Electronic Transitions in Different Redox States of Trinuclear 5,6,11,12,17,18-Hexaazatrinaphthylene-Bridged Titanium Complexes: Spectroelectrochemistry and Quantum Chemistry

Multinuclear transition metal complexes bridged by ligands with extended π-electronic systems show a variety of complex electronic transitions and electron transfer reactions. While a systematic understanding of the photochemistry and electrochemistry has been attained for binuclear complexes, much less is known about trinuclear complexes such as hexaphenyl-5,6,11,12,17,18-hexaazatrinaphthylene-tristitanocene [(Cp₂Ti)₃HATN(Ph)₆]. The voltammogram of [(Cp₂Ti)₃HATN(Ph)₆] shows six oxidation and three reduction waves. Solution spectra of [(Cp₂Ti)₃HATN(Ph)₆] and of the electrochemically formed oxidation products show electronic transitions in the UV, visible and the NIR ranges. Density functional theory (DFT) and linear response time-dependent DFT show that the three formally titanium(II) centers transfer an electron to the HATN ligand in the ground state. The optically excited transitions occur exclusively between ligand-centered orbitals. The charged titanium centers only provide an electrostatic frame to the extended π-electronic system. Complete active self-consistent field (CASSCF) calculation on a structurally simplified model compound, which considers the multi-reference character imposed by the three titanium centers, can provide an interpretation of the experimentally observed temperature-dependent magnetic behavior of the different redox states of the title compound in full consistency with the interpretation of the electronic spectra.     

竖直恒温面自然对流边界层不稳定性研究

在无扰动、随机式扰动以及正弦式扰动下,通过对竖直恒温面处状态Ra为1.328×10^9、Pr为6.24的自然对流进行模拟,探索了热边界层的不稳定性和共振强化自然对流换热。结果表明:(1)竖直自然对流边界层上游位置的随机式扰动对热边界层的影响主要体现在稳定阶段;(2)该状态下的竖直自然对流边界层的特征频率为15 067,且相比于无扰动状态,频率为15 067的正弦式扰动能在竖直恒温面处提高5.15%的换热量;(3)在竖直自然对流边界层上游位置加入特征频率的正弦式扰动,竖直恒温面处的局部努塞尔数Nu均出现明显波动,且波动随着边界层高度的增加而增大。     

Switching of heating and cooling modes using thermal radiation films

We study emissivity (ε)-dependent radiative heat transfer phenomena in remote and contact configurations. To demonstrate the emissivity-dependent radiative heating mode in a remote configuration, we fabricated miniature greenhouses covered with low (0.34)- and high-ε (0.86) polyethylene films and monitored temperatures on the floors, insides, and covers of the greenhouses during 24 h. The high-ε greenhouse yielded a 9-°C increase in floor temperature relative to the low-ε greenhouse at a one-sun solar irradiance because the high-ε film effectively trapped floor radiation. In contrast, the cover temperature remained lower in the high-ε greenhouse due to intensified radiation released from the high-ε film. This self-cooling effect was more evident when an emissive film was in physical contact with an object. While bare copper heated up to 55 °C, a high-ε film coated copper substrate was kept cooler by 4 and 2 °C compared with the bare and low-ε film coated copper samples, respectively.     

Comparison of monomethoxy‐, dimethoxy‐, and trimethoxysilane anchor groups for surface‐initiated RAFT polymerization from silica surfaces

The immobilization of reversible addition–fragmentation chain transfer (RAFT) agents on silica for surface‐initiated RAFT polymerizations (SI‐RAFT) via the Z‐group approach was studied systematically in dependence of the functionality of the RAFT‐agent anchor group. Monoalkoxy‐, dialkoxy‐, and trialkoxy silyl ether groups were incorporated into trithiocarbonate‐type RAFT agents and bound to planar silica surfaces as well as to silica nanoparticles. The immobilization efficiency and the structure of the bound RAFT‐agent film varied strongly in dependence of the used solvent (toluene vs. 1,2‐dimethoxyethane) and the anchor group functionality, as evidenced by atomic force microscopy, transmission electron microscopy, dynamic light scattering, and UV/Vis spectroscopy. Surface‐initiated RAFT polymerizations using functionalized silica nanoparticles revealed that grafted oligomers, which often occur in SI‐RAFT, are not formed within the crosslinked structures that originate from the immobilization, and that RAFT‐agent films that show less aggregation during the immobilization are more efficient during SI‐RAFT in terms of polymer grafting density. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 103–113     

Synthesis and liquid crystalline behavior of bulky poly(methacrylamide)s

N‐(Bis(4‐(2‐ethylhexyloxy)phenyl)(phenyl)‐methyl)methacrylamide was synthesized and polymerized via reversible addition‐fragmentation chain‐transfer (RAFT) polymerization. The chain‐transfer agent (4‐cyano‐4‐(phenylcarbonothioylthio) pentanoic acid (CPADB)), combined with a chiral additive, and a radical initiator yielded polymers with dispersities between 1.2 and 1.4. At low concentrations, the polymers are soluble in hexanes and chloroform while at higher concentrations they swell in these solvents. Characterization of the polymers by wide‐angle X‐ray scattering (WAXS) revealed an interplanar distance of 19.0 Å. The WAXS data combined with polarized optical microscopy support a lamellar crystallization and lyotropic liquid crystalline behavior in hexanes and chloroform. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2563–2568     

