. According to our results, their molecular conductances fall within a factor of ca. 9 in an ordering aromatic < metallaaromatic < quasi-aromatic. The experimental trends are rationalised by quantum transport calculations based on density functional theory (DFT).
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.
Electron-Rich Diruthenium Complexes with π-Extended Alkenyl Ligands and Their F4TCNQ 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.