A5052770432- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Porphyrin and Phthalocyanine Chemistry
- Luminescence and Fluorescent Materials
- Metal-Catalyzed Oxygenation Mechanisms
- Supramolecular Chemistry and Complexes
- Molecular Sensors and Ion Detection
- Photosynthetic Processes and Mechanisms
- Porphyrin Metabolism and Disorders
- Synthesis and Properties of Aromatic Compounds
- Surface Chemistry and Catalysis
- Crystallography and molecular interactions
- Photochromic and Fluorescence Chemistry
- Photodynamic Therapy Research Studies
- Catalytic C–H Functionalization Methods
- Metal complexes synthesis and properties
- Remote-Sensing Image Classification
- Electrochemical sensors and biosensors
- Organic Light-Emitting Diodes Research
- Axial and Atropisomeric Chirality Synthesis
- Oxidative Organic Chemistry Reactions
- Heme Oxygenase-1 and Carbon Monoxide
- Traditional and Medicinal Uses of Annonaceae
- Vehicle License Plate Recognition
- Fluorine in Organic Chemistry
Hunan Normal University
2014-2025
Shanghai University
2024
Ministry of Education of the People's Republic of China
2021-2023
Laboratoire de Synthèse Organique
2021
Changsha University
2021
All-aza smaragdyrin, a historic but elusive pentapyrrolic macrocycle, was successfully synthesized and characterized for the first time. [22]Smaragdyrin BF2-complex 3 smoothly by 2-fold SNAr reaction of 1,9-dibromo-5-mesityldipyrrin with 5,10-dimesityltripyrrane. Treatment methanesulfonic acid gave [20]smaragdyrin 5 as stable antiaromatic compound. Reduction NaBH4 under inert conditions [22]smaragdyrin 6 an aromatic congener, which easily oxidized back to in air. Complex interconvertible its...
Abstract β,β‐tripyrrin‐bridged earring porphyrins were synthesized through Suzuki–Miyaura cross coupling reactions. These porphyrinoids have multiple cavities and can accommodate two or three metal ions per molecule. The structures of the been elucidated by x‐ray diffraction analysis, feature curved π planes. electronic spectra exhibit near‐infrared (NIR) absorptions insertion leads to red‐shifted intensified absorption features. Electrochemical analysis transient measurements indicated that...
Abstract A reaction sequence of regioselective peripheral bromination, Suzuki–Miyaura coupling with 2‐borylated thiophene or pyrrole, and oxidative ring‐closure FeCl 3 allowed the synthesis heterole‐fused earring porphyrins 4Pd 9Pd from parent porphyrin 1 . Differently pyrrole‐fused 5H 6H their Pd II complexes 5Pd 6Pd were also synthesized. The structures , 5H, 8Pd have been revealed by X‐ray analysis to be slightly twisted owing constraints imposed structures. exhibits an intensified band...
Electron transfer-based long-lived radicals are highly challenging because of the limited control over relative orientation, distance, electronic coupling, and nonradiative recombination channels donor acceptor on a molecular level. Herein, cavity macrocyclic cucurbit[8]uril (Q[8]) was found to exhibit excellent advantages in controlling orientation distance moieties via spatial organization, i.e., 4-carboxylphenyl appended viologen-derived guest (BcpV2+) elegantly rearranged as rigid linear...
Oxidation of B-tolyl B III 5,10,15-tritolylsubporphyrin with tris(4-bromophenyl)ammoniumyl hexachloroantimonate gave its cation radical instantaneously, which slowly dissociated to give subporphyrin borenium in 89% after stirring overnight. This is a...
In order to examine the effects of fused heterole on electronic properties aromatic and antiaromatic smaragdyrins, 2,3‐thiophene‐ 2,3‐indole‐fused [20]smaragdyrins were synthesized by Suzuki‐Miyaura coupling subsequent oxidative fusion reaction, reduced with NaBH4 corresponding [22]smaragdyrins. Fused‐thiophene‐ fused‐pyrrole‐bridged [20]‐ [22]smaragdyrin dimers also in similar manner. The installed heteroles mitigate paratropic ring current [20]smaragdyrin but exert only minor diatropic...
