Direct synthesis of disubstituted aromatic polyimine chelates

Dietrick-Buchecker, C.O.; Marnot, Pascal A.; Sauvage, Jean Pierre

doi:10.1016/s0040-4039(00)85821-9

Cited by 189 publications

(119 citation statements)

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Section: Introductionmentioning

confidence: 99%

“…[12][13][14] Although artificial molecular machines are yet to make an impact on our everyday lives, the field is currently undergoing a rapid expansion both in terms of what man-made molecules can accomplish and the areas of expertise of the scientists drawn to the field. In many ways, this development, envisioned already in 1959 by Richard Feynman in his prophetic "There's Plenty of Room at the Bottom" lecture, [15] is testament to the groundbreaking work on the design and synthesis of molecular machines [16][17][18][19][20][21][22][23][24][25] for which Jean-Pierre Sauvage, Sir J. Fraser Stoddart and Bernard (Ben) L. Feringa were awarded the Nobel Prize in Chemistry 2016.While a molecular machine can be defined as "an assembly of a discrete number of molecular components designed to perform mechanical-like movements (output) as a consequence of appropriate external stimuli (input)," [2] this tutorial review focuses on the subset of such systems known as molecular motors. Loosely speaking, molecular motors are molecules that can produce net work by absorbing external energy and converting the energy into directed (non-random) mechanical motion in a controllable fashion.…”

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Quantum chemical design of rotary molecular motors

Oruganti

Wang

Durbeej

2017

Int J of Quantum Chemistry

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This tutorial review describes how recent quantum chemical calculations and non-adiabatic molecular dynamics simulations have provided valuable guidelines and insights for the design of more powerful synthetic rotary molecular motors. Following a brief overview of the various types of rotary motors synthesized to date, we present computationally identified steric and electronic approaches to significantly reduce the free-energy barriers of the critical thermal isomerization steps of chiral overcrowded alkenes, a main class of motors whose potential for many different kinds of applications is well documented. Furthermore, we describe how computational research in this field has provided new motor designs that differ from overcrowded alkenes by either (1) completing a full 3608 rotation through fewer steps, (2) exhibiting more efficient photochemical steps, or (3) requiring fewer chiral features for their function, including a design that even in the absence of a stereocenter achieves unidirectional rotary motion from two Z/E photoisomerizations alone.chirality, molecular motors, non-adiabatic molecular dynamics, photoisomerization, steric interactions | I N TR ODU C TI ONIn this tutorial review, we give an account of how quantum chemical research has contributed to advance the field of artificial molecular machines.This field [1][2][3][4][5][6][7][8][9][10][11] is devoted to the fabrication of molecular systems capable of performing the same type of machine-like functions that Nature-made protein complexes carry out in order to, among other things, propel cells, store energy in cells, equip cells with transport systems, and generate biomechanical forces. [12][13][14] Although artificial molecular machines are yet to make an impact on our everyday lives, the field is currently undergoing a rapid expansion both in terms of what man-made molecules can accomplish and the areas of expertise of the scientists drawn to the field. In many ways, this development, envisioned already in 1959 by Richard Feynman in his prophetic "There's Plenty of Room at the Bottom" lecture, [15] is testament to the groundbreaking work on the design and synthesis of molecular machines [16][17][18][19][20][21][22][23][24][25] for which Jean-Pierre Sauvage, Sir J. Fraser Stoddart and Bernard (Ben) L. Feringa were awarded the Nobel Prize in Chemistry 2016.While a molecular machine can be defined as "an assembly of a discrete number of molecular components designed to perform mechanical-like movements (output) as a consequence of appropriate external stimuli (input)," [2] this tutorial review focuses on the subset of such systems known as molecular motors. Loosely speaking, molecular motors are molecules that can produce net work by absorbing external energy and converting the energy into directed (non-random) mechanical motion in a controllable fashion. The ability to produce net work is the distinguishing feature of molecular motors vis-a-vis molecular switches, the latter of which sustain back-and-forth motion but not the continuous m...

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Section: Introductionmentioning

confidence: 99%

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confidence: 99%

Quantum chemical design of rotary molecular motors

Oruganti

Wang

Durbeej

2017

Int J of Quantum Chemistry

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“…The ligand 6,6 0 -diphenyl-2,2 0 -bipyridine, dpbpy, was obtained from the reaction of four equivalents of phenyllithium with 2,2 0 -bipyridine in THF followed by oxidation of the intermediate tetrahydro-species with MnO 2 according to the general procedure of Sauvage et al 8 The reaction of dpbpy with the chloro-bridged dimer [(ppy) 2 ) and the complex is luminescent exhibiting an emission in MeCN solution with a maximum at 595 nm with a lifetime t = 0.6 ms and a quantum yield (PLQE) of 3%.…”

