Directed Self-Assembly of C4-Symmetric, Oxidovanadate-Centered, Vanadyl(V) Quadruplexes for Ba2+- and Hg2+-Specific Recognition, Transport, and Recovery

Chen, Chien‐Tien; Liao, Yi‐Ya; Salunke, Santosh B.; Lin, Yow-Jian; Kuo, Ting‐Shen

doi:10.1021/acs.inorgchem.8b01454

Cited by 3 publications

(4 citation statements)

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“…In addition, the ion pairing interaction of Hg(NO 3 ) + with the central oxidovanadate in cluster complex 3′ - Hg(NO 3 ) should be significantly stronger than that of Na + in 3′ - Na . It has been known that there remained one nitrate ligand sitting on top of Hg 2+ in a capped prism complexation mode for a 3,5-dibromo-substituted cluster reported previously by us . One would expect 3′ - Hg(NO 3 ) to hold a similar complexation geometry.…”

Section: Resultssupporting

confidence: 55%

“…In the past 15 years, we have developed several C 4 -symmetric, chiral vanadyl quartets/quadruplexes based on N -salicylidene l - t -leucinate ligands as ion-channel protein memetics for filtering monovalent K + and Ag(CH 3 CN) + as well as divalent Ba 2+ and Hg(NO 3 ) + -specific encapsulation and transport (Figure ). , In particular, the strength of the K + ion complexation ( K a ≈ 10 10 M –1 ) by a square planar motif was estimated to be at least 100 times stronger than that exerted by dicylohexano-18-crown-6. Inspired by these successful advances and catalysis applications, , we sought to append a 4-heptoxyphenyl group at the C5 position of the salicylidene template to impart a nematic LC functional unit directly into the vanadyl monomer (Figure A).…”

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

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Metal-Ion Specific Recognition with Amplified Transcription from Subnanometer to Submillimeter or Real-Time Domain by Self-Assembled Vanadyl Quartets

Chen

Weng

2022

Inorg. Chem.

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Vanadyl(V) complexes 1 and 2 bearing a nematic liquid crystal (LC) like a p-heptoxyphenyl group or a fluorous-tag pnonafluoroheptoxyphenyl (NFH) group at the C5 position of the Nsalicylidene template were designed and synthesized. Each complex was subjected to MVO 3 -induced self-assembly to form metal-ion, encapsulated quartet clusters 3-M and 3′-M. The Na + in cluster complex 3-Na or 3′-Na can be readily replaced by Rb + , Ag + , or Hg 2+ in an aqueous layer to form cluster complexes by ion swapping at the H 2 O/CDCl 3 bilayer interface. Selectivity profiles were examined with alkali-metal ions, Ag + , and Hg 2+ through metal-ion competition experiments. The 3′-Na has an exclusive selectivity for Hg 2+ in the presence of Zn 2+ and Cd 2+ . Cluster complexes 3-M were utilized as chiral dopants to nematic LC materials. The effects of the encapsulated metal ions within the alkali family and Ag + on Cano's line widths and helical pitch changes were viewed in wedge cells under a polarized microscope. Their correlations with the ionic radius were identified. The subnano information of the metal ions can thus be asymmetrically amplified to Cano's line spacings of the submilimeter domain. Conversely, the effects of the encapsulated alkali metal ions and Hg 2+ in 3′-M on the interactions of their NFH tails toward fluorous silica gel (FSG) were performed via HPLC analyses. Their retention times became longer as the sizes of encapsulated, alkali metal ions increased. The increasing ion size from Na + to Cs + caused the four lower rim NFH tags of the cluster to be closer due to reduced cone angles. Their interactions among NFH tail groups on FSG became larger, thus leading to distinctive separations with t R from 7.36 to 10.27 min. The retention time difference between 3′-Na and 3′-Hg on HPLC was ∼3.6 min, resulting in discernible separation. The individual ion size differences on the subnano scale can thus be amplified and unambiguously established in the real time domain.

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Section: Resultssupporting

confidence: 55%

Section: Introductionmentioning

confidence: 97%

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Metal-Ion Specific Recognition with Amplified Transcription from Subnanometer to Submillimeter or Real-Time Domain by Self-Assembled Vanadyl Quartets

Chen

Weng

2022

Inorg. Chem.

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“…Therefore, one can conclude that the best results were derived from catalysts 4c and 4d . − This trend may have to do with delicate hydrogen-bonding interactions between methanol and the 3-chloro or 3-bromo group in the salicylidene template, but it also exerts enough steric shielding effect to steer the methoxy trapping event to the benzylic position of styrene (vide infra). Further improvements in terms of yields and extent of asymmetric induction can be achieved by performing these two catalytic reactions at 0 °C (data in parentheses in entries 3 and 4).…”

Section: Resultsmentioning

confidence: 99%

Asymmetric Radical-Type 1,2-Alkoxy-Sulfenylation of Benzoxazole-2-Thiols to Vinylarenes Catalyzed by Chiral Vanadyl Complexes

Liu,

Tsui,

Chien

et al. 2024

ACS Catal.

