Merging of a Supramolecular Ligand with a Switchable Luminophore - Light-Responsiveness, Photophysics and Bioimaging.

: In this contribution we report on a novel approach towards luminescent light-responsive ligands. To this end, cyanostilbene- guanidiniocarbonyl-pyrrole hybrids were designed and investigated. Merging of a luminophore with a supramolecular bioactive ligand bears numerous advantages by overcoming the typical drawbacks of drug-labelling, influencing the overall performance of the active species by attachment of a large luminophore. Here we were able to establish a simple and easily accessible synthesis route to different cyanostyryl-guanidininiocarbonyl-pyrrole (CGCP) derivatives. These compounds were investigated regarding their light-responsive double bond isomerisation, their molecular structures in single crystals by means of X-ray diffractometry, their emission properties by state of the art photophysical characterisation as well as bioimaging and assessment of cell toxicity.

Indium(III)-Catalyzed Haloalkynylation Reaction of Alkynes.

Green chemistry strives for sustainability at the molecular level and is gaining increasing relevance in the development of chemical reactions. The haloalkynylation reaction is a highly atom-economical C-C coupling reaction that was previously only achieved using transition metal catalysts. It enables the introduction of an alkyne unit and a halogen atom into the target molecule. Herein, we present a haloalkynylation reaction catalyzed by indium(III) halides. The use of indium(III) bromide as a catalyst leads exclusively to the cis addition products with yields up to 86 %. In addition, iodoacetylenes can be applied for the first time for the haloalkynylation reaction of internal alkynes which is an important step forward in the development of industrially relevant and sustainable catalysts. In contrast to gold catalysis, which proceeds via a similar mechanism, the use of alkyl-substituted haloacetylenes as reagents is also possible. Based on 13C labeling experiments and quantum chemical calculations, we postulate two possible mechanisms for the indium(III)-catalyzed haloalkynylation reactions.

Catalytic hydroboration of aldehydes and ketones with an electron-rich acyclic metallasilylene.

The application of main group metal complexes in catalytic reactions is of increasing interest. Here we show that the electron-rich, acyclic metallasilylene L'(Cl)GaSiL C (L' = HC[C(Me)NDipp]2, Dipp = 2,6-iPr2C6H3; L = PhC(NtBu)2) acts as a precatalyst in the hydroboration of aldehydes with HBPin. Mechanistic studies with iso-valeraldehyde show that silylene C first reacts with the aldehyde with [2 + 1] cycloaddition in an oxidative addition to the oxasilirane 1, followed by formation of the alkoxysilylene LSiOCH[Ga(Cl)L']CH2CHMe2 (2), whose formation formally results from a reductive elimination reaction at the Si center. Alkoxysilylene 2 represents the active hydroboration catalyst and shows the highest catalytic activity with n-hexanal (reaction time: 40 min, yield: >99%, TOF = 150 h-1) at room temperature with a catalytic load of only 1 mol%. Furthermore, the hydroboration reaction catalysed by alkoxysilylene 2 is a living reaction with good chemoselectivity. Quantum chemical calculations not only provide mechanistic insights into the formation of alkoxysilylene 2 but also show that two completely different hydroboration mechanisms are possible.

Activation of non-polar bonds by an electron-rich gallagermylene.

The electron-rich germylene LGa(µ-Cl)GeArMes (1) (L = CH[C(Me)N(Dipp)]2, Dipp = 2,6-iPr2C6H3, ArMes = 2,6-Mes2C6H3, Mes = 2,4,6-Me3C6H2) shows promising potential in the σ-bond activation of unpolar molecules as is shown in oxidative addition reactions with H2 and P4, yielding L(Cl)GaGe(H)2ArMes (2) and L(Cl)Ga(P4)GeArMes (3). Compounds 2 and 3 were characterised spectroscopically (1H, 13C{1H}, (31P{1H}), IR) and by single-crystal X-ray diffraction (sc-XRD).

Metal-metal cooperativity boosts Lewis basicity and reduction properties of the bis(gallanediyl) CyL2Ga2.