As a new core-modified variant of BIII subporphyrins, suboxochlorins were synthesized from meso-2-formylphenylsubporphyrins via addition reaction with mesitylmagnesium bromide, Friedel-Crafts type cyclization effected BF3·OEt2, and oxidation 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) or AgPF6. The are equipped fused conjugated benzocyclohexene unit at the periphery display broad blue-shifted Soret bands red-shifted vibronic structured Q-bands as compared usual triarylsubporphyrins....
Rhodium-catalyzed C-H/N-H [5 + 2] annulations of 8-(pyrrol-2-yl)-appended boron-complexed dipyrromethenes (BODIPYs) with internal alkynes have been established to afford a series azepine-fused BODIPYs good yields and excellent regioselectivity, in which the pyrrol-2-yl unit serves as directing group rare example. A RhI intermediate was obtained indicate RhI/RhIII catalytic process involved this reaction. Importantly, C-H annulation is demonstrated concise strategy change optical properties BODIPY.
Abstract As isomers of the regular porphyrins, N-confused porphyrins have attracted extensive attention chemists because their unique chemical structures, reactivities, and physical properties, which result in promising applications fields catalytic chemistry, biochemistry material science. Typically, are synthesized via acid catalyzed condensation following oxidation during lactams often formed as byproducts. Here we report doubly ring-contracted [24]hexaphyrin(1.1.0.1.1.0) mono-...
Abstract Direct β‐to‐β linked branched and cyclic porphyrin trimers pentamers have been synthesized by the Suzuki–Miyaura coupling of β‐borylporphyrins β‐bromoporphyrins. The trimer, smallest directly wheel to date, its twined pentamer, exhibit small electrochemical HOMO–LUMO gaps, broad nonsplit Soret bands, red‐shifted Q‐bands, thus indicating large electronic interactions between constituent units.
Smaragdyrin had been an important but elusive expanded porphyrin until our recent first synthesis (Xie et al., J. Am. Chem. Soc. 2018, 140, 16553). In this paper, we report the of singly and doubly neo-confused [22]smaragdyrin BF2-complexes 13 15 both as stable smaragdyrin mutants by nucleophilic substitution reactions 1,9-dibromo-5-mesityldipyrrin 1 with N-confused tripyrranes, 10 11, respectively. Demetalation methanesulfonic acid furnished free bases 16 18, respectively, air-sensitive...
Porphyrin-diazaporphyrin hetero oligomers were constructed through a Suzuki–Miyaura cross-coupling reaction. Hetero nanotapes exhibiting strong NIR absorption obtained via further oxidation of these oligomers.
Abstract Rhodium‐catalyzed reaction of meso‐pyrrol‐2‐yl Ni II porphyrins with internal alkynes proceeded smoothly to give singly, doubly, and quadruply seven‐membered‐ring fused as the first example [5+2] annulation for porphyrin substrates, where meso‐appended pyrrole unit serves a directing group. These reactions are operationally quite simple easy. A plausible mechanism was proposed on basis isolation key intermediate. The structures representative products have been revealed be...
BIII subporphyrins are the legitimate ring-contracted porphyrins consisting of three pyrroles and meso-carbons their chemistry has been extensively developed since first synthesis in 2006. However, subporphyrin free bases have never synthesized, despite tremendous attempts to remove ion. Here we report that Suzuki-Miyaura coupling between α,α'-diborylated tripyrrane 1 tetrabromide 5 gave 6, 6 A, base dimer 7 %, 4 2 % yields as examples. Subporphyrin exhibit curved bowl-like structures...
The one-pot self-coupling reaction of 3-amino-5-bromo-BODIPY 9 under Buchwald-Hartwig amination conditions gave nitrogen-bridged cyclic BODIPY tetramer 10, pentamer 11, and hexamer 12. Oxidation 12 in the presence alkali metal ions provided 13, 15, 16, respectively, as first examples expanded azaporphyrins possessing more than six pyrrole rings. Curiously, oxidation even absence same complexes a result spontaneous complexation. 10-12 showed large association constants (104 -106 M-1 ) with K+...
