Transition‐Metal Nitrosyls for Photocontrolled Nitric Oxide Delivery

Xiang, Huijing; Guo, Min; Liu, Jingang

doi:10.1002/ejic.201601135

Cited by 68 publications

(64 citation statements)

References 126 publications

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“…The quite short PN length of 1.515(3) Å in 7 can be viewed as indicative of a very strong double bond, it actually being shorter than the reference PN double-bond length of 1.57 Å, 35 and in any case shorter than the values of 1.54-1.65 Å measured in all previous complexes having -N=PX3 ligands bearing alkyl, aryl or even NR2 substituentes. 36 3; N3P2 = 1.515 (3). Mo2Mo1N1 = 96.0(1); Mo1Mo2N2 = 101.9(1).…”

Section: Scheme 5 Reactions Of Compounds 1a With Phosphitesmentioning

confidence: 99%

N–O Bond Activation and Cleavage Reactions of the Nitrosyl-Bridged Complexes [M₂Cp₂(μ-PCy₂)(μ-NO)(NO)₂] (M = Mo, W)

et al. 2018

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The title complexes (1a,b) were prepared in two steps by first reacting the hydrides [M2Cp2(-H)(-PCy2)(CO)4] with [NO](BF4) in the presence of Na2CO3 to give dinitrosyls [M2Cp2(-PCy2)(CO)2(NO)2](BF4), which were then fully decarbonylated upon reaction with NaNO2 at 323 K. An isomer of the Mo2 complex having a cisoid arrangement of the terminal ligands (cis-1a) was prepared upon irradiation of toluene solutions of 1a with visible-UV light at 288 K. The structure of these trinitrosyl complexes was investigated using X-ray diffraction and density functional theory (DFT) calculations, these revealing a genuine pyramidalization of the bridging NO that might be associated in part to an increase of charge at the N atom, and also anticipated a weakening of the NO bond upon reaction with bases or reducing reagents. Complexes 1a,b reacted with [FeCp2](BF4) to give first the radicals [M2Cp2(-PCy2)(-NO)(NO)2](BF4) according to CV experiments, which then underwent H-abstraction to yield the nitroxyl-bridged complexes [M2Cp2(-PCy2)(- 1 : 2-HNO)(NO)2](BF4), alternatively prepared upon protonation with HBF4•OEt2. The novel coordination mode of the nitroxyl ligand in these products was thermodynamically favored over its tautomeric hydroximido form, according to DFT calculations, and similar nitrosomethane-bridged cations [M2Cp2(-PCy2)(- 1 : 2-MeNO)(NO)2] + were prepared by reacting 1a,b with CF3SO3Me or [Me3O]BF4. Complexes 1 reacted with M(Hg) (M = Zn, Na) in tetrahydrofuran to give the amido-bridged derivatives [M2Cp2(-PCy2)(-NH2)(NO)2] with retention of stereochemistry, a transformation also induced by using mild O-atom scavengers such as CO and phosphites in the presence of water. In the absence of water, phosphites accomplished a deoxygenation of the bridging NO of the Mo2 complexes to yield the phosphoraniminato-bridged derivatives [Mo2Cp2(-PCy2){-NP(OR)3}(NO)2] (R = Et, Ph), also with retention of stereochemistry.

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Section: Scheme 5 Reactions Of Compounds 1a With Phosphitesmentioning

confidence: 99%

N–O Bond Activation and Cleavage Reactions of the Nitrosyl-Bridged Complexes [M₂Cp₂(μ-PCy₂)(μ-NO)(NO)₂] (M = Mo, W)

et al. 2018

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“…The combination of rubbery matrices and liquid-phase inclusions has enabled the development of highly compliant and stretchable composites with exceptional thermal or electrical performance. These properties include high dielectric constant and breakdown, [7][8][9] enhanced thermal conductivity, [10][11][12][13] high electrical conductivity with limited electromechanical coupling, [14][15][16][17][18] extreme toughness, [19][20][21][22] and electrically self-healing ability. [23][24][25] However, despite the extraordinary promise of LMEEs, a potential limitation for their use in real-world applications is the relatively high crystallization temperature of the metal alloys used for the dispersion phase.…”