The interplay of two proximate gallium centres equips the bimetallic complex CyL2Ga2 (1, CyL2 = 1,2-trans-Cy[NC(Me)C(H)C(Me)N(Dip)]2, Dip = 2,6-i-Pr2C6H3) with increased Lewis basicity and higher reducing power compared to the monometallic gallanediyl LGa (2, L = HC[MeCN(Dip)]2) as evidenced by cross-over experiments. Quantum chemical calculations were employed to support the experimental findings.

From Neutral Diarsenes to Diarsene Radical Ions and Diarsene Dications.

Diarsene [L(MeO)GaAs]2 (L=HC[C(Me)N(Ar)]2, Ar=2,6-iPr2C6H3, 4) reacts with MeOTf and MeNHC (MeNHC=1,3,4,5-tetra-methylimidazol-2-ylidene) to the diarsene [L(TfO)GaAs]2 (5) and the carbene-coordinated diarsene [L(MeO)GaAsAs(MeNHC)Ga(OMe)L] (6). The NHC-coordination results in an inversion of the redox properties of the diarsene 4, which shows only a reversible reduction event at E1/2=-2.06 V vs Fc0/+1, whereas the carbene-coordinated diarsene 6 shows a reversible oxidation event at E1/2=-1.31 V vs Fc0/+1. Single electron transfer reactions of 4 and 6 yielded [K[2.2.2.]cryp][L(MeO)GaAs]2 (8) and [L(MeO)GaAsAs(MeNHC)-Ga(OMe)L][B(C6F5)4] (9) containing the radical anion [L(MeO)GaAs]2⋅- (8⋅-) and the NHC-coordinated radical cation [L(MeO)GaAsAs(MeNHC)Ga(OMe)L]⋅+ (9⋅+), respectively, while the salt-elimination reaction of the triflate-coordinated diarsene 5 with Na[B(C6F5)4] gave [LGaAs]2[B(C6F5)4]2 (11) containing the dication [LGaAs]2 2+ (112+). Compounds 1-11 were characterized by 1H and 13C NMR, EPR (8, 9), IR, and UV-Vis spectroscopy and by single crystal X-ray diffraction (sc-XRD). DFT calculations provided a detailed understanding of the electronic nature of the diarsenes (4, 6) and the radical ions (8⋅-, 9⋅+), respectively.

Structural characterization and reactivity of a room-temperature-stable, antiaromatic cyclopentadienyl cation salt.

The singlet states of cyclopentadienyl (Cp) cations are considered as true prototypes of an antiaromatic system. Unfortunately, their high intrinsic reactivity inhibited their isolation in the solid state as a salt, and controlled reactions are also scarce. Here we present the synthesis and solid state structure of the room-temperature-stable Cp cation salt [Cp(C6F5)5]+[Sb3F16]-. Although the aromatic triplet state of the [Cp(C6F5)5]+ cation is energetically favoured in the gas phase according to quantum chemical calculations, coordination of the cation by either [Sb3F16]- or C6F6 in the crystal lattice stabilizes the antiaromatic singlet state, which is present in the solid state. The calculated hydride and fluoride ion affinities of the [Cp(C6F5)5]+ cation are higher than those of the perfluorinated tritylium cation [C(C6F5)3]+. Reactions of [Cp(C6F5)5]+[Sb3F16]- with CO, which probably yields the corresponding carbonyl complex, and of radical Cp(C6F5)5∙ with selected model substrates (Cp2Fe, (Ph3C∙)2 and Cp*Al) are also presented.

Gallaphosphene L(Cl)GaPGaL: A novel phosphinidene transfer reagent.

Gallaphosphene L(Cl)GaPGaL 1 (L=HC[C(Me)N(Ar)]2; Ar=2,6-iPr2C6H3) reacts with N-heterocyclic carbenes RNHC (RNHC=[CMeN(R)]2C; R=Me, iPr) to RNHC-coordinated phosphinidenes RNHC→PGa(Cl)L (R=Me 2 a, iPr 2 b) and with isonitriles RNC (R=iPr, Cy) to 1,3-phosphaazaallenes L(Cl)GaP=C=N-R (R=iPr 3 a, Cy 3 b), respectively. Quantum chemical calculations reveal that 2 a/2 b possess two localized lone pair of electrons, whereas 3 a/3 b only show one localized lone pair as was reported for gallaphosphene 1. 2 b reacts with 2.5 equivalents of a borane (THF ⋅ BH3) to the NHC-stabilized phosphinidene-borane complex [iPrNHC→P(BH2)]2(BH3)3 4 with concomitant formation of LGa(H)Cl 5. 2-5 are characterized by heteronuclear (1H, 13C{1H}, 31P{1H}) NMR and IR spectroscopy, elemental analysis, and single crystal X-ray diffraction (sc-XRD).

