Switching in harmony: Tailoring the properties of functional materials with orthogonal stimuli

Chemical Physics Reviews, Journal Year: 2024, Volume and Issue: 5(1)

Published: Feb. 1, 2024

Bridging the current gap between precision and efficiency demonstrated by natural systems synthetic materials requires interfacing independently controlling multiple stimuli-responsive building blocks in a single platform. The mentioned orthogonal control over material properties (i.e., ability to selectively activate one moiety without affecting another) could pave way for multitude of applications, including logic-gated optoelectronics, on-demand drug delivery platforms, molecular shuttles, example. In this Review, we highlight recent successful strategies achieve using combination independent stimuli. We begin surveying fundamental studies multi-stimuli-responsive systems, which utilize variety stimuli (e.g., spiropyran, diarylethene, or dihydroazulene derivatives), because these lay foundation design containing more than controlled fragment. As next step, overview emerging field focusing on are composed unique unit that can respond stimuli, distinct excitation wavelengths, light, heat, pH, potential, ionic strength. Recent advances clearly demonstrate how strategic coupling orthogonally units allow selective modulation range properties, such as conductivity, catalytic performance, biological activity. Thus, highlighted foreshadow role with impact generation photopharmacology, nanotechnology, biomimetics.

Language: Английский

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Broadly Applicable Copper(I)-Catalyzed Alkyne Semihydrogenation and Hydrogenation of α,β-Unsaturated Amides Enabled by Bifunctional Iminopyridine Ligands

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 16, 2025

A highly active bifunctional catalyst consisting of a copper(I)/N-heterocyclic carbene complex and basic 2-iminopyridine subunit allows for copper hydride chemistry under low H2 pressure, achieving efficient catalysis reaching 1 bar (balloon pressure). The tolerates remarkable variety functional groups in catalytic alkyne semihydrogenations. Furthermore, this design gives rise to high reactivity that the hydrogenation α,β-unsaturated amides (a substrate class hitherto unreactive catalysis) at pressure first time. In manner, late-stage modification isotope labeling amides, common subunits biologically compounds, can be realized through using first-row transition metal based on abundant copper. Preliminary mechanistic experiments indicate operates via an iminopyridine-mediated proximity effect. We hypothesize coordination alcohol as proton source copper(I) facilitates overall reactions rapid proto-decupration step.

Language: Английский

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Synthesis of luminescent coumarin-substituted phosphinoamide-bridged polynuclear gold(i) metallacycles and reactivity studies

Inorganic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(18), P. 6079 - 6088

Published: Jan. 1, 2024

In this work, coumarin-substituted phosphinoamine gold( i ) chloride complexes were synthesized. Further reactions with KO t Bu led to isolation of unexpected cyclic rings, which investigated for their luminescence properties and reactivity.

Language: Английский

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Tris(tetramethylguanidinyl)phosphine: The Simplest Non‐ionic Phosphorus Superbase and Strongly Donating Phosphine Ligand

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 28(3)

Published: Nov. 18, 2021

We report the synthesis and properties of much sought-after tris(1,1,3,3-tetramethylguanidinyl) phosphine P(tmg)

Language: Английский

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Ferrocenyl Gold Complexes as Efficient Catalysts

European Journal of Inorganic Chemistry, Journal Year: 2022, Volume and Issue: 2022(12)

Published: Jan. 25, 2022

Abstract More than half a century after the discovery of ferrocene structure in 1951, it remains as suitable building block many research areas, including catalysis with development key chiral catalysts. On other hand, gold‐mediated has been raised recent years, allowing creation great variety C−C bonds and C‐heteroatom bonds. In this context, review covers advances made combination these two iconic figures organometallic chemistry field, since first gold catalyzed reaction using ligand reported 1986. The excellent properties versatility metallocene, allowed obtainment plethora ligands for metal catalysis, although their use joined to is still scarcely explored.