Section: Introductionmentioning

confidence: 99%

Liquid Metal Supercooling for Low‐Temperature Thermoelectric Wearables

Malakooti

Kazem

Yan

et al. 2019

Adv Funct Materials

167

143

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Elastomers embedded with droplets of liquid metal (LM) alloy represent an emerging class of soft multifunctional composites that have potentially transformative impact in wearable electronics, biocompatible machines, and soft robotics. However, for these applications it is crucial for LM alloys to remain liquid during the entire service temperature range in order to maintain high mechanical compliance throughout the duration of operation. Here, we introduce LM-based functional composites that do not freeze and remain soft and stretchable at extremely low temperatures. We show that the confinement of LM droplets to micro-/nanometer length scales significantly suppresses their freezing temperature (down to-84.1 C from-5.9 C) and melting point (down to-25.6C from +17.8C) independent of the choice of matrix material and processing conditions. Such a supercooling effect allows the LM inclusions to preserve their fluidic nature at low temperatures and stretch with the surrounding polymer matrix without introducing significant mechanical resistance or inducing internal stress concentrations. These results indicate that LM composites with highly stabilized droplets are capable of operation over a wide temperature range and open up new possibilities for these emerging materials, which we demonstrate with self-powered wearable thermoelectric devices for bio-sensing and personal health monitoring at low temperatures.

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“…Ruthenium ion is known to form relatively tight binding complex with nitrosyl ligands, so that ruthenium‐NO (Ru‐NO) complexes are generally stable under ambient conditions, while the complexes release NO upon photoirradiation. The stable and photoactivatable property of Ru‐NO would be advantageous for biological application, and they were adopted for cellular and in vivo experiments ,. Furthermore, the Ru‐NO complexes also show the useful property of absorption band shift depending on the ligands at the distal site, which was adopted to develop the complex activatable by longer wavelength suitable for biological applications…”

Section: Photocontrollable No Releasersmentioning

confidence: 99%

Photo‐Controlled Release of Small Signaling Molecules to Induce Biological Responses

Nakagawa

2018

The Chemical Record

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Chemical modifications of proteins or cofactors, including acetylation and oxidation of amino acid residues of various signal proteins, whether transient or successive, play key roles in modulating biological functions. Small molecules that have signaling functions in biological systems through the chemical modification of proteins include nitric oxide (NO), hydrogen peroxide, carbon monoxide, and hydrogen sulfide. To investigate the pathophysiological roles of these molecules, caged compounds have been developed that allow precise spatiotemporal control of the release of these species in response to photoirradiation in the ultraviolet or visible region. For example, photocontrollable NO releasers can regulate the responses of blood vessels in vivo and ex vivo. In addition, photocontrollable (caged) inhibitors of histone deacetylase (HDAC) can be used to regulate HDAC activity in response to photoirradiation. Such photocontrol technology has provided chemical tools for a variety of biological studies, including investigations of epigenetic mechanisms.

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Transition‐Metal Nitrosyls for Photocontrolled Nitric Oxide Delivery

Cited by 68 publications

References 126 publications

N–O Bond Activation and Cleavage Reactions of the Nitrosyl-Bridged Complexes [M₂Cp₂(μ-PCy₂)(μ-NO)(NO)₂] (M = Mo, W)

N–O Bond Activation and Cleavage Reactions of the Nitrosyl-Bridged Complexes [M₂Cp₂(μ-PCy₂)(μ-NO)(NO)₂] (M = Mo, W)

Liquid Metal Supercooling for Low‐Temperature Thermoelectric Wearables

Photo‐Controlled Release of Small Signaling Molecules to Induce Biological Responses

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Transition‐Metal Nitrosyls for Photocontrolled Nitric Oxide Delivery

Cited by 68 publications

References 126 publications

N–O Bond Activation and Cleavage Reactions of the Nitrosyl-Bridged Complexes [M2Cp2(μ-PCy2)(μ-NO)(NO)2] (M = Mo, W)

N–O Bond Activation and Cleavage Reactions of the Nitrosyl-Bridged Complexes [M2Cp2(μ-PCy2)(μ-NO)(NO)2] (M = Mo, W)

Liquid Metal Supercooling for Low‐Temperature Thermoelectric Wearables

Photo‐Controlled Release of Small Signaling Molecules to Induce Biological Responses

Contact Info

Product

Resources

About

N–O Bond Activation and Cleavage Reactions of the Nitrosyl-Bridged Complexes [M₂Cp₂(μ-PCy₂)(μ-NO)(NO)₂] (M = Mo, W)

N–O Bond Activation and Cleavage Reactions of the Nitrosyl-Bridged Complexes [M₂Cp₂(μ-PCy₂)(μ-NO)(NO)₂] (M = Mo, W)