The Origin of Dual-Emission in PLICT Compounds - an Empirical Approach.

Fluorescence spectroscopy proves to be a powerful and versatile tool in scientific research, demanding ongoing advancements of fluorescence probes to cater to a broad range of applications. The particular interest lies in the development of fluorophores with multiplexing capability, emitting from more than one excited state depending on the polarity and viscosity of the surrounding medium. Here, we present a variety of novel dual planarized intramolecular charge transfer (PLICT) emitters based on cyano-1-aminoindole structures. We have chosen a combination of experimental studies, theoretical calculations and the creation of a unique fluorophore cataloging map. This map serves as a useful tool for empirically determining the origin of both fluorescence bands.

Multiple ethylene activation by heteroleptic L(Cl)Ga-substituted germylenes.

Ethylene insertion into the Ga-Ge bond of the L(Cl)Ga-substituted germylene LGa(µ-Cl)GeDMP 1 (L = HC(C(Me)NAr)2, Ar = 2,6-iPr2C6H3; DMP = 2,6-Mes2C6H3, Mes = 2,4,6-Me3C6H2) at ambient temperature is followed by dimerization of the as-formed germylene to give the digermene 3, which further reacted with ethylene in a [2 + 2] cycloaddition to give the 1,2-digermacyclobutane 4. In marked contrast, the amino-substituted germylene L(Cl)GaGeN(SiMe3)Ar 2 reacted directly to the 1,2-digermacyclobutane 5. Quantum chemical calculations confirmed the assumed reaction mechanism, hence demonstrating the crucial role of the substituent on the reaction mechanism.

Homoleptic and heteroleptic ketodiiminate zinc complexes for the ROP of cyclic l-lactide.

Homo- and heteroleptic ketodiiminate zinc complexes L12Zn2 (1, L1 = [Me2NC2H4NC(Me)CH]2CO), L2(ZnCp)2 (2, L2 = [Me2NC3H6NC(Me)CH]2CO, Cp = C5H5) and L2HZnCp* (3, Cp* = C5Me5) were synthesized and characterized by 1H and 13C NMR and IR spectroscopy as well as by elemental analysis and single crystal X-ray diffraction (sc-XRD, 2, 3). The catalytical activity of heteroleptic complexes 2 and 3 were tested in the ring-opening polymerization (ROP) of l-lactide. Homobimetallic complex 2 showed the highest activity and selectivity for the synthesis of cyclic polylactide (cPLLA; TOF = 17 460 h-1) at 100 °C in toluene solution, while linear polymers are formed with mononuclear complex 3.

Design and Synthesis of Artificial Nucleobases for Sequence-Selective DNA Recognition within the Major Groove.

We present the design and synthesis of artificial specific nucleobases, each one recognizing a single base pair within the major groove of duplex DNA. Computational calculations indicate that PNAs modified with these nucleobases enable the formation of highly stable triple helices with no sequence restrictions through multiple hydrogen bonding and π⋅⋅⋅π stacking interactions, without significantly widening the DNA double helix. New synthetic routes were developed to the structures of these fused heterocycles which have rarely been described in the literature. NMR titration experiments indicate specific hydrogen bonding at the Hoogsteen sites. The new building blocks allow the construction of four PNA monomers for each canonic base pair and their covalent connection to PNA oligomers. These can be designed complementary to any given DNA sequence. With high efficiency and relative simplicity of operation, the described methodologies and strategies hence form the basis for a new supramolecular ligand system targeting double-stranded DNA without strand invasion.

Syntheses and Structures of 5-Membered Heterocycles Featuring 1,2-Diphospha-1,3-Butadiene and Its Radical Anion.