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confidence: 99%

Two are not always better than one: ligand optimisation for long-living light-emitting electrochemical cells

et al. 2009

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The complex [Ir(ppy) 2 (dpbpy)] [PF 6 ] (Hppy = 2-phenylpyridine, dpbpy = 6,6 0 -diphenyl-2,2 0 -bipyridine) has been prepared and evaluated as an electroluminescent component for light-emitting electrochemical cells (LECs); the complex exhibits two intramolecular face-to-face p-stacking interactions and long-lived LECs have been constructed; the device characteristics are not significantly improved in comparison to analogous LECs with 6-phenyl-2,2 0 -bipyridine.Light-emitting electrochemical cells (LECs) are a minimalist derivative of organic light-emitting devices (OLEDs) and in their simplest form consist of a film of an ionic transition metal complex placed between two electrodes. 1,2 LECs offer considerable technological advantages over OLEDs as they require a less reactive cathode material (Al instead of Ca or Mg) because the device is no longer dependent upon the work function of the electrode and hence do not require stringent protection from environmental oxygen or water. The disadvantage of LECs is the short operating lifetime, in the order of hours to days, compared to OLEDs. [3][4][5] We have recently reported the use of intra-and intermolecular face-to-face p-stacking for the stabilisation of the ground and excited state of electroluminescent iridium complexes and shown that this leads to exceptionally long-living LEC devices. 6,7 The long lifetimes of these devices establish LECs as a viable alternative to OLED technology. In [Ir(ppy)(pbpy)] + (Hppy = 2-phenylpyridine, pbpy = 6-phenyl-2,2 0 -bipyridine) the pendant phenyl group of the pbpy ligand forms a face-to-face p-stack with the metallated ring of a ppy ligand (3.2-3.5 Å ). This interaction minimises the expansion of the metal-ligand bonds in the excited state and precludes the attack by water and other nucleophiles resulting in the long observed lifetimes. We concluded that analogous complexes with 6,6 0 -diphenyl-2,2 0 -bipyridine would have an even greater stabilisation of the excited state as the two pendant phenyl groups would stack with different ppy ligands giving a very ''tight'' complex.The ligand 6,60 -diphenyl-2,2 0 -bipyridine, dpbpy, was obtained from the reaction of four equivalents of phenyllithium with 2,2 0 -bipyridine in THF followed by oxidation of the intermediate tetrahydro-species with MnO 2 according to the general procedure of Sauvage et al. ) and the complex is luminescent exhibiting an emission in MeCN solution with a maximum at 595 nm with a lifetime t = 0.6 ms and a quantum yield (PLQE) of 3%.We have determined the structure of [Ir(ppy) 2 (dpbpy)][PF 6 ]z and the [Ir(ppy) 2 (dpbpy)] + cation present in the lattice is shown in Fig. 1a. The Ir-N(ppy) (2.0504(17), 2.0341(17) Å ) and Ir-C(ppy) distances (2.0120 (18) . We stress here that the intramolecular p-stacking is a direct and inevitable consequence of the ligand structure and will be present in the solid state, solution and thin film phases. To summarise, as observed from the crystal structure, the use of the dpbpy ligand for optimising the

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“…Recently, we found that iridium(I) complexes comprised of an air-stable, easily available 1/2[Ir(OMe)(COD)] 2 precursor and a simple, commercially available 2,2'-bipyridine (bpy) or 4,4'-di-tert-butyl-2,2'-bipyridine (dtbpy) ligand effectively catalyzed aromatic C-H silylation of neat arenes with 1,2-di-tert-butyl-1,1,2,2-tetrafluorodisilane (t-BuF 2 Si) 2 at 120 °C to give the corresponding aryl fluorosilanes in high yields with high regioselectivities. 4,5 Also, synthetic utility of the aryl fluorosilanes was demonstrated by their palladium-catalyzed cross-coupling 6 with aromatic electrophiles and rhodium-catalyzed 1,4-addition 7 to enones. 4 As an extension of our methodology to other aromatic substrates, we describe here the iridium(I)-catalyzed aromatic C-H silylation of five-membered heteroarenes with (t-BuF 2 Si) 2 in octane at 120 °C (Scheme 1).…”

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confidence: 99%

“…GC analyses were performed on a Hitachi G-3500 instrument equipped with a glass column (OV-101 on Uniport B, 2 m). 1,2-Di-tert-butyl-1,1,2,2-tetrafluorodisilane, 1 methyl 3-thiophenecarboxylate, 2 1-triisopropylsilylpyrrole, 3 1-triisopropylsilylindole, 4 [Ir(OMe)(COD)] 2 , 5 2,9-dibutyl-1,10-phenanthroline, 6 2,9-ditert-butyl-1,10-phenanthroline, 6 and 2-tert-butyl-1,10-phenanthroline 7 were synthesized by the reported procedures. 2,9-Diisopropyl-1,10-phenanthroline and 2-isopropyl-1,10-phenanthroline were prepared by the methods similar to those for 2,9-di-sec-butyl-1,10-phenanthroline 8 and 2-sec-butyl-1,10-phenanthroline, 9 respectively.…”

mentioning

confidence: 99%