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Chiral vanadyl complex derived from N-salicylidene-tert-butyl-l-glycinate bearing a 3-(2,5-dimethyl)phenyl-5-bromo substituent was first tested for the catalytic feasibility of asymmetric intermolecular 1,2-alkoxy-sulfenylation of styrene with three different types of six- and five-membered ring heteroaromatic thiols in the presence of t-butyl hydroperoxide in methanol at ambient temperature. Among them, 2-mercapto-benzoxazole (BzOxz-SH) was identified as the best candidate. A variety of chiral vanadyl complexes bearing 3-aryl-5-bromo, 3,5-dihalo-, and benzo-fused salicylidene templates were further examined for optimizing yields and enantio-control. The best scenario involved the use of 5 mol % 3,5-dibromo or -dichloro catalyst at 0 °C with BzOxz-SH in MeOH. The asymmetric catalytic cross-coupling reactions proceeded smoothly with enantioselectivities of up to 94% ee of (R)-configuration by using the 3,5-dichloro catalyst for various 1° alcohols by screening through various 4-, 3-, 3,4-, 3,5-, and 2-substituted (including Me/t-Bu, Ph, OR, Cl/Br, OAc, NO2, C(O)Me, CO2Me, CN, and benzo-fused) vinylarenes. Further improvement to 96% ee was achieved by the use of 5-methyl-BzOxz-SH. The origin and catalytic mechanism of enantiocontrol through homolytic methoxy delivery to incipient benzylic radical intermediates by vanadyl-bound methoxide were proposed.

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Asymmetric Cross Couplings of Trifluoromethyl Radical to Vinylarenes with N‐Hydroxy‐oxazinediones and Subsequent Aerobic Oxidative Homocoupling of 2‐Naphthols Catalysed by Chiral Vanadyl Complexes

Chen,

Hung,

Tsai

et al. 2023

Adv Synth Catal

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Asymmetric three‐component, 1,2‐aminoxy‐trifluoromethylation of styrenes with N‐hydroxy‐1,3‐benz/naphthoxazine‐2,4‐diones (i. e., N‐OH‐(B/Np)OxzOn) catalysed by chiral vanadyl complexes derived from N‐salicylidene‐L‐t‐leucinate were explored. Among 14 different solvents and 13 different catalysts screened, the best reaction scenarios were in 2‐propanol with 3‐(2,5‐dimethyl)phenyl‐5‐bromo (DMP), or 3‐t‐butyl‐5‐bromo substituted catalysts that led to the corresponding complementary (R)‐ and (S)‐products with potential biological activities in 45–91% yields and up to 85 and 75% ee, respectively. Further optimisation with the DMP catalyst led to the best combination of 3‐halo/3,5‐dihalo‐styrenes with 6‐/7‐Br−N−OH‐(B/Np)OxzOn as the trapping agents. The corresponding eight different products were isolated in 52–75% yields with ees in a range of 88–93% (R). Based on Density Functional Theory (DFT) calculations with conformational searches, the origin of enantiocontrol and the working mechanism were proposed by resorting to a bidentate‐chelation between the amide or carbamate C=O group and N−OH group in the trapping agent to the vanadyl center followed by asymmetric benzylic radical trapping in an SH2 fashion. Subsequent Fragment Molecular Orbital (FMO)/Pair Interaction Energy Decomposition Analysis (PIEDA) calculations with the DMP catalyst were carried out to rationalize the extent of asymmetric induction. One representative product derived from p‐methyl‐styrene and NpOxzOn was hydrolyzed in basic MeOH with decarboxylation to unmask its carbamate moiety. The resulting chiral (R)‐N‐benzoxy‐3‐hydroxy‐2‐naphthamide was subjected to aerobic, oxidative homo‐coupling catalysed by the DMP catalyst in CCl4. The corresponding 2,2‐binaphthol product was isolated in 90% (brsm) yield with nearly complete diastereo‐control at the created (M)‐axial chirality, allowing for sequential, bi‐functional asymmetric cross‐coupling applications.

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Directed Self-Assembly of C₄-Symmetric, Oxidovanadate-Centered, Vanadyl(V) Quadruplexes for Ba²⁺- and Hg²⁺-Specific Recognition, Transport, and Recovery

Cited by 3 publications

References 124 publications

Metal-Ion Specific Recognition with Amplified Transcription from Subnanometer to Submillimeter or Real-Time Domain by Self-Assembled Vanadyl Quartets

Metal-Ion Specific Recognition with Amplified Transcription from Subnanometer to Submillimeter or Real-Time Domain by Self-Assembled Vanadyl Quartets

Asymmetric Radical-Type 1,2-Alkoxy-Sulfenylation of Benzoxazole-2-Thiols to Vinylarenes Catalyzed by Chiral Vanadyl Complexes

Asymmetric Cross Couplings of Trifluoromethyl Radical to Vinylarenes with N‐Hydroxy‐oxazinediones and Subsequent Aerobic Oxidative Homocoupling of 2‐Naphthols Catalysed by Chiral Vanadyl Complexes

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