Language: Английский

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Syntheses, Characterization, and Redox Activity of Ferrocene-Containing Titanium Complexes

ACS Omega, Journal Year: 2024, Volume and Issue: 9(26), P. 29017 - 29024

Published: June 24, 2024

The chemistry of bis(π-η

Language: Английский

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A ligand-assisted proximity effect allows for H2-driven copper hy-dride chemistry under mild conditions

Published: Oct. 16, 2024

A bifunctional copper(I)/N-heterocyclic carbene complex bearing a highly basic 2-iminopyridine subunit effects variety of copper(I) hydride-based reductive transformations at low H2 pressure. The catalyst allows for the first time to employ only catalytic amounts alkoxide additive and is with highest reactivity towards re-ported so far. We can demonstrate that efficient alkyne semihydrogenations, conjugate reductions as well 1,2-reductions carbonyl compounds be carried out very new protocol circumvents need previously required high-pressure equipment. At same time, use iminopyridine-based ligand tolerance an unprecedented functional groups in realm copper(I)-catalyzed hydrogenations. possible working model featuring iminopyridine-mediated proximity effect coordinates key close reactive cop-per(I) center proposed account observed significant rise reactivity. Mechanistic studies directed support-ing this current hypothesis are presented.

Language: Английский

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Heterobimetallic Gold/Ruthenium Complexes Synthesized via Post‐functionalization and Applied in Dual Photoredox Gold Catalysis

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(57)

Published: Aug. 4, 2022

The synthesis of heterobimetallic AuI /RuII complexes the general formula syn- and anti-[{AuCl}(L1∩L2){Ru(bpy)2 }][PF6 ]2 is reported. ditopic bridging ligand L1∩L2 refers to a P,N hybrid composed phosphine bipyridine substructures, which was obtained via post-functionalization strategy based on Diels-Alder reaction between phosphole maleimide moiety. It found that stereochemistry at phosphorus atom resulting 7-phosphanorbornene backbone can be controlled by executing metal coordination cycloaddition in different order. All precursors, as well mono- multimetallic complexes, were isolated fully characterized various spectroscopic methods such NMR, IR, UV-vis spectroscopy cyclic voltammetry. Photophysical measurements show efficient phosphorescence for investigated monometallic complex anti-[(L1∩L2){Ru(bpy)2 bimetallic analogue syn-[{AuCl}(L1∩L2){Ru(bpy)2 , thus indicating small influence {AuCl} fragment photoluminescence properties. are both active catalysts P-arylation aryldiazonium salts promoted visible light with H-phosphonate affording arylphosphonates yields up 91 %. Both dinuclear outperform their counterparts.

Language: Английский

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Asymmetrically Difunctionalized 1,1′‐Ferrocenyl Metalloligands and Their Transition Metal Complexes

European Journal of Inorganic Chemistry, Journal Year: 2021, Volume and Issue: 2022(4)

Published: Dec. 13, 2021

Abstract The synthesis and full characterization of novel 1,1′‐difunctionalized ferrocene metalloligands is described. While one cyclopentadienyl ring has been functionalized with 2,2′‐bipyridine for secondary coordination, the second Cp decorated different aryl moieties containing electron withdrawing groups such as 4‐(CF 3 )C 6 H 4 ( 2A ) 3,5‐(CF 2 C 2B or 4‐(NO 2C ). newly developed were reacted [Pd(cod)Cl ] 3A – ), CuCl 4A trans ‐[(PPh Ni(Mes)Br] 5A , B to obtain corresponding square‐planar dimeric square‐pyramidal complexes. electrochemical behaviour ligands complexes was investigated aid cyclic voltammetry compared monofunctionalized derivatives. influence implemented functional on nickel then confirmed reductive elimination reaction an ether induced by oxidation methoxides 6A D experimental findings are supported quantum chemical calculations.

Language: Английский

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From Stable PH‐Ylides to α‐Carbanionic Phosphines as Ligands for Zwitterionic Catalysts

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(30)

Published: May 30, 2022

Abstract Although ylides are commonly used reagents in organic synthesis, the parent methylphosphine MePH 2 only exists its phosphine form condensed phase. Its ylide tautomer H 3 P + −CH − is considerably higher energy. Here, we report on formation of bis(sulfonyl)methyl‐substituted phosphines type (RO S) C(H)−PR 2, which stable PH under ambient conditions, amongst first examples an acyclic form. Depending exact substitution pattern equilibrium between and or exist as one both extremes. These were found to be ideal starting systems for facile α‐carbanionic phosphines. The carbanion‐functionalization leads a switch from electron‐poor highly electron‐rich with strong donor abilities high basicities. Thus, readily react different electrophiles exclusively at phosphorus atom not carbanionic center. Furthermore, anionic nature allows zwitterionic complexes demonstrated by isolation gold(I) complex cationic metal gold center catalytic activity hydroamination alkyne without requiring further activation step.

Language: Английский

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