A series of π-extended BODIPY derivatives fused with an indolizine scaffold were prepared smoothly <italic>via</italic> rhodium-catalyzed C–H functionalization/annulation. These fluorophores show significantly red-shifted absorption, reaching to the near infrared (NIR) region.
Symmetry-breaking charge transfer is one of the key process in photosynthetic reaction centers and specific artificial optoelectronic devices such as dye-sensitized solar cells. Here we report synthesis aromatic-bridged BF2-smaragdyrin dimers, meso-free BF2-smaragdyrin, its meso-meso-linked dimer. The decays S1-states these dimers are accelerated with an increase solvent polarity a decrease distance between two units, suggesting symmetry-breaking transfer. fluorescence lifetimes become...
5,10,23-Trimesityl-substituted [24]hexaphyrin(1.1.0.0.1.0) was synthesized as a stable antiaromatic molecule by base-catalyzed twofold SNAr reaction and reduced to the corresponding [26]hexaphyrin, which an unstable aromatic because it easily oxidized [24]hexaphyrin. The [24]hexaphyrin served ligand give bis-PdII complex tris-RhI with unique structures. former has two square-planar-coordinated PdII ions bridged acetate anion shows strong paratropic ring current, while latter three RhI...
Cu
Rosenthal's-reagent-mediated intramolecular cyclometallation of α,α-dialkynyldipyrrin nickel(II) complex and subsequent acid treatment afforded a 1,3-butadiene-embedded porphyrin(2.1.2.1), 6, which served as reactive diene towards dienophiles such dimethyl acetylenedicarboxylate (DMAD) benzyne to give corresponding Diels-Alder adducts. reaction 6 benzdiyne gave adducts 14, 15 a, b along with trace amount porphyrin(2.1.2.1) barrel 13. Stepwise routes using 14 or a/15 substrate allowed for the...
2,7,12,17-Tetrakis(pinacolatoboryl) NiII porphyrin 5 Ni was synthesized in 75 % yield by Ir-catalyzed borylation of porphine followed metalation and has been demonstrated to be a useful synthon, giving 2,7,12,17-tetraaryated porphyrins 6 a-d, peripherally octaarylated 8 quadruply bridged face-to-face non-offset -porphyrin dimer 12, cross-shaped β-meso singly linked pentamers nonamers. Oxidation 14 Zn gave fused pentameric tapes 15 Zn. The structures Zn, have revealed X-ray diffraction...
Abstract β‐to‐β 2,5‐Pyrrolylene linked cyclic porphyrin oligomers have been synthesized by Suzuki–Miyaura coupling of 2,5‐diborylpyrrole and 3,7‐dibromoporphyrin. The exhibit roughly coplanar structures, strong excitonic coupling, small electrochemical HOMO–LUMO gaps, ultrafast excitation energy transfer between the neighboring porphyrins via pyrrolylene bridge.
meso-Trimesityl-substituted [20]smaragdyrin freebase was synthesized by p-toluenesulfonic acid catalyzed reaction of 5-mesityldipyrromethane and 2,14-dibromodipyrrin in an improved yield 63 %. Unexpectedly, treatment the with BF3 ⋅ OEt2 triethylamine (TEA) gave a stable radical species, which BF2 unit is coordinated at tripyrrin site, probably ready release hydrogen atom [22]smaragdyrin complex. Similar free base produced another complex, dipyrrin site. The site neutral oxidized AgSbF6 to...
The oxidation of NiII-porphyrin dimer 10 with PbO2 or MnO2 resulted in the simultaneous implementation an N-heterocycle-fused bridge and a modified pyrrole to give three unprecedented porphyrin dimers 11, 12, 13. reduction 12 smoothly afforded 14. structures these were all unambiguously confirmed by X-ray crystallographic analysis. These show significantly red-shifted absorption bands perturbed electrochemical properties decreasing HOMO-LUMO gap order 14 > 13 11 12.