@article{RienschSwobodaLiketal.2021, author = {Riensch, Nicolas Alexander and Swoboda, Lukas and Lik, Artur and Krummenacher, Ivo and Braunschweig, Holger and Helten, Holger}, title = {Conjugated Bis(triarylboranes) with Disconnected Conjugation}, series = {Zeitschrift f{\"u}r anorganische und allgemeine Chemie}, volume = {647}, journal = {Zeitschrift f{\"u}r anorganische und allgemeine Chemie}, number = {5}, doi = {10.1002/zaac.202000476}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-258020}, pages = {421-424}, year = {2021}, abstract = {A series of methylene-bridged bis(triarylboranes) has been synthesized via two complementary routes using metal-free catalytic Si/B exchange condensation under mild conditions. The title compounds comprise two borane moieties that show effective internal π-conjugation involving the respective boron centers and the adjacent hetaryl groups. Conjugation between both borane units, however, is disrupted by the aliphatic linker. Cyclic voltammetry revealed minimal electronic communication between the boron centers, as evidenced by two closely spaced reduction processes. The UV-vis spectra showed bathochromic shifted absorption bands compared to related monoboranes, which is attributed to the methylene bridge. A further red-shift results upon introduction of methyl or SiMe\(_3\) groups at the terminal thiophene rings.}, language = {en} } @article{BachmannHelbigCrumbachetal.2022, author = {Bachmann, Jonas and Helbig, Andreas and Crumbach, Merian and Krummenacher, Ivo and Braunschweig, Holger and Helten, Holger}, title = {Fusion of Aza- and Oxadiborepins with Furans in a Reversible Ring-Opening Process Furnishes Versatile Building Blocks for Extended π-Conjugated Materials}, series = {Chemistry - A European Journal}, volume = {28}, journal = {Chemistry - A European Journal}, number = {63}, doi = {10.1002/chem.202202455}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-293926}, year = {2022}, abstract = {A modular synthesis of both difurooxa- and difuroazadiborepins from a common precursor is demonstrated. Starting from 2,2′-bifuran, after protection of the positions 5 and 5' with bulky silyl groups, formation of the novel polycycles proceeds through opening of the furan rings to a dialkyne and subsequent re-cyclization in the borylation step. The resulting bifuran-fused diborepins show pronounced stability, highly planar tricyclic structures, and intense blue light emission. Deprotection and transformation into dibrominated building blocks that can be incorporated into π-extended materials can be performed in one step. Detailed DFT calculations provide information about the aromaticity of the constituent rings of this polycycle.}, language = {en} } @article{CrumbachBachmannFritzeetal.2021, author = {Crumbach, Merian and Bachmann, Jonas and Fritze, Lars and Helbig, Andreas and Krummenacher, Ivo and Braunschweig, Holger and Helten, Holger}, title = {Dithiophene-Fused Oxadiborepins and Azadiborepins: A New Class of Highly Fluorescent Heteroaromatics}, series = {Angewandte Chemie International Edition}, volume = {60}, journal = {Angewandte Chemie International Edition}, number = {17}, doi = {10.1002/anie.202100295}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-238996}, pages = {9290 -- 9295}, year = {2021}, abstract = {Access to dithiophene-fused oxadiborepins and the first azadiborepins attained via a modular synthesis route are presented. The new compounds emit intense blue light, some of which demonstrate fluorescence quantum yields close to unity. Cyclic voltammetry (CV) revealed electrochemically reversible one-electron reduction processes. The weak aromatic character of the novel 1,2,7-azadiborepin ring is demonstrated with in-depth theoretical investigations using nucleus-independent chemical shift (NICS) scans and anisotropy of the induced current density (ACID) calculations.