79109-69-6Relevant academic research and scientific papers
Experimental and theoretical studies of charge delocalization in biruthenium-alkynyl complexes bridged by thiophenes
Ou, Ya-Ping,Xia, Jianlong,Zhang, Jing,Xu, Meng,Yin, Jun,Yu, Guang-Ao,Liu, Sheng Hua
, p. 2023 - 2032 (2013)
A series of binuclear ruthenium-alkynyl complexes that are bridged by thiophene groups (thiophene, bithiophene, and terthiophene) have been synthesized. All of these complexes have been well-characterized by NMR spectroscopy, X-ray diffraction, and elemen
Silole-acetylene π-electronic systems with low bandgaps: Synthesis, structure, and UV-vis absorption spectra of 2,5-diethynylsiloles derivatives and their polymers
Yamaguchi, Shigehiro,Iimura, Kazuo,Tamao, Kohei
, p. 89 - 90 (1998)
A series of 2,5-diethynylsilole derivatives and their polymers, prepared by the Stille coupling reaction, show unique optical properties such as long-wavelength absorptions in their UV-vis absorption spectra.
Five-Membered Heterocycles as Linking Units in Strongly Coupled Homobimetallic Group 8 Metal Half-Sandwich Complexes
Pfaff, Ulrike,Hildebrandt, Alexander,Korb, Marcus,Schaarschmidt, Dieter,Rosenkranz, Marco,Popov, Alexey,Lang, Heinrich
, p. 2826 - 2840 (2015)
The synthesis and characterization of a series of alkynyl half-sandwich complexes of type 2,5-((η5-C5H5)(dppe)MC≡C)2-cC4H2E (E = O (11), S (12); M = Fe (a), Ru (b); dppe = 1,2-bis(diphenylphosphino)ethane) are reported. The molecular structures of 11a and 12a,b in the solid state have been determined by single-crystal X-ray diffraction. The influence of different metals and the variation of the heterocyclic bridge on the electronic interactions between the terminal redox-active units in 11a,b and 12a,b was studied using electrochemical (cyclic and square wave voltammetry) and spectroelectrochemical (in situ UV-vis/NIR, ESR, and IR spectroscopy) methods and DFT calculations. Electrochemical studies demonstrated that mixed-valent species 11a,b+ and 12a,b+ exhibit high thermodynamic stabilities with respect to disproportionation (KC values from 6.87 × 104 to 9.33 x 105). In situ spectroelectrochemical ESR and IR measurements display delocalization of the single electron between the metal centers M/M+, revealing that within this setup five-membered heterocycles are well suited to promote intramolecular metal-metal interactions. Furthermore, the UV-vis/NIR spectra of mixed-valent 11a,b+ and 12a,b+ show intense, narrow, and nonsolvatochromic π(dπ) → π(dπ) absorptions in the NIR region with a high-energy shoulder. Both experimental and computational results suggest that at least two thermally accessible rotation conformers of the organometallic termini of 11a,b and 12a,b contribute to the electronic spectra of these compounds. One of the conformers can clearly be characterized as a delocalized class III system, while the other shows a more localized behavior. (Figure Presented).
