Effect of Meso Substituents in Tin (IV) Corrole on Chemosensing: Highly Selective Coloro/Fluorimetric Sensing of F⁻ and CN⁻ Ions and Their Practical Applicability

Luminescence, Год журнала: 2025, Номер 40(5)

Опубликована: Май 1, 2025

ABSTRACT Here, we synthesized tin (IV)‐based chemosensors (5,10,15‐tris(4‐cyanophenyl)corrolato)tin (IV)‐chloride (Sn1) and (5,10,15‐tris(methyl‐5‐formyl‐2‐methoxybenzoate)corrolato)tin(IV)‐chloride (Sn2) thoroughly characterized them by various spectroscopic techniques. These receptors, Sn1 Sn2, exhibit selective colorimetric fluorogenic responses towards fluoride (F − ) cyanide (CN anions. The addition of these analytes significantly enhances the fluorescence intensity. exhibits a limit detection (LOD) 1.65 μM for F 1.7 CN ions, while Sn2 has an LOD 4.8 using fluorometric method. association constant was calculated to be 2.42 × 10 4 1.45 complexation with 1.21 . larger binding lower demonstrated ability sense even traces target analytes. sensing comprehensively evaluated through optical, electrochemical, theoretical studies. Benesi–Hildebrand Job's plots suggested 1:1 interaction between Sn1/Sn2 respective ESI mass spectra Sn receptor + anion complexes revealed that mechanism involved exchange axial Cl atom incoming In that, real‐time analysis also carried out ion present in toothpaste RGB depict applicability (IV) receptors applications.

Язык: Английский

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Size and Electronic Effects on the Performance of (Corrolato)cobalt-Modified Electrodes for Oxygen Reduction Reaction Catalysis

Inorganic Chemistry, Год журнала: 2023, Номер 62(35), С. 14147 - 14151

Опубликована: Авг. 24, 2023

Considering the worldwide efforts for designing catalysts that are not based on platinum group metals while still reserving many advantages thereof, this study focused variables dictate performance of cathodes used fuel cells, regarding efficient and selective reduction oxygen to water. This was done by investigating two kinds porous carbon electrodes, modified molecular cobalt(III) complexes chelated corroles differ very much in size electron-withdrawing capability. Examination electronic effect uncovered shifts CoII/CoIII redox potentials also large differences affinity cobalt center external ligands. Spontaneous absorption found depend corrole's substituents (C6F5 ≫ CF3 H) metal's axial ligands (PPh3 versus pyridine), as well porosity electrodes (BP2000 > Vulcan). The better-performing cobalt-based were almost active 20% Vulcan terms onset potential only 2-10% undesirable formation hydrogen peroxide. Durability addressed using best-performing cathode a proper anion-exchange membrane cell setup, revealing little voltage change during 12 h operation.

Язык: Английский

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Highly Efficient β‐Functionalized Oxidomolybdenum(V) Corroles for Catalytic Oxidative Bromination of Phenols at Room Temperature

European Journal of Inorganic Chemistry, Год журнала: 2023, Номер 26(34)

Опубликована: Сен. 19, 2023

Abstract Two new β ‐functionalized oxidomolybdenum(V) corroles, oxido[3‐formyl‐5,10,15‐triphenylcorrolato]molybdenum(V) ( Mo‐1 ) and oxido[3‐dicyanovinyl‐5,10,15‐triphenylcorrolato]molybdenum(V) Mo‐2 were synthesized characterized by various spectroscopic techniques electrochemical studies. manifests splitted B bands due to x y polarizations highly red shifted longest Q the electron‐deficient nature of dicyanovinyl group. EPR data showed that these complexes exhibit an axial compression with d xy 1 configuration. DFT studies revealed HOMO LUMO orbitals are stabilized in relative . exhibits two successive reversible reductions oxidation potentials cyclic voltammetry. Surprisingly, three oxidations; one extra reduction could possibly be moiety. The catalytic activities for oxidative bromination phenols using H 2 O ‐KBr‐HClO 4 mixture water have been explored exhibited excellent activity at a very low catalyst loading 0.0030 0.0028 mol%, respectively. Both Mo(V) corroles manifest much higher conversion TOF (59801–71174 h −1 earlier reported meso (20781–61646 ). Hence, mimic vanadium bromoperoxidase (VBPO) act as functional models applications. These catalysts reused upto 3 cycles rate 82 % indicating their thermal chemical stabilities.

Язык: Английский

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Inverse Hypercorroles

Опубликована: Янв. 29, 2024

Ground-state and time-dependent density functional theory (TDDFT) calculations with the long-range-corrected, Coulomb-attenuating CAMY-B3LYP exchange-correlation large, all-electron STO-TZ2P basis sets have been used to examine potential “inverse hypercorrole” character of meso-p-nitrophenyl-appended dicyanidocobalt(III) corrole dianions. The effect is most dramatic for 5,15-bis(p-nitrophenyl) derivatives, where it manifests itself in intense NIR absorptions. 10-aryl groups these complexes play a minor modulatory role. TDDFT (CAMY-B3LYP) ascribe features clearly transition from corrole’s a2u- like HOMO (retaining D4h irrep metalloporphyrins) nitrophenyl-based LUMO. outward nature this contrasts usual phenyl-to-macrocycle direction charge transfer transitions many hyperporphyrins hypercorroles. studied, therefore, are aptly described as inverse

Язык: Английский

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Sb(v) dihalide corroles: efficient singlet oxygen photosensitisers

Chemical Communications, Год журнала: 2024, Номер 60(30), С. 4096 - 4099

Опубликована: Янв. 1, 2024

Sb( v ) dihalide corrole complexes, in particular difluoro-5,15-di(4-cyanophenyl)-10-(2,4,5-trimethoxyphenyl)corrolatoantimony( (complex 1), show distinct emission properties and efficient intersystem crossing rates.