LGa(P2 OC)cAAC 2 features a 1,2-diphospha-1,3-butadiene unit with a delocalized π-type HOMO and a π*-type LUMO according to DFT calculations. [LGa(P2 OC)cAAC][K(DB-18-c-6)] 3[K(DB-18-c-6] containing the 1,2-diphospha-1,3-butadiene radical anion 3⋅- was isolated from the reaction of 2 with KC8 and dibenzo-18-crown-6. 3 reacted with [Fc][B(C6 F5 )4 ] (Fc=ferrocenium) to 2 and with TEMPO to [L-H Ga(P2 OC)cAAC][K(DB-18-c-6)] 4[K(DB-18-c-6] containing the 1,2-diphospha-1,3-butadiene anion 4- . The solid state structures of 2, 3K(DB-18-c-6], and 4[K(DB-18-c-6] were determined by single crystal X-ray diffraction (sc-XRD).

Metal-coordinated distibene and dibismuthene dications - isoelectronic analogues of butadiene dications.

We report the synthesis and solid-state structures of DMAP-coordinated ([L(DMAP)GaPn]2[OTf]2; Pn = Sb 3, Bi 4) and base-free dipnictene dications ([LGaPn]2[BArFx]2, Pn = Sb: x = 24, 5a; 20, 5b; Bi: x = 24, 6a; 20, 6b). Quantum chemical calculations indicate that the dications 52+ and 62+ represent isoelectronic analogues of the butadiene dication.

Chalcogen-Bond-Induced Double Helix Based on Self-Assembly of a Small Planar Building Block.

As a rule, helical structures at the molecular level are formed by non-planar units. This makes the design of helices, starting from planar building blocks via self-assembly, even more fascinating. Until now, however, this has only been achieved in rare cases, where hydrogen and halogen bonds were involved. Here, we show that the carbonyl-tellurium interaction motif is suitable to assemble even small planar units into helical structures in solid phase. We found two different types of helices: both single and double helices, depending on the substitution pattern. In the double helix, the strands are connected by additional Te⋅⋅⋅Te chalcogen bonds. In the case of the single helix, a spontaneous enantiomeric resolution occurs in the crystal. This underlines the potential of the carbonyl-tellurium chalcogen bond to generate complex three-dimensional patterns.

Multifunctional Organocatalysts - Singly-Linked and Macrocyclic Bisphosphoric Acids for Asymmetric Phase-Transfer and Brønsted-Acid Catalysis.

The linking of phosphoric acids via covalent or mechanical bonds has proven to be a successful strategy for the design of novel organocatalysts. Here, we present the first systematic investigation of singly-linked and macrocyclic bisphosphoric acids, including their synthesis and their application in phase-transfer and Brønsted acid catalysis. We found that the novel bisphosphoric acids show dramatically increased enantioselectivities in comparison to their monophosphoric acid analogues. However, the nature, length and number of linkers has a profound influence on the enantioselectivities. In the asymmetric dearomative fluorination via phase-transfer catalysis, bisphosphoric acids with a single, rigid bisalkyne-linker give the best results with moderate to good enantiomeric excesses. In contrast, bisphosphoric acids with flexible linkers give excellent enantioselectivities in the transfer-hydrogenation of quinolines via cooperative Brønsted acid catalysis. In the latter case, sufficiently long linkers are needed for high stereoselectivities, as found experimentally and supported by DFT calculations.

Modulating the frontier orbitals of L(X)Ga-substituted diphosphenes [L(X)GaP]2 (X = Cl, Br) and their facile oxidation to radical cations.