Electronic Structures of Divinylchalcogenophene-Bridged Biruthenium Complexes: Exploring Trends from O to Te
Liu, Wen-Xia,Yan, Feng,Qian, Shu-Li,Ye, Jin-Yu,Liu, Xu,Yu, Ming-Xia,Wu, Xiao-Hui,Le, Meng-Lei,Zhou, Zhi-You,Liu, Sheng-Hua,Low, Paul J.,Jin, Shan
, p. 5015 - 5026 (2017)
An homologous series of divinylchalcogenophene-bridged binuclear ruthenium complexes [{(PMe3)3Cl(CO)Ru}2(μ-CH=CH-C4H2E-CH=CH)] (4a–4d, E = O, S, Se, Te) have been synthesised and fully characterised by X-ray crystallography and various spectroscopic techniques. The single-crystal X-ray diffraction results reveal a distinct short/long bond-length alternation along the polyene-like hydrocarbon backbone, with geometric constraints imposed by the chalcogenophene leading to an increasing distance between the two metal centres (dRu–Ru) in complexes 4a–4d as the heteroatom in the five-membered ring is changed from oxygen (9.980 ? in 4a) to tellurium (11.063 ? in 4d). The complexes undergo two sequential one-electron oxidation processes, the half-wave potential and separation of which appear to be sensitive to a range of factors, including aromatic stabilisation and re-organisation energies. Analysis of [4a–4d]n+ (n = 0, 1, 2) by UV/Vis/NIR and IR spectroelectrochemical methods, supported by DFT calculations (n = 0, 1), revealed that the redox character of the complexes is dominated by the polyene-like backbone with the chalcogenide playing a subtle but influential, structural rather than electronic, role. In the radical cations [4a–4d]+, the charge is rather effectively delocalised over the 10-atom Ru–[4-s-cis-all-trans-(CH=CH)4]–Ru chain, giving rise to a species with spectroscopic properties not dissimilar to oxidised polyaceylene.
Butterfly-Like Triarylamines with High Hole Mobility and On/Off Ratio in Bottom-Gated OFETs
Devibala, Panneerselvam,Balambiga, Balu,Mohamed Imran, Predhanekar,Bhuvanesh, Nattamai S. P.,Nagarajan, Samuthira
supporting information, p. 15375 - 15381 (2021/10/06)
Highly π-extended butterfly-shaped triarylamine dyads with aryleneethynylene spacer were constructed using an efficient synthetic route. These aryleneethynylene-bridged dyads are highly fluorescent and exhibited high HOMO levels, and low bandgaps, which a
Role of Substituents at 3-position of Thienylethynyl Spacer on Electronic Properties in Diruthenium(II) Organometallic Wire-like Complexes
Roy, Sourav Saha,Chowdhury, Sabyasachi Roy,Mishra, Sabyashachi,Patra, Sanjib K.
supporting information, p. 3304 - 3313 (2020/09/09)
A series of organometallic complexes [Cl(dppe)2Ru?C≡C-(3-R?C4H2S)-C≡C?Ru(dppe)2Cl] (3-R-C4H2S=3-substituted thienyl moiety; R=?H, ?C2H5, ?C3H7, ?C4H9, ?C6H13, ?OMe, ?CN in 5 a–5 g respectively) have been synthesized by systematic variation of 3-substituents at the thienylethynyl bridging unit. The diruthenum(II) wire-like complexes (5 a–5 g) have been achieved by the reaction of thienylethynyl bridging units, HC≡C-(3-R-C4H2S)-C≡CH (4 a–4 g) with cis-[Ru(dppe)2Cl2]. The wire-like diruthenium(II) complexes undergo two consecutive electrochemical oxidation processes in the potential range of 0.0 - 0.8 V. Interestingly, the wave separation between the two redox waves is greatly influenced by the substituents at the 3-position of the thienylethynyl. Thus, the substitution on 3-position of the thienylethynyl bridging unit plays a pivotal role for tuning the electronic properties. To understand the electronic behavior, density functional theory (DFT) calculations of the selected diruthenium wire-like complexes (5 a–5 e) with different alkyl appendages are performed. The theoretical data demonstrate that incorporation of alkyl groups to the thienylethynyl entity leaves unsymmetrical spin densities, thus affecting the electronic properties. The voltammetric features of the other two Ru(II) alkynyl complexes 5 f and 5 g (with ?OMe and ?CN group respectively) show an apparent dependence on the electronic properties. The electronic properties in the redox conjugate, (5 a+) with Kc of 3.9×106 are further examined by UV-Vis-NIR and FTIR studies, showing optical responses in NIR region along with changes in “?Ru?C≡C?“ vibrational stretching frequency. The origin of the observed electronic transition has been assigned based on time-dependent DFT (TDDFT) calculations.