Язык: Английский

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Alternatively Connected Corrole‐Porphyrin Multimetallic Complexes: Synthesis, Structure, and Properties

European Journal of Inorganic Chemistry, Год журнала: 2024, Номер 27(20)

Опубликована: Апрель 22, 2024

Abstract Synthetic multimetallic porphyrinoids are potential candidates in catalysis, molecular magnetism and as modern optoelectronic materials. Introducing electronic heterogenity these multi‐porphyrinoids shall bring novel redox characteristics. In this direction, herein we report four discrete Corrole‐Porphyrin‐Corrole C[10] ⋅ P[5,15] hybrids that have both corrole porphyrin units covalently connected together. Metal ions diverse oxidation states been incorporated into respective cores to achieve homo heterotrinuclear metal complexes. Selective metalation at the was achieved by step‐wise insertion of Zn(II)/Cu(II), Zn(II)/Ga(III) Cu(II)/Cu(II) suit dianionic trianionic pockets, respectively. Single crystal X‐ray diffraction studies reveal solid‐state structural evidence for homo‐, hetero‐trinuclear The Zn(II) Ga(III) moieties two distinct geometries assembly. geometry core is a perfect square planar, whereas pyramidal with pyridine an axial ligand. case homotrinuclear Cu(II) complex, adopt planar irrespective core. Similar all trimers, trimers exhibit significant excitonic coupling between absorption spectra. cyclic voltametric investigations also individual chromophores despite non‐coplanar arrangement amongst macrocycles.

Язык: Английский

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Corrins and porphyrins: two of nature’s pigments of life

Journal of Coordination Chemistry, Год журнала: 2024, Номер 77(11), С. 1161 - 1210

Опубликована: Апрель 22, 2024

Given the relative scarcity of cobalt in earth's crust, its retention biological systems, principally (but not exclusively) corrinoids or derivatives vitamin B12, may be surprising. The chemistry these compounds and much more widely utilized iron porphyrins, is compared contrasted an attempt made to explain biology.

Язык: Английский

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Inverse Hypercorroles

Inorganic Chemistry, Год журнала: 2024, Номер 63(19), С. 8739 - 8749

Опубликована: Май 2, 2024

Ground-state and time-dependent density functional theory (TDDFT) calculations with the long-range-corrected, Coulomb-attenuating CAMY-B3LYP exchange-correlation large, all-electron STO-TZ2P basis sets have been used to examine potential "inverse hypercorrole" character of meso-p-nitrophenyl-appended dicyanidocobalt(III) corrole dianions. The effect is most dramatic for 5,15-bis(p-nitrophenyl) derivatives, where it manifests itself in intense NIR absorptions. 10-aryl groups these complexes play a modulatory role, as evinced by experimental UV–visible spectroscopic electrochemical data series corroles. TDDFT (CAMY-B3LYP) ascribe features clearly transition from corrole's a2u-like HOMO (retaining D4h irrep metalloporphyrins) nitrophenyl-based LUMO. outward nature this contrasts usual phenyl-to-macrocycle direction charge transfer transitions many hyperporphyrins hypercorroles; thus, studied are aptly described inverse hypercorroles.

Язык: Английский

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Panchromatic and Perturbed Absorption Spectral Features and Multiredox Properties of Dicyanovinyl- and Dicyanobutadienyl-Appended Cobalt Corroles

Inorganic Chemistry, Год журнала: 2023, Номер 62(49), С. 19956 - 19970

Опубликована: Ноя. 27, 2023

Four new β-functionalized π-extended cobalt corroles with one and two dicyanovinyl (DCV) or dicyanobutadienyl (DCBD) moieties at the 3- 3,17-positions have been synthesized characterized by various spectroscopic techniques. Interestingly, DCV- DCBD-appended displayed panchromatic near-infrared absorption in range 300–1100 nm CH2Cl2 pyridine solvents. (MN)2-(Cor)Co A2MN2-(Cor)Co exhibited 8–9 times enhancement molar absorptivity of Q band compared to parent corrole ((Cor)Co). The unique spectral features these are splitting, broadening, red-shifting Soret bands. One DCV unit brings a 30–46 red shift, whereas DCBD 40–75 shift corresponding precursors. This is rare that intensity longest greater than equal Soret-like These derivatives exhibit UV–vis similar those chlorophyll a. A 220 mV positive per group 160 were observed first oxidation potentials (Cor)Co desired direction for utility complexes electrocatalysis. DFT studies revealed HOMO LUMO stabilized after appending groups on macrocycle “push–pull” behavior leading promising material applications nonlinear optics (NLO) catalysis.

Язык: Английский

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Surface crystallization of CoIIIcorroles towards accelerating electrocatalyzed hydrogen evolutions and oxygen reductions

International Journal of Hydrogen Energy, Год журнала: 2023, Номер 49, С. 764 - 774

Опубликована: Авг. 4, 2023

Язык: Английский

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