Investigation of Suzuki–Miyaura catalyst‐transfer polycondensation of AB‐type fluorene monomer using coordination‐saturated aryl Pd(II) halide complexes as initiators

Novel triarylamine‐based coordination‐saturated aryl Pd(II) halide complexes ligated by PEt₃, PCy₃, and P(o‐tol)₃ were successfully synthesized by direct oxidative addition of aryl halide to the corresponding Pd(0) precursors. Suzuki–Miyaura coupling polymerization of 2‐(7‐halide‐9,9‐dioctylfluoren‐2‐yl)?1,3,2‐dioxaborinane with these Pd(II) complexes as initiators was investigated for the synthesis of poly(fluorene)s with triarylamine end group. Pd(II) complexes with PCy₃ or P(o‐tol)₃ exhibited catalytic activity and realized the catalyst‐transfer polycondensation at 75 °C and room temperature, respectively, while the polymerization using Pd(II) catalyst ligated by PEt₃ did not proceed, which indicated that the bulky phosphine ligands could facilitate the reductive elimination and further promote the polymerization. In addition, the dimeric Pd(II) complex with P(o‐tol)₃ can convert into monomeric Pd(II) intermediate with an open coordination site, which had a higher activity. The end groups of the afforded polyfluorene were analyzed by matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectrometry, in which the Ar/H end groups are indicative of the catalyst‐transfer polymerization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1457–1463     

Protic Anions [H(B12X12)]− (X=F,Cl, Br,I) That Act as Brønsted Acids in the Gas Phase

The acidity of protic cations and neutral molecules has been studied extensively in the gas phase, and the gas‐phase acidity has been established previously as a very useful measure of the intrinsic acidity of neutral and cationic compounds. However, no data for any anionic acids were available prior to this study. The protic anions [H(B₁₂X₁₂)]^? (X=F, Cl, Br, I) are expected to be the most acidic anions known to date. Therefore, they were investigated in this study with respect to their ability to protonate neutral molecules in the gas phase by using a combination of mass spectrometry and quantum‐chemical calculations. For the first time it was shown that in the gas phase protic anions are also able to protonate neutral molecules and thus act as Brønsted acids. According to theoretical calculations, [H(B₁₂I₁₂)]^? is the most acidic gas‐phase anion, whereas in actual protonation experiments [H(B₁₂Cl₁₂)]^? is the most potent gas‐phase acidic anion for the protonation of neutral molecules. This discrepancy is explained by ion pairing and kinetic effects.     

Role of the Bridge in Photoinduced Electron Transfer in Porphyrin–Fullerene Dyads

The role of π‐conjugated molecular bridges in through‐space and through‐bond electron transfer is studied by comparing two porphyrin–fullerene donor–acceptor (D–A) dyads. One dyad, ZnP–Ph–C₆₀ (ZnP=zinc porphyrin), incorporates a phenyl bridge between D and A and behaves very similarly to analogous dyads studied previously. The second dyad, ZnP–EDOTV–C₆₀, introduces an additional 3,4‐ethylenedioxythienylvinylene (EDOTV) unit into the conjugated bridge, which increases the distance between D and A, but, at the same time, provides increased electronic communication between them. Two essential outcomes that result from the introduction of the EDOTV unit in the bridge are as follows: 1) faster charge recombination, which indicates enhanced electronic coupling between the charge‐separated and ground electronic states; and 2) the disappearance of the intramolecular exciplex, which mediates photoinduced charge separation in the ZnP–Ph–C₆₀ dyad. The latter can be interpreted as a gradual decrease in electronic coupling between locally excited singlet states of D and A when introducing the EDOTV unit into the D–A bridge.     

Synthesis of tertiary amine‐based pH‐responsive polymers by RAFT Polymerization

Well‐defined tertiary amine‐based pH‐responsive homopolymers and block copolymers were synthesized via reversible addition‐fragmentation chain transfer (RAFT) polymerization using 4‐cyanopentanoic acid dithiobenzoate (CPAD) as the RAFT agent for homopolymers and a poly(ethylene glycol) (PEG) macro‐RAFT agent for the block copolymers. ¹H NMR and gel permeation chromatography results confirmed the successful synthesis of these homopolymers and block copolymers. Kinetics studies indicated that the formation of both the homopolymers and the block copolymers were well defined. The pKa titration experiments suggested that the homopolymers and the related block copolymers have a similar pKa. The dynamic light scattering investigation showed that all of the block copolymers underwent a sharp transition from unimers to micelles around their pKa and the hydrodynamic diameter (D_h) was not only dependent on the molecular weight but also on the composition of the block copolymers. The polymer solution of PEG‐b‐PPPDEMA formed the largest micelle compare to the PEG‐b‐PDPAEMA and PEG‐b‐PDBAEMA with a similar molecular weight. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1010–1022