Amorphous formability and temperature-sensitive luminescence of lanthanide coordination glasses linked by thienyl, naphthyl, and phenyl bridges with ethynyl groups
Hirai, Yuichi,Da Rosa, Pedro Paulo Ferreira,Nakanishi, Takayuki,Kitagawa, Yuichi,Fushimi, Koji,Hasegawa, Yasuchika
supporting information, p. 322 - 326 (2017/05/09)
The glass-transition properties and temperature-sensitive luminescence of lanthanide (Ln(III)) coordination compounds are reported. The glass formability was systematically provided by incorporation of bent-angled phosphine oxide (2,5-bis-(diphenylphosphorylethynyl)thiophene: dpet, 2,7-bis(diphenylphosphorylethynyl)naphthalene: dpen, 1,3-bis(diphenylphosphorylethynyl)benzene: m-dpeb) ligands with thienyl, naphthyl, phenyl cores, and ethynyl groups. The glass-transition points were clearly identified for all Ln(III) coordination compounds (Tg = 65-87°C). The Tb(III)/Eu(III) mixed coordination glass [Tb,Eu(hfa)3(m-dpeb)]3 (hfa: hexafluoroacetylacetonate) also showed green, yellow, orange, and red photoluminescence depending on temperature.
Electronically Strongly Coupled Divinylheterocyclic-Bridged Diruthenium Complexes
Pfaff, Ulrike,Hildebrandt, Alexander,Korb, Marcus,O?wald, Steffen,Linseis, Michael,Schreiter, Katja,Spange, Stefan,Winter, Rainer F.,Lang, Heinrich
, p. 783 - 801 (2016/01/15)
Complexes [{Ru(CO)Cl(PiPr3)2}2(μ-2,5-(CH=CH)2-cC4H2E] (E=NR; R=C6H4-4-NMe2 (10a), C6H4-4-OMe (10b), C6H4-4-Me (10c), C6H5 (10d), C6H4-4-CO2Et (10e), C6H4-4-NO2 (10f), C6H3-3,5-(CF3)2 (10g), CH3 (11); E=O (12), S (13)) are discussed. The solid state structures of four alkynes and two complexes are reported. (Spectro)electrochemical studies show a moderate influence of the nature of the heteroatom and the electron-donating or -withdrawing substituents R in 10a-g on the electrochemical and spectroscopic properties. The CVs display two consecutive one-electron redox events with ΔE°′=350-495 mV. A linear relationship between ΔE°′ and the σp Hammett constant for 10a-f was found. IR, UV/Vis/NIR and EPR studies for 10+-13+ confirm full charge delocalization over the {Ru}CH=CH-heterocycle-CH=CH{Ru} backbone, classifying them as Class III systems according to the Robin and Day classification. DFT-optimized structures of the neutral complexes agree well with the experimental ones and provide insight into the structural consequences of stepwise oxidations.
The synthesis of π-electron molecular rods with a thiophene or thieno[3,2-b]thiophene core unit and sulfur alligator clips
Seidler, Arno?t,Svoboda, Ji?í,Dekoj, Václav,Chocholou?ová, Jana Vacek,Vacek, Jaroslav,Stará, Irena G.,Stary, Ivo
supporting information, p. 2795 - 2798 (2013/06/05)
A series of short oligo(p-phenylene-ethynylene)- and oligo(p- phenylenevinylene)-type molecular rods with an electronically rich thiophene or thieno[3,2-b]thiophene core unit and sulfur anchoring groups (AcS-, t-BuS-) at the termini have been synthesised
Synthesis of functionalized thiophenes and oligothiophenes by selective and iterative cross-coupling reactions using indium organometallics
Montserrat Martinez,Pena-Lopez, Miguel,Sestelo, Jose Perez,Sarandeses, Luis A.
experimental part, p. 3892 - 3898 (2012/06/04)
The synthesis of unsymmetrical 2,5-disubstituted thiophenes by selective and sequential palladium-catalyzed cross-coupling reactions of indium organometallics with 2,5-dibromothiophene is reported. Following an iterative coupling sequence, α-oligothiophenes were synthesized in good yields and with high atom economy.
