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81.
82.
Bijesh Sekaran Youngwoo Jang Prof. Dr. Rajneesh Misra Prof. Dr. Francis D'Souza 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(56):12991-13001
A new set of free-base and zinc(II)-metallated, β-pyrrole-functionalized unsymmetrical push–pull porphyrins were designed and synthesized via β-mono- and dibrominated tetraphenylporphyrins using Sonogashira cross-coupling reactions. The ability of donors and acceptors on the push–pull porphyrins to produce high-potential charge separated states was investigated. The porphyrins were functionalized at the opposite β,β′-pyrrole positions of porphyrin ring bearing triphenylamine push groups and naphthalimide pull groups. Systematic studies involving optical absorption, steady-state and time-resolved emission revealed existence of intramolecular type interactions both in the ground and excited states. The push–pull nature of the molecular systems was supported by frontier orbitals generated on optimized structures, wherein delocalization of HOMO over the push group and LUMO over the pull group connecting the porphyrin π-system was witnessed. Electrochemical studies were performed to visualize the effect of push and pull groups on the overall redox potentials of the porphyrins. Spectroelectrochemical studies combined with frontier orbitals helped in characterizing the one-electron oxidized and reduced porphyrins. Finally, by performing transient absorption studies in polar benzonitrile, the ability of push–pull porphyrins to produce charge-separated states upon photoexcitation was confirmed and the measured rates were in the range of 109 s−1. The lifetime of the final charge separated state was around 5 ns. This study ascertains the importance of push–pull porphyrins in solar energy conversion and diverse optoelectronic applications, for which high-potential charge-separated states are warranted. 相似文献
83.
Farah Naz Bibimaryam Mousavi Zhixiong Luo Christia Jabbour Philippe M. Heynderickx Somboon Chaemchuen Francis Verpoort 《应用有机金属化学》2019,33(5)
A series of spray dried zeolitic imidazolate frameworks (ZIFs = ZIF‐8, ZIF‐67, and Zn/Co‐ZIF) are used as a catalyst for the bulk ring‐opening polymerization of δ‐valerolactone without any co‐catalyst to generate polyvalerolactone. Interestingly, using the same catalyst under the same reaction conditions could manipulate the structure of the product polymer, and thus its physical properties. Thus, using a dried substrate leads to the formation of the cyclic polymer while a linear polymer was formed on using the commercially available substrate. An activated monomer mechanism has been suggested where the propagating zinc alkoxide undergoes an intramolecular transesterification to release cyclic or linear polyvalerolactone. The ROP of δ‐VL without drying shows that the polymeric zwitterions have little tendency to cyclize in the presence of moisture. At 140 °C, ZIF‐8 shows a superior catalytic activity resulting in the production of cyclic polyvalerolactone having a high molecular weight as compared to ZIF‐67 or Zn/Co‐ZIF due to the presence of highly active sites. The catalyst could be recycled and reused without any significant loss of catalytic activity. 相似文献
84.
THE REACTIONS OF N3P3CL6 AND RELATED COMPOUNDS WITH DIFUNCTIONAL REAGENTS. COMPARISONS AND CONTRASTS
Abdulla H. Alkubaisi W. Francis Deutsch Michael B. Hursthouse Harold G. Parkes Leylacaron S. Shaw Robert A. Shaw 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):229-237
Abstract The reactions of N3P3Cl6 with a variety of difunctional reagents are discussed. NMR spectroscopic and X-ray crystallographic investigations are presented. 相似文献
85.
Saeed Kamali Hongxin Wang Devrani Mitra Hideaki Ogata Wolfgang Lubitz Brian C. Manor Thomas B. Rauchfuss Deborah Byrne Violaine Bonnefoy Francis E. Jenney Michael W. W. Adams Yoshitaka Yoda Ercan Alp Jiyong Zhao Stephen P. Cramer 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2013,125(2):752-756
86.
Borane-tetrahydrofuran complex reduces trifluoromethyl oximes to trifluoromethyl hydroxylamines in good yields. 相似文献
87.
Corrigendum: An NMR‐Driven Crystallography Strategy to Overcome the Computability Limit of Powder Structure Determination: A Layered Aluminophosphate Case 下载免费PDF全文
88.
89.
Francis X. Smith Brian D. Williams Eric Gelsleichter Judy A. Podcasy John T. Sisko David M. Hrubowchak 《合成通讯》2013,43(6):765-769
It was found that 3‐acyl derivatives of oxindoles, benzo[b]furan‐2‐ones, and benzo[b]thiophen‐2‐ones could be efficiently and conveniently reduced to the corresponding alkyl derivatives by pelletized sodium borohydride in acetic acid. A typical procedure involves heating the acylated substrates for approximately 90 min in a slurry of glacial acetic acid and sodium borohydride to provide the 3‐alkyl product in yields ranging from 62% to 96%. This synthetic methodology represents a convenient approach to the synthesis of the alkyl derivatives. 相似文献
90.
Francis J. Chung 《Journal of Fourier Analysis and Applications》2015,21(3):628-665
We show that measurements of a Neumann-to-Dirichlet map, with either inputs or outputs restricted to part of the boundary, can determine an electric potential on that domain. Given a convexity condition on the domain, either the set on which measurements are taken, or the set on which input functions are supported, can be made to be arbitrarily small. The result is analogous to the result by Kenig, Sjöstrand, and Uhlmann for the Dirichlet-to-Neumann map. The main new ingredient in the proof is an improved Carleman estimate for the Schrödinger operator with appropriate boundary conditions. This is proved by Fourier analysis of a conjugated operator along the boundary of the domain. 相似文献