Modulating the electronic structures of main group element compounds is crucial to control their chemical reactivity. Herein we report on the synthesis, frontier orbital modulation, and one-electron oxidation of two L(X)Ga-substituted diphosphenes [L(X)GaP]2 (X = Cl 2a, Br 2b; L = HC[C(Me)N(Ar)]2, Ar = 2,6-i-Pr2C6H3). Photolysis of L(Cl)GaPCO 1 gave [L(Cl)GaP]22a, which reacted with Me3SiBr with halide exchange to [L(Br)GaP]22b. Reactions with MeNHC (MeNHC = 1,3,4,5-tetramethylimidazol-2-ylidene) gave the corresponding carbene-coordinated complexes L(X)GaPP(MeNHC)Ga(X)L (X = Cl 3a, Br 3b). DFT calculations revealed that the carbene coordination modulates the frontier orbitals (i.e. HOMO/LUMO) of diphosphenes 2a and 2b, thereby affecting the reactivity of 3a and 3b. In marked contrast to diphosphenes 2a and 2b, the cyclic voltammograms (CVs) of the carbene-coordinated complexes each show one reversible redox event at E 1/2 = -0.65 V (3a) and -0.36 V (3b), indicating their one-electron oxidation to the corresponding radical cations as was confirmed by reactions of 3a and 3b with the [FeCp2][B(C6F5)4], yielding the radical cations [L(X)GaPP(MeNHC)Ga(X)L]B(C6F5)4 (X = Cl 4a, Br 4b). The unpaired spin in 4a (79%) and 4b (80%) is mainly located at the carbene-uncoordinated phosphorus atoms as was revealed by DFT calculations and furthermore experimentally proven in reactions with n Bu3SnH, yielding the diphosphane cations [L(X)GaPHP(MeNHC)Ga(X)L]B(C6F5)4 (X = Cl 5a, Br 5b). Compounds 2-5 were fully characterized by NMR and IR spectroscopy as well as by single crystal X-ray diffraction (sc-XRD), and compounds 4a and 4b were further studied by EPR spectroscopy, while their bonding nature was investigated by DFT calculations.

Tuning the Fluorescence in Dynamic Covalent Bonded Liquid Crystals.

A series of emissive liquid crystalline materials based on salicylidene derivatives is reported and investigated with respect to their thermoresponsive and mechanochromic properties. Single-crystal analysis and temperature-dependent powder X-ray diffraction measurements allowed us to correlate the intermolecular organization of the mesogens with thermoresponsive changes in the fluorescence behavior. As a proof-of-principle study, we employed the dynamics of the imine bond in transamination reactions for postsynthetic tuning of the fluorescence behavior as a further step toward the development of adaptive materials.

Fluorinated ß-diketonate complexes M(tfac)2(TMEDA) (M = Fe, Ni, Cu, Zn) as precursors for the MOCVD growth of metal and metal oxide thin films.

Partially fluorinated ß-diketonate complexes M(tfac)2(TMEDA) (M = Fe 1, Ni 2, Cu 3, Zn 4; tfac = 1,1,1-trifluoro-2,4-pentanedionate; TMEDA = N,N,N',N'-tetramethylethylenediamine) were synthesized and structurally (sc-XRD) and thermochemically (TGA) characterised. A new polymorph of Fe(tfac)2(TMEDA) was found. The structural and physicochemical properties of 1-4 were compared with related M(acac)2(TMEDA) and M(hfac)2(TMEDA) (acac = 2,4-pentanedionate, hfac = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate) ß-diketonate complexes to evaluate the effect of the degree of fluorination. A positive effect on the thermal behaviour of the metal acetylacetonates was observed, but no discernible trends. Application of complexes 1-4 as precursors in a MOCVD process yielded either metal (Ni, Cu) or metal oxide thin films (Fe3O4, ZnO), which were further oxidized to NiO, CuO and α-Fe2O3 films by calcination in air at 500 °C.

Structurally characterised intermediate of the oxidative addition of a heteroleptic germylene to gallanediyle.

Bond activation reactions using main group metal complexes are gaining increasing interest. We report on reactions of LGa (L = HC[C(Me)N(Ar)]2, Ar = Dipp = 2,6-i-Pr2C6H3,) with heteroleptic tetrylenes L'ECl (E = Ge, Sn; L' = N(SiMe3)Ar), yielding the donor-acceptor complex LGa-Sn(Cl)L' (1) or the oxidative addition product L(Cl)GaGeL' (3). The reaction with DMPGeCl (DMP = 2,6-Mes2C6H3, Mes = 2,4,6-Me3C6H2) yielded LGa(µ-Cl)GeDMP (2), which represents an intermediate of the oxidative addition reaction. 1-3 were characterized by NMR and IR spectroscopy as well as by single crystal X-ray diffraction (sc-XRD), while their electronic nature was analyzed by quantum chemical calculations.