Self-Assembly of Chiral Metallacycles and Metallacages from a Directionally Adaptable BINOL-Derived Donor

Ye, Yang; Cook, Timothy R.; Wang, Shu Ping; Wu, Jing; Li, Shijun; Stang, Peter J.

doi:10.1021/jacs.5b07529

Cited by 108 publications

(101 citation statements)

References 66 publications

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“…[20] BINOL-based buildingb locks have also been investigated as chiral units for the construction of supramolecular chiral structures. [21][22][23][24][25][26] In this contribution, we report BINOL-based building blocks for the construction of Fe II 2 L 3 -type cages by using the typical Nitschke subcomponent self-assembly strategy.V arious Fe II 2 L 3 cages were prepared, and within this series, the extent to which the chiral informationa tt he BINOL building blocks could be transferred to the coordination centers was evaluated. We concludet hat enantiopure single-isomer cages only form if, next to the BINOL building blocks, chiral amines are used to steer the chirality at the coordination complexes aroundiron.…”

Section: Introductionmentioning

confidence: 99%

“…The use of 1,1′‐bi‐2‐naphthol (BINOL) as a chiral scaffold is interesting, as it has successfully been applied as a versatile chiral element in asymmetric catalysis, and as such, a diverse set of building blocks is available . BINOL‐based building blocks have also been investigated as chiral units for the construction of supramolecular chiral structures . In this contribution, we report BINOL‐based building blocks for the construction of Fe II 2 L 3 ‐type cages by using the typical Nitschke subcomponent self‐assembly strategy.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Characterization of Self‐Assembled Chiral Fe^II₂L₃ Cages

Sun

Nurttila

Reek

2018

Chemistry A European J

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We present here the synthesis of chiral BINOL‐derived (BINOL=1,1′‐bi‐2‐naphthol) bisamine and bispyridine‐aldehyde building blocks that can be used for the self‐assembly of novel chiral FeII 2L3 cages when mixed with an iron(II) precursor. The properties of a series of chiral cages were studied by NMR and circular dichroism (CD) spectroscopy, cold‐spray ionization MS, and molecular modeling. Upon formation of the M2L3 cages, the iron corners can adopt various isomeric forms: mer, fac‐Δ, or fac‐Λ. We found that the coordination geometry around the metal centers in R‐Cages 1 and 2 were influenced by the chiral BINOL backbone only to a limited extent, as a mixture of cages was formed with fac and mer configurations at the iron corners. However, single cage species (fac‐RR‐Cage and fac‐RS‐Cage) that are enantiopure and highly symmetric were obtained by generating these chiral M2L3 cages by using the bispyridine‐aldehyde building blocks in combination with chiral amine moieties to form pyridylimine ligands for coordination to iron. Next to consistent NMR spectra, the CD spectra confirm the configurations fac‐(Λ,Λ) and fac‐(Δ,Δ) corresponding to RR‐ and RS‐Cage, respectively.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Self‐Assembled Chiral Fe^II₂L₃ Cages

Sun

Nurttila

Reek

2018

Chemistry A European J

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“…1) that occurs when two donor building blocks (1 and 3) are mixed with cis-(PEt 3 ) 2 Pt(OTf) 2 (2). When combined in a 4:2:8 ratio, precursors 1, 3, and 2 act as the edges, faces, and vertices of the metallacage (4), respectively, under the principles of edge-directed and face-directed directional bonding (12)(13)(14)(15)(16). The core of 3 is a TPE moiety whose intramolecular aromatic ring rotation becomes restricted on coordination.…”

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confidence: 99%

Tetraphenylethene-based highly emissive metallacage as a component of theranostic supramolecular nanoparticles

Cook

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

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166

114

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A theranostic agent combines diagnostic reporter with therapeutic activity in a single entity, an approach that seeks to increase the efficacy of cancer treatment. Herein, we describe the synthesis of a highly emissive tetraphenylethene-based metallacage using multicomponent coordination-driven self-assembly that exhibits a coordination-triggered aggregation-induced emission (AIE) enhancement. The formation of metallacage-loaded nanoparticles (MNPs) occurs when the assembly is treated with two variants of a 1,2-distearoyl-phosphatidylethanolamine (DSPE)/polyethylene glycol (PEG) conjugate, mPEG-DSPE, and biotin-PEG-DSPE. This combination endows the resultant MNPs with excellent stability and targeting ability, specifically enabling selective delivery of the metallacages to cancer cells that overexpress biotin receptors via receptor-mediated endocytosis. Although the mechanism of activity is based on existing Pt(II) anticancer drugs such as oxaliplatin, carboplatin, and cisplatin, in vitro and in vivo studies indicate that the MNPs are more active and show low systemic activity while also possessing emissive properties that allow for fluorescence-based imaging. This pioneering example of a metallacage that combines biologically active components with AIE imaging establishes supramolecular coordination complexes imbedded within nanoparticles as a promising potential theranostic platform for cancer treatment.ver the past decades, platinum-based coordination complexes have been a mainstay of clinical drugs for the treatment of many solid tumors, including testicular, colorectal, genitourinary, and nonsmall cell lung cancers (1, 2). Cisplatin, oxaliplatin, and carboplatin have been approved as first-line chemotherapeutics for the treatment of carcinoma in combination with other anticancer drugs. However, their chemotherapeutic applications are greatly limited by severe side effects that include acute nephrotoxicity, neurotoxicity, ototoxicity, and emetogenesis (3, 4). The search for low-dose platinum-based drugs/prodrugs with high selectivity to tumor tissues motivates the development of targeting drug delivery systems that may reduce side effects and show an improved therapeutic index. Further modifications are sought to address drawbacks of poor solubility, rapid clearance, and a lack of selectivity (5, 6). Although fluorescence-based techniques provide a means to track the processes of translocation, drug release and excretion of anticancer agents, the aforementioned species are intrinsically nonfluorescent under treatment conditions (7-10).In sharp contrast to the aggregation-caused quenching (ACQ) effect, Tang and colleagues developed a novel class of organic luminogens that are nonemissive in solution but become intensely emissive on aggregation, with pioneering studies based on tetraphenylethene (TPE) and hexaphenylsilole (HPS). This so-called aggregation-induced emission (AIE) effect is attributed to the restriction of intramolecular rotation (RIR) of the aromatic rings of AIEgens (11). Since the discovery of...

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“…[17][18][19][20] An enormous range of structures are available by using different metals and coordinating sites, many of which potentially have useful properties, such as electrochemical activity, host-guest chemistry, redox activity, magnetic behavior, etc. [21][22][23][24] In this work, binuclear half-sandwich complexes based on Cp*Ir/Cp*Rh units have been used as building blocks. These half-sandwich units have advantages in solubility, thermal stability and flexibility in fine-tuning processes, and therefore are suitable candidates for metallosupramolecular assembly.…”

Section: Introductionmentioning

confidence: 99%

Half-sandwich rhodium and iridium fragments and carboxylate ligands as building blocks for the formation of metallamacrocycles

Lin

Fan

Jin

2017

Journal of Organometallic Chemistry

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A series of half-sandwich rhodium and iridium complexes containing carboxylate ligands were synthesized and characterized. Reactions between [Cp*MCl 2 ] 2 (M = Ir or Rh) and 1,3,6bis(2-pyridyl)-1,2,4,5-tetrazine (L1) gave binuclear complexes 1 and 2 under different conditions. The half-sandwich iridium and rhodium metallamacrocycles complexes 3-5 were constructed in a stepwise manner by the addition of carboxylate ligands (sodium acetate or the conjugate bases of pyrazine-2,3-dicarboxylic acid or 3-(2-pyridyl)acrylic acid) to the solution of the binuclear precursors prepared from the reactions of [Cp*MCl 2 ] 2 (M = Rh or Ir) with linear N,N′-donor ligands (4,4′bipyridine or trans-1,2-bis(4-pyridyl)ethylene), respectively. The structures of binuclear complexes and tetranuclear macrocycles were confirmed by elemental analysis, IR, 1 H NMR spectroscopy and single-crystal X-ray diffraction.

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Self-Assembly of Chiral Metallacycles and Metallacages from a Directionally Adaptable BINOL-Derived Donor

Cited by 108 publications

References 66 publications

Synthesis and Characterization of Self‐Assembled Chiral Fe^II₂L₃ Cages

Synthesis and Characterization of Self‐Assembled Chiral Fe^II₂L₃ Cages

Tetraphenylethene-based highly emissive metallacage as a component of theranostic supramolecular nanoparticles

Half-sandwich rhodium and iridium fragments and carboxylate ligands as building blocks for the formation of metallamacrocycles

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Self-Assembly of Chiral Metallacycles and Metallacages from a Directionally Adaptable BINOL-Derived Donor

Cited by 108 publications

References 66 publications

Synthesis and Characterization of Self‐Assembled Chiral FeII2L3 Cages

Synthesis and Characterization of Self‐Assembled Chiral FeII2L3 Cages

Tetraphenylethene-based highly emissive metallacage as a component of theranostic supramolecular nanoparticles

Half-sandwich rhodium and iridium fragments and carboxylate ligands as building blocks for the formation of metallamacrocycles

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Synthesis and Characterization of Self‐Assembled Chiral Fe^II₂L₃ Cages

Synthesis and Characterization of Self‐Assembled Chiral Fe^II₂L₃ Cages