38215-38-2Relevant articles and documents
Synthesis of organoplatinum poly (dendrimer)s: Pronounced effect of size and geometry of small organoplatinum linkers on the copolymerization efficiency with bifunctional dendritic macromonomers
Cheung, Siu-Yin,Chow, Hak-Fun
, p. 8874 - 8879 (2009)
The copolymerizations of two series of surface functionalized bis(acetylene) G1-G3 dendrimers, one (S-Gn) having a structural rigid skeleton and the other (L-Gn) a relatively more flexible architecture, with two platinum linkers, cis-[(Et2PCH2CH2PEt 2)PtCl2] (2) and [Cl-(Et3P)2Pt- C≡C-P-C6H4-], (3) were investigated. For both series of dendrimers, only linear and/or cyclic oligomers were formed when the cis-platinum linker 2 was used. However, high molecular weight (100-200 kD) organoplatinum poly(dendrimer)s were obtained from both series when the elongated linear rod-liked platinum linker 3 was employed and the formation of cyclic oligomers was greatly suppressed for both the structural rigid S-Gn and the structural flexible L-Gn series. These results are in sharp contrast to our earlier findings (S.-Y. Cheung, H.-F. Chow, T. Ngai, X. Wei, Chem. Eur. J. 2009, 75, 2278-2288) obtained by using a shorter linear platinum linker trans-[Pt-(PEt3)2Cl2] (1), where a larger amount of cyclic oligomers was formed from the structural flexible L-Gn dendrimers. A model was proposed to rationalize how the geometry and size of the platinum linker could control the copolymerization behaviours of these dendritic macromonomers.
Synthetic control of the pore dimension and surface area in conjugated microporous polymer and copolymer networks
Jiang, Jia-Xing,Su, Fabing,Trewin, Abbie,Wood, Colin D.,Niu, Hongjun,Jones, James T. A.,Khimyak, Yaroslav Z.,Cooper, Andrew I.
, p. 7710 - 7720 (2008)
A series of rigid microporous poly(aryleneethynylene) (PAE) networks was synthesized by Sonogashira-Hagihara coupling chemistry. PAEs with apparent Brunauer-Emmet-Teller surface areas of more than 1000 m2/g were produced. The materials were found to have very good chemical and thermal stability and retention of microporosity under a variety of conditions. It was shown that physical properties such as micropore size, surface area, and hydrogen uptake could be controlled in a "quantized" fashion by varying the monomer strut length, as for metal-organic and covalent organic frameworks, even though the networks were amorphous in nature. For the first time, it was demonstrated that these properties can also be fine-tuned in a continuous manner via statistical copolymerization of monomer struts with differing lengths. This provides an unprecedented degree of direct synthetic control over micropore properties in an organic network.
Conformational Tuning of the Intramolecular Electronic Coupling in Molecular-Wire Biruthenium Complexes Bridged by Biphenyl Derivatives
Kong, Dan-Dan,Xue, Lu-Sha,Jang, Rui,Liu, Bin,Meng, Xiang-Gao,Jin, Shan,Ou, Ya-Ping,Hao, Xiao,Liu, Sheng-Hua
, p. 9895 - 9904 (2015)
The synthesis and characterization of a series of biphenyl-derived binuclear ruthenium complexes with terminal {RuCl(CO)(PMe3)3} moieties and different structural arrangements of the phenyl rings are reported. Electrochemical studies
Understanding the Role of Parallel Pathways via In-Situ Switching of Quantum Interference in Molecular Tunneling Junctions
Asyuda, Andika,Chiechi, Ryan C.,Hong, Wenjing,Soni, Saurabh,Ye, Gang,Zhang, Yanxi,Zharnikov, Michael,Zheng, Jueting
, p. 14308 - 14312 (2020)
This study describes the modulation of tunneling probabilities in molecular junctions by switching one of two parallel intramolecular pathways. A linearly conjugated molecular wire provides a rigid framework that allows a second, cross-conjugated pathway
Modular Approach to Kekulé Diradicaloids Derived from Cyclic (Alkyl)(amino)carbenes
Hansmann, Max M.,Melaimi, Mohand,Munz, Dominik,Bertrand, Guy
, p. 2546 - 2554 (2018/02/28)
A modular approach for the synthesis of Kekulé diradicaloids is reported. The key step is the insertion of a carbene, namely, a cyclic (alkyl)(amino)carbene (CAAC), into the C-H bonds of two terminal alkynes linked by a spacer. Subsequent hydride abstraction, followed by two-electron reduction of the corresponding bis(iminium) salts, affords the desired diradicaloids. This synthetic route readily allows for the installation of communicating spacers, featuring different degrees of aromaticity and lengths, and gives the possibility of generating unsymmetrical compounds with two different CAACs. Electron paramagnetic resonance (EPR), NMR, UV-vis, and X-ray studies in combination with quantum-chemical calculations give insight into the electronic nature of the deeply colored Kekulé diradicaloids. They feature a singlet ground state with varying degrees of diradical character in combination with small singlet/triplet gaps. Upon lengthening of the spacer, the properties of the compounds approach those of monoradicals in which steric protection of the propargyl radical moiety is necessary to inhibit decomposition pathways. Most of these diradicaloids are stable at room temperature, both in solution and in the solid state, but are highly oxygen-sensitive. They represent the first diradicaloids derived from iminium salts.