}, language = {en} } @article{SchorrSchopperRienschetal.2021, author = {Schorr, Fabian and Schopper, Nils and Riensch, Nicolas and Fantuzzi, Felipe and Neder, Marco and Dewhurst, Rian D. and Thiess, Thorsten and Br{\"u}ckner, Tobias and Hammond, Kai and Helten, Holger and Finze, Maik and Braunschweig, Holger}, title = {Controlled Synthesis of Oligomers Containing Main-Chain B(sp\(^{2}\))-B(sp\(^{2}\)) Bonds}, series = {Chemistry—A European Journal}, volume = {27}, journal = {Chemistry—A European Journal}, number = {64}, doi = {10.1002/chem.202103366}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-257274}, pages = {16043-16048}, year = {2021}, abstract = {A number of novel alkynyl-functionalized diarylbis(dimethylamino)diboranes(4) are prepared by salt metathesis, and the appended alkynyl groups are subjected to hydroboration. Their reactions with monohydroboranes lead to discrete boryl-appended diborane(4) species, while dihydroboranes induce their catenation to oligomeric species, the first known examples of well-characterized macromolecular species with B-B bonds. The oligomeric species were found to comprise up to ten repeat units and are soluble in common organic solvents. Some of the oligomeric species have good air stability and all were characterized by NMR and vibrational spectroscopy and size-exclusion chromatography techniques.}, language = {en} } @article{BrosgeLorenzHeltenetal.2019, author = {Brosge, Felix and Lorenz, Thomas and Helten, Holger and Bolm, Carsten}, title = {BN- and BO-Doped Inorganic-Organic Hybrid Polymers with Sulfoximine Core Units}, series = {Chemistry - A European Journal}, volume = {25}, journal = {Chemistry - A European Journal}, number = {55}, doi = {10.1002/chem.201903289}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-206194}, pages = {12708-12711}, year = {2019}, abstract = {While polysulfones constitute a class of well-established, highly valuable applied materials, knowledge about polymers based on the related sulfoximine group is very limited. We have employed functionalized diaryl sulfoximines and a p -phenylene bisborane as building blocks for unprecedented BN- and BO-doped alternating inorganic-organic hybrid copolymers. While the former were accessed by a facile silicon/boron exchange protocol, the synthesis of polymers with main-chain B-O linkages was achieved by salt elimination.}, language = {en} } @article{HahnLuxenhoferHeltenetal.2021, author = {Hahn, Lukas and Luxenhofer, Robert and Helten, Holger and Forster, Stefan and Fritze, Lars and Polzin, Lando and Keßler, Larissa}, title = {ABA Type Amphiphiles with Poly(2-benzhydryl-2-oxazine) Moieties: Synthesis, Characterization and Inverse Thermogelation}, series = {Macromolecular Chemistry and Physics}, volume = {222}, journal = {Macromolecular Chemistry and Physics}, number = {17}, doi = {10.1002/macp.202100114}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-265124}, year = {2021}, abstract = {Thermoresponsive polymers are frequently involved in the development of materials for various applications. Here, polymers containing poly(2- benzhydryl-2-oxazine) (pBhOzi) repeating units are described for the first time. The homopolymer pBhOzi and an ABA type amphiphile comprising two flanking hydrophilic A blocks of poly(2-methyl-2-oxazoline) (pMeOx) and the hydrophobic aromatic pBhOzi central B block (pMeOx-b-pBhOzi-b-pMeOx) are synthesized and the latter is shown to exhibit inverse thermogelling properties at concentrations of 20 wt.\% in water. This behavior stands in contrast to a homologue ABA amphiphile consisting of a central poly(2-benzhydryl-2-oxazoline) block (pMeOx-b-pBhOx-b-pMeOx). No inverse thermogelling is observed with this polymer even at 25 wt.\%. For 25 wt.\% pMeOx-b-pBhOzi-b-pMeOx, a surprisingly high storage modulus of ≈22 kPa and high values for the yield and flow points of 480 Pa and 1.3 kPa are obtained. Exceeding the yield point, pronounced shear thinning is observed. Interestingly, only little difference between self-assemblies of pMeOx-b-pBhOzi-b-pMeOx and pMeOx-b-pBhOx-b-pMeOx is observed by dynamic light scattering while transmission electron microscopy images suggest that the micelles of pMeOx-b-pBhOzi-b-pMeOx interact through their hydrophilic coronas, which is probably decisive for the gel formation. Overall, this study introduces new building blocks for poly(2-oxazoline) and poly(2-oxazine)-based self-assemblies, but additional studies will be needed to unravel the exact mechanism.}